Co-reporter:Xu Li;Junran Lu;Yi Li
Chinese Journal of Chemistry 2017 Volume 35(Issue 5) pp:716-722
Publication Date(Web):2017/05/01
DOI:10.1002/cjoc.201600594
AbstractThe side-chain alkylation of toluene with methanol over alkali-cation-containing zeolite Y is an important reaction for industrial production of styrene, but the exact mechanism of this reaction is still unclear. The most accepted opinion is that the Lewis acid–base sites in zeolite Y activate the transformation from methanol to formaldehyde, the side-chain alkylation of toluene with formaldehyde, and the formation of 2-phenylethanol and styrene afterwards. In this study, we investigate the roles of various types of hydroxyl groups that could possibly exist in zeolite Na-Y during this reaction, including the Brönsted acid sites and the terminal Al—OH and Si—OH groups, respectively. Through density functional theory (DFT) calculations, we find that the Brönsted acid sites in Na-Y may catalyze the ring alkylation of toluene and be responsible for the formation of xylene, a side product discovered in experiments. More importantly, we find, for the first time, a new reaction pathway from 2-phenylethanol to styrene over various types of hydroxyl groups in Na-Y, which is kinetically more favorable than the conventional pathway. According to our calculation results, the most possible mechanism for this styrene production process may involve reactions over both the Lewis acid–base sites and the hydroxyl groups in Na-Y.
Co-reporter:Junran Lu;Lin Li;Hongxiao Cao;Yi Li
Physical Chemistry Chemical Physics 2017 vol. 19(Issue 2) pp:1276-1280
Publication Date(Web):2017/01/04
DOI:10.1039/C6CP06217B
To boost function-led discovery of new zeolites with desired pores and properties, millions of hypothetical zeolite structures have been predicted via various computational approaches. It is now well accepted that most of these predicted structures are experimentally unrealisable under conventional synthetic conditions. Many structure evaluation criteria have been proposed to screen out unfeasible structures, among which the framework density–framework energy correlation criterion and the local interatomic distances criteria are the most frequently used. However, many hypothetical structures passing these criteria have been found unfeasible because of the existence of highly distorted framework rings. Here, we propose a new set of structure evaluation criteria to screen out such unfeasible structures. After optimising all existing zeolite structures as silica polymorphs, we find that the closest non-adjacent O⋯O distances in existing zeolite rings generally show a normal distribution. By comparing the closest non-adjacent O⋯O distances between existing and hypothetical zeolite structures, we are able to screen out many unfeasible hypothetical zeolite structures with distorted rings that are deemed feasible according to previous structure evaluation methods.
Co-reporter:Shuang Hao;Yuchuan Liu;Chuning Shang;Zhiqiang Liang
Polymer Chemistry (2010-Present) 2017 vol. 8(Issue 11) pp:1833-1839
Publication Date(Web):2017/03/14
DOI:10.1039/C6PY02091G
A series of imidazole ionic liquid (IL) functionalized porous organic polymers (POPs) with high surface areas has been successfully prepared based on p-dichloroxylene (p-DCX) and N-methylimidazole (N-MI) as fundamental building blocks through the FeCl3-catalyzed Friedel–Crafts alkylation reaction. The IL-functionalized POPs show CO2 uptake up to 73.6 cm3 g−1 (273 K, 1 bar). Their isosteric heat of adsorption can be increased from 7.84 to 17.35 kJ mol−1 by adjusting the molar ratios of N-MI to p-DCX. These materials could also be used as reusable acid catalysts in the syntheses of benzimidazole derivatives from aromatic aldehydes and o-phenylene diamine in good yields (87–91%).
Co-reporter:Yuanzheng Cui;Yuchuan Liu;Jiancong Liu;Jianfeng Du;Yue Yu;Shun Wang;Zhiqiang Liang
Polymer Chemistry (2010-Present) 2017 vol. 8(Issue 33) pp:4842-4848
Publication Date(Web):2017/08/22
DOI:10.1039/C7PY00856B
Luminescent porous organic polymers have shown potential applications in sensing, light-harvesting, photocatalysis and photo-voltaic or electronic devices. In this paper, a luminescent porous Tröger's base polymer (LMOP-15) with a tetraphenylethene unit has been synthesized by a simple method through the reaction of 1,1,2,2-tetrakis(4-aminophenyl)ethene and dimethoxymethane in acid solution at room temperature. The N2 adsorption of LMOP-15 at 77 K reveals the type I isotherm of microporous materials, and the calculated Brunauer–Emmett–Teller surface area is 484 m2 g−1. The CO2 uptake capacity of LMOP-15 at 273 K and 1 bar is 48.8 cm3 g−1, while the isosteric heat for CO2 reaches 53.7 kJ mol−1 due to the presence of the Tröger's base moiety. The CO2/N2 adsorption selectivity calculated from the initial slopes of the CO2 and N2 adsorption isotherms at 273 K is up to 61.7. LMOP-15 also exhibits strong green luminescence (λmax = 517 nm) in ethanol suspension. Furthermore, LMOP-15 shows highly selective fluorescence quenching detection abilities for Cu2+ ions and picric acid.
Co-reporter:Shuting Du;Qiming Sun;Ning Wang;Xiaoxin Chen;Mingjun Jia
Journal of Materials Chemistry A 2017 vol. 5(Issue 17) pp:7992-7998
Publication Date(Web):2017/05/03
DOI:10.1039/C6TA10044A
In this work, we report a hydrothermal route to synthesize hierarchical TS-1 zeolites with abundant mesopores (5–40 nm) inside the zeolite crystals by using polydiallyldimethylammonium chloride (PDADMAC) as a mesopore-directing template. The textural parameters of the hierarchical TS-1 zeolites can be adjusted by changing the amount of PDADMAC in the synthesis system; in particular, a hierarchical TS-1C sample with abundant and uniform mesopores (around 10 nm) can be obtained by optimizing the amount of PDADMAC. The resultant hierarchical TS-1 zeolite exhibits excellent catalytic activity in the oxidation of bulky organosulfur compounds. Moreover, the hierarchical TS-1 catalysts possess high structural stability and can be easily recycled without any post treatment. This work demonstrates a facile route to synthesize hierarchical TS-1 zeolites with abundant intracrystalline mesopores by using a cheap and easily available mesoporous template, which will open new perspectives for the potential application of hierarchical TS-1 zeolites in catalytic oxidation of bulky organic compounds.
Co-reporter:Duo Wang;Jie Chen;Li Ren;Qinglan Li;Dongdong Li
Inorganic Chemistry Frontiers 2017 vol. 4(Issue 3) pp:468-472
Publication Date(Web):2017/03/14
DOI:10.1039/C6QI00488A
Aggregation-induced emission luminogens (AIEgens), tetraphenylethene, were post grafted onto mesoporous silica nanoparticles to form AIEgen-functionalised mesoporous materials. The obtained blue-emitting materials can serve as a fluorescence resonance energy transfer (FRET) donor for monitoring the release process of doxorubicin hydrochloride (DOX) as an acceptor by the change of the fluorescent signal, showing potential application in imaging-guided therapy.
Co-reporter:Zhiying Fan;Li Ren;Wenjing Zhang;Dongdong Li;Guoqing Zhao
Inorganic Chemistry Frontiers 2017 vol. 4(Issue 5) pp:833-839
Publication Date(Web):2017/05/16
DOI:10.1039/C7QI00046D
A multifunctional nanotheranostic system for imaging guided chemo- and photothermal synergistic therapy for cancer has been developed, in which the aggregation-induced emission (AIE) luminogen functionalised mesoporous silica nanoparticles (MSNs) act as anticancer drug carriers and biological imaging agents, and CuS nanoparticles attached to the silica nanosphere surface as the photothermal agent. The obtained nanocomposites (denoted as CFMSNs) exhibit a blue emission and have good biocompatibility, and can be used as an effective luminescent bioprobe for intracellular imaging. Furthermore, the nanoplatform can induce obvious thermal effects after the exposure to an 808 nm laser and serve as an effective pH-dependent NIR-responsive release system. More importantly, the combination of chemotherapy and photothermal therapy shows a better therapeutic effect than the individual therapies, thus demonstrating a synergistic action towards anticancer therapy.
Co-reporter:Yilin Wang;Yunchen Wang;Jie Su;Xiaowei Song;Wei Wan
Inorganic Chemistry Frontiers 2017 vol. 4(Issue 10) pp:1654-1659
Publication Date(Web):2017/10/10
DOI:10.1039/C7QI00309A
Silicogermanate (JU110) with an interrupted open-framework has been synthesized by using a hydrothermal method using 1,1′-(1,4-phenylenebis(methylene))bis(1-methylpyrrolidin-1-ium) hydroxide as an organic structure-directing agent (OSDA). Silicon and fluoride anions were introduced to the concentrated-gel synthesis system, and different synthetic parameters influencing the synthesis were discussed. The structure of JU110 was characterised by using rotation electron diffraction (RED) and high-resolution powder X-ray diffraction. JU110 crystallizes in the space group Fm2m (No. 42) with a = 13.9117(2) Å, b = 18.2980(3) Å and c = 32.7800(6) Å. The structure is constructed by the sti layers found in the STI framework that are pillared by D4R/Ge7 units to form a large cavity, showing 10-ring openings along [100] and 9-ring openings along [110]. Thermal stability studies showed that the framework was maintained with the loss of water molecules, but collapsed with the removal of charge-compensating cations.
Co-reporter:Guangrui Chen;Qiming Sun
Chemical Communications 2017 vol. 53(Issue 100) pp:13328-13331
Publication Date(Web):2017/12/14
DOI:10.1039/C7CC07508A
Nano-sized SAPO-34 catalysts have been for the first time prepared using morpholine as the sole template by using a one-pot nanoseed-assisted method. The obtained nano-sized SAPO-34 catalysts exhibit about 4-fold prolonged lifetime and nearly 5% increased selectivity for ethylene and propylene compared to conventional micron-sized counterparts in methanol-to-olefin reactions.
Co-reporter:Qiming Sun, Ning Wang, Qiming Bing, Rui Si, ... Jihong Yu
Chem 2017 Volume 3, Issue 3(Volume 3, Issue 3) pp:
Publication Date(Web):14 September 2017
DOI:10.1016/j.chempr.2017.07.001
•Synthesis of subnanometric hybrid bimetallic clusters within zeolites•The nanocatalysts possessed excellent activity for hydrogen generation•The nanocatalysts exhibited shape-selective catalytic performance•The nanocatalysts showed superior thermal stability and recyclabilityHybrid multi-metallic nanocatalysts have attracted increasing attention because of the synergistic effect of metal species and considerably improved catalytic activity but often suffer from severe sintering and poor stability. Zeolites are known as ideal supports for confinement synthesis of metal nanoparticles. In this work, subnanometric hybrid Pd-M(OH)2 (M = Ni, Co) clusters encapsulated within purely siliceous zeolites were synthesized via a hydrothermal synthesis method. The hybrid bimetallic nanocatalysts exhibit superior thermal stability at 600°C–700°C and afford the highest initial turnover frequency value, up to 5,803 hr−1 toward complete formic acid decomposition without any additives at 60°C. The hybrid bimetallic nanoclusters confined in zeolites have potential practical application in dehydrogenation of formic acid as a viable and effective chemical hydrogen storage medium for fuel cells, and also raise more possibilities for other important high-performance catalytic reactions.Hybrid multi-metallic nanocatalysts have attracted increasing attention because of the synergistic effect of metal species and considerably improved catalytic performance, but they often suffer from severe sintering and poor stability. Here, we show a facile strategy for preparing subnanometric hybrid bimetallic clusters Pd-M(OH)2 (M = Ni, Co) within silicalite-1 (S-1) zeolite via a hydrothermal synthesis method. The hybrid bimetallic nanocatalysts exhibit excellent shape-selective catalytic performance and superior thermal stability. The incorporation of secondary Ni(OH)2 species in S-1 can considerably increase the catalytic activity of the Pd nanoclusters for the dehydrogenation of formic acid (FA) as a result of the electron-enriched Pd surface and bimetallic interfacial effect. Notably, the 0.8Pd0.2Ni(OH)2@S-1 catalyst affords the highest initial turnover frequency value, up to 5,803 hr−1 toward complete FA decomposition without any additives at 60°C. The superior catalytic properties and excellent stability of the subnanometric hybrid bimetallic clusters confined in zeolites create new prospects for their practical high-performance catalytic application.Download high-res image (265KB)Download full-size image
Co-reporter:Jun-Ran Lu, Chao Shi, Yi Li, Ji-Hong Yu
Chinese Chemical Letters 2017 Volume 28, Issue 7(Volume 28, Issue 7) pp:
Publication Date(Web):1 July 2017
DOI:10.1016/j.cclet.2017.04.010
In silico prediction of potential synthetic targets is the prerequisite for function-led discovery of new zeolites. Millions of hypothetical zeolitic structures have been predicted via various computational methods, but most of them are experimentally inaccessible under conventional synthetic conditions. Screening out unfeasible structures is crucial for the selection of synthetic targets with desired functions. The local interatomic distance (LID) criteria are a set of structure rules strictly obeyed by all existing zeolite framework types. Using these criteria, many unfeasible hypothetical structures have been detected. However, to calculate their LIDs, all hypothetical structures need to be fully optimized without symmetry constraints. When evaluating a large number of hypothetical structures, such calculations may become too computationally expensive due to the forbiddingly high degree of freedom. Here, we propose calculating LIDs among structures optimized with symmetry constraints and using them as new structure evaluation criteria, i.e., the LIDsym criteria, to screen out unfeasible hypothetical structures. We find that the LIDsym criteria can detect unfeasible structures as many as the original non-symmetric LID criteria do, yet require at least one order of magnitude less computation at the initial geometry optimization stage.The symmetric LIDsym criteria detect unfeasible hypothetical zeolite structures one order of magnitude faster than the original non-symmetric LID criteria.Download high-res image (174KB)Download full-size image
Co-reporter:Ning Wang; Qiming Sun; Risheng Bai; Xu Li; Guanqi Guo
Journal of the American Chemical Society 2016 Volume 138(Issue 24) pp:7484-7487
Publication Date(Web):June 1, 2016
DOI:10.1021/jacs.6b03518
Well-dispersed and ultrasmall Pd clusters in nanosized silicalite-1 (MFI) zeolite have been prepared under direct hydrothermal conditions using [Pd(NH2CH2CH2NH2)2]Cl2 as precursor. High-resolution scanning transmission electron microscopy studies indicate that the Pd clusters are encapsulated within the intersectional channels of MFI, and the Pd clusters in adjacent channels visually aggregate, forming nanoparticles (NPs) of ∼1.8 nm. The resultant catalysts show an excellent activity and highly efficient H2 generation toward the complete decomposition of formic acid (FA) under mild conditions. Notably, thanks to the further reduced Pd NP size (∼1.5 nm) and the additionally introduced basic sites, the Pd/S-1-in-K catalyst affords turnover frequency values up to 856 h–1 at 25 °C and 3027 h–1 at 50 °C. The easy in situ confinement synthesis of metal clusters in zeolites endows the catalysts with superior catalytic activities, excellent recyclability, and high thermal stability, thus opening new perspectives for the practical application of FA as a viable and effective H2 storage material for use in fuel cells.
Co-reporter:Ying Mu, Ning Wang, Zaicheng Sun, Jing Wang, Jiyang Li and Jihong Yu
Chemical Science 2016 vol. 7(Issue 6) pp:3564-3568
Publication Date(Web):12 Feb 2016
DOI:10.1039/C6SC00085A
Hydrophilic N-doped carbogenic nanodots (denoted as CNDs) have been prepared from a N-methylpiperazine-templated zeolite precursor by calcination and NaOH treatment. The isolated CNDs exhibit tunable photoluminescence according to the concentration and pH value of aqueous dispersions of the CNDs. Fine-tuning of the fluorescence emission wavelength across the entire visible spectrum can be easily achieved by varying the concentration of the CND dispersions. Meanwhile, both the emission wavelength and intensity of the photoluminescence can be tuned by controlling the pH value of the CND dispersion. The pyrolysis of organic templates confined in nanoporous zeolites represents a new approach to controlling the optical properties of CNDs, which may open more opportunities in applications such as multimodal sensing and full-color displays.
Co-reporter:Yi Li and Jihong Yu
Chemical Science 2016 vol. 7(Issue 6) pp:3472-3481
Publication Date(Web):29 Mar 2016
DOI:10.1039/C6SC00123H
Since the launch of the Materials Genome Initiative by the US government in 2011, many computer techniques have been developed to predict the structures and properties of advanced materials, providing important guidance for laboratory experimentation and a promising new direction for future materials innovation. However, lots of inorganic materials are difficult for computers to process because of their complex three-dimensionally extended structures. Fortunately, many of these materials are built from well-defined stacking layer modules, and the stacking sequences of their layer modules unambiguously determine their three-dimensional structures. Such one-dimensional stacking sequence representation is naturally accessible for computer processing, easing the problems not only of structure elucidation, but also in the enumeration, evaluation, and screening of a large number of unknown materials with desired properties. More importantly, with the aid of various computational methods, we may reveal the relationship between the stacking sequences and the properties of these materials, which is a key prerequisite for function-led targeted synthesis. This Minireview covers the most recent progress in this emerging area.
Co-reporter:Risheng Bai, Qiming Sun, Ning Wang, Yongcun Zou, Guanqi Guo, Sara Iborra, Avelino Corma, and Jihong Yu
Chemistry of Materials 2016 Volume 28(Issue 18) pp:6455
Publication Date(Web):September 6, 2016
DOI:10.1021/acs.chemmater.6b03179
Co-reporter:Shuting Du, Xiaoxin Chen, Qiming Sun, Ning Wang, Mingjun Jia, Valentin Valtchev and Jihong Yu
Chemical Communications 2016 vol. 52(Issue 17) pp:3580-3583
Publication Date(Web):28 Jan 2016
DOI:10.1039/C5CC10232D
Hierarchical TS-1 zeolites with secondary macropores have been successfully prepared by using two different fluoride-containing chemical etching post-treated routes. Hierarchical TS-1 zeolites exhibited a chemical composition similar to that of the parent material and showed remarkably enhanced catalytic activity in oxidative desulfurization reaction.
Co-reporter:Shuting Du, Fen Li, Qiming Sun, Ning Wang, Mingjun Jia and Jihong Yu
Chemical Communications 2016 vol. 52(Issue 16) pp:3368-3371
Publication Date(Web):22 Jan 2016
DOI:10.1039/C5CC08441E
Hierarchical TS-1 zeolites with uniform intracrystalline mesopores have been successfully synthesized through the hydrothermal method by using the green and cheap surfactant Triton X-100 as the mesoporous template. The resultant materials exhibit remarkably enhanced catalytic activity in oxidative desulfurization reactions compared to the conventional TS-1 zeolite.
Co-reporter:Xiaoxin Chen, Dongyang Xi, Qiming Sun, Ning Wang, Zhenyu Dai, Dong Fan, Valentin Valtchev, Jihong Yu
Microporous and Mesoporous Materials 2016 Volume 234() pp:401-408
Publication Date(Web):1 November 2016
DOI:10.1016/j.micromeso.2016.07.045
•SAPO-34 zeolites were synthesized by three different types of templates.•Secondary pores in zeolite crystals were formed by etching with HF-NH4F solutions.•Crystal morphology and physicochemical properties of zeolites were studied.•Organic templates impacted the etching process by fluoride route.•Hierarchical SAPO-34 exhibited improved selectivity and some diminished lifetime.A facile and effective fluoride post-treated route has been systematically applied for the preparation of hierarchical zeolite catalysts in three different SAPO-34 systems using morpholine, triethylamine and tetraethylammonium hydroxide as template, respectively. Secondary pores in SAPO-34 zeolite crystals are formed by etching with HF-NH4F containing solutions under ultrasonic condition. The samples were characterized by XRD, SEM, N2 adsorption-desorption, XRF, TG, 29Si MAS NMR and NH3-TPD techniques. The set of experimental data demonstrate that the organic templates impact the etching process by fluoride route, most probably the distribution of active sites, thus influence the catalytic properties. It is worth underline that the selectivity to C2H4 and C3H6 over the obtained hierarchical SAPO-34 catalysts in the methanol-to-olefin (MTO) reaction is improved as compared to the parent SAPO-34 catalysts, while an undesired diminished catalyst lifetime is observed for hierarchical SAPO-34 templated by morpholine and tetraethylammonium hydroxide.
Co-reporter:Guodong Feng;Peng Cheng;Wenfu Yan;Mercedes Boronat;Xu Li;Ji-Hu Su;Jianyu Wang;Yi Li;Ruren Xu;Avelino Corma
Science 2016 Volume 351(Issue 6278) pp:1188-1191
Publication Date(Web):11 Mar 2016
DOI:10.1126/science.aaf1559
Radically faster synthesis
Zeolite synthesis normally proceeds under basic conditions that allow the oxide bridges between aluminum and silicon atoms to break and reform. Feng et al. show that the formation of hydroxyl radicals, either by irradiation with ultraviolet light or with the Fenton reagent, can speed up the formation of the crystallized zeolite by about a factor of 2.
Science, this issue p. 1188
Co-reporter:Zhiying Fan;Dr. Dongdong Li;Xue Yu;Dr. Yuping Zhang; Yong Cai; Jingji Jin; Jihong Yu
Chemistry - A European Journal 2016 Volume 22( Issue 11) pp:3681-3685
Publication Date(Web):
DOI:10.1002/chem.201504377
Abstract
Hollow mesoporous silica nanospheres functionalized with aggregation-induced emission (AIE) luminogen tetraphenylethene were prepared by postgrafting method. The as-prepared inorganic–organic hybrid nanospheres show bright blue emission and good biocompatibility as shown by MTT assays. The large cavities of the materials enable high loading of the anticancer drug doxorubicin hydrochloride (DOX), and the mesoporous silica shells allow pH-dependent drug release. The materials can be effectively taken up by cells and function as luminescent bioprobes, demonstrating their potential application in imaging-guided therapy.
Co-reporter:Jiyang Li, Avelino Corma and Jihong Yu
Chemical Society Reviews 2015 vol. 44(Issue 20) pp:7112-7127
Publication Date(Web):05 Mar 2015
DOI:10.1039/C5CS00023H
The search for new zeolites is of continuous interest in the field of zeolite science because of their widespread application in catalysis and adsorption–separation. To this end, considerable efforts have been devoted to the preparation of new zeolites with novel porous architectures and compositions. Taking account of the key factors governing the formation of zeolites (e.g., guest species, framework elements, construction processes, etc.), several synthetic strategies have been developed recently. These allow the discovery of many new zeolites with unprecedented structural features, such as hierarchical pores, odd-ring numbers (11-, 15-rings), extra-large pores (16-, 18-, 20-, 28-, and 30-rings), chiral pores, and extremely complex framework topologies, etc. In this review, we will present the advances in the synthesis of new zeolite structures in the last decade, which are achieved by utilization of the synthetic strategies based on pre-designed structure-directing agents, heteroatom substitution, and topotactic transformations.
Co-reporter:Bert M. Weckhuysen and Jihong Yu
Chemical Society Reviews 2015 vol. 44(Issue 20) pp:7022-7024
Publication Date(Web):24 Sep 2015
DOI:10.1039/C5CS90100F
A graphical abstract is available for this content
Co-reporter:Junbiao Wu, Chunyao Tao, Yi Li, Jiyang Li and Jihong Yu
Chemical Science 2015 vol. 6(Issue 5) pp:2922-2927
Publication Date(Web):05 Mar 2015
DOI:10.1039/C5SC00291E
A novel zinc gallophosphate zeolitic material |(C12H14N2)4F1.33|[Ga13.33Zn6.67(PO4)20] (denoted as JU101) has been prepared by using in situ generated methyl viologen (MV) as the template. The framework of JU101 features two building units including an unprecedented fused d6r and a novel [412·64·82·102] cavity. The connection of these two building units forms a 3D intersecting pore system containing 8-rings along the [010] direction, and 10-rings along the [001] and [100] directions. The MV-templated JU101 zeolitic material offers a new type of electron transfer system, which endows the material with interesting photochromism, thermochromism, and tuneable photovoltaic activity in response to light and heating. Importantly, JU101 shows an extended photochromism range from UV to visible light, high thermal stability, as well as a long-lived charge-separated state for potential application in solar energy conversion.
Co-reporter:Dongdong Li, Yuping Zhang, Zhiying Fan, Jie Chen and Jihong Yu
Chemical Science 2015 vol. 6(Issue 11) pp:6097-6101
Publication Date(Web):20 Jul 2015
DOI:10.1039/C5SC02044A
Aggregation-induced emission (AIE) and aggregation-caused quenching (ACQ) materials are important for various fluorescence-based applications but cannot easily collaborate because of their opposite luminescence behaviours. Here, we demonstrate a strategy to integrate AIE and ACQ chromophores in periodic mesoporous organosilicas (PMOs) for high-efficiency multicolour emission. Tetraphenylethene (TPE)-bridged AIE-PMOs are prepared as hosts to encapsulate ACQ dyes (e.g. RhB), which enables fine-tuning of ACQ@AIE-PMO emissions over the entire visible spectrum in the solid and film states. Significantly, high-quality white light is achieved with CIE coordinates of (0.32, 0.33) and a quantum yield of up to 49.6%. Because of their high stability and solution processability, the ACQ@AIE-PMOs can be applied in solid-state lighting and bioimaging. This design concept opens up new perspectives for developing high-performance luminescent materials by the combination of a wide variety of AIE and ACQ chromophores.
Co-reporter:Qiming Sun, Ning Wang, Guanqi Guo, Xiaoxin Chen and Jihong Yu
Journal of Materials Chemistry A 2015 vol. 3(Issue 39) pp:19783-19789
Publication Date(Web):20 Aug 2015
DOI:10.1039/C5TA04642D
Hierarchically porous zeolites with different levels of porosity have emerged as an important class of materials because of their enhanced mass transport and improved catalytic performance. Silicoaluminophosphate zeolite SAPO-34 is one of the best catalysts for methanol-to-olefin (MTO) conversion, but suffers from rapid deactivation due to the narrow 8-ring pore openings. To overcome this inherent diffusion bottleneck and improve the MTO performance, in this work, tri-level hierarchically porous SAPO-34 zeolite with intracrystalline micro–meso–macroporosity has been first synthesized by an Al-rich method coupled with the use of the polyethylene glycol 2000 polymer under hydrothermal conditions. The as-synthesized hierarchically porous SAPO-34 catalysts exhibit superior catalytic performance in the MTO reaction with about six times prolonged catalytic lifetime and nearly 5% improvement of selectivity for ethylene and propylene compared to the conventional microporous SAPO-34.
Co-reporter:Qiming Sun, Ning Wang, Guanqi Guo and Jihong Yu
Chemical Communications 2015 vol. 51(Issue 91) pp:16397-16400
Publication Date(Web):16 Sep 2015
DOI:10.1039/C5CC07343J
Nano-sized SAPO-34 zeolites with high crystallinity are obtained in 10 minutes by fast heating the reaction gel in a stainless steel tubular reactor combined with the seed-assisted method, which show outstanding performance in methanol-to-olefin (MTO) reaction.
Co-reporter:Dongdong Li, Yuping Zhang, Zhiying Fan and Jihong Yu
Chemical Communications 2015 vol. 51(Issue 72) pp:13830-13833
Publication Date(Web):23 Jul 2015
DOI:10.1039/C5CC05173H
Mesoporous silica nanoparticles functionalised with aggregation-induced emission (AIE) luminogen via a carbon–nitrogen double bond are fabricated into films by a dip-coating method. The as-made films can serve as efficient fluorescent sensors for the naked-eye detection of volatile acid gases by colour and emission changes, as well as for the detection of 2,4-dinitrotoluene vapours by fluorescence quenching.
Co-reporter:Dongyang Xi, Qiming Sun, Xiaoxin Chen, Ning Wang and Jihong Yu
Chemical Communications 2015 vol. 51(Issue 60) pp:11987-11989
Publication Date(Web):19 Jun 2015
DOI:10.1039/C5CC03904E
A facile and green route has been developed for the synthesis of hierarchical zeolite catalysts by recycling of waste mother-liquors. After three recycles of mother-liquors, the obtained hierarchical SAPO-34 zeolites retain high crystallinity, texture properties, and acidity, as well as excellent MTO catalytic performance as compared to the initially prepared catalysts.
Co-reporter:Yanjun Sun, Yan Yan, Yanyan Wang, Yi Li, Jiyang Li and Jihong Yu
Chemical Communications 2015 vol. 51(Issue 45) pp:9317-9319
Publication Date(Web):06 May 2015
DOI:10.1039/C5CC03116H
A new open-framework aluminophosphate Na6[(AlPO4)8(OH)6]·8H2O (JU103) has been synthesized by utilization of the organotemplate-free synthetic route in alkali metal-containing system. The as-prepared JU103 possesses two-dimensional intersecting 8-ring channels. Sodium ions and water molecules in the channels facilitates JU103 excellent proton conductivity up to 3.59 × 10−3 S cm−1 (293 K, 98% RH).
Co-reporter:Ying Mu, Yanyan Wang, Yi Li, Jiyang Li and Jihong Yu
Chemical Communications 2015 vol. 51(Issue 11) pp:2149-2151
Publication Date(Web):15 Dec 2014
DOI:10.1039/C4CC08964B
A new open-framework magnesium aluminophosphate MgAlP2O7(OH)(H2O)2 (denoted as JU102) has been hydrothermally synthesized by using an organotemplate-free synthetic route in the Al2O3–P2O5–MgO–H2O system. JU102 exhibits novel 4-connected zeolite-like topology with 8-ring channels. The existence of coordinated water and extensive H-bonds in the structure endows JU102 with unique proton conduction properties.
Co-reporter:Libo Sun, Zhiqiang Liang and Jihong Yu
Polymer Chemistry 2015 vol. 6(Issue 6) pp:917-924
Publication Date(Web):15 Oct 2014
DOI:10.1039/C4PY01284D
The Heck coupling reaction of vinyl-terminated double four-ring siloxane cages (octavinylsilsesquioxane) with aromatic bromide monomers (4,4′-dibromobiphenyl, 1,4-dibromonaphthalene, 2,6-dibromonaphthalene and 1,2-bis(4-bromophenyl)-1,2-diphenylethene) was used to construct a class of luminescent nanoporous inorganic–organic hybrid polymers (PS-n). The structures of these polymers were confirmed by solid state 13C CP/MAS and 29Si MAS NMR spectra, as well as Fourier transform infrared spectroscopy (FTIR). The results identify polymers with Brunauer–Emmett–Teller (BET) surface areas of up to 685 m2 g−1. The luminescence properties of these polymers were utilized for picric acid detection. Furthermore, PS-1-n (n = 6, 12, 24, 48 or 72 h) samples polymerized for different lengths of time were investigated for their energy transfer behaviour with Coumarin 6.
Co-reporter:Yi Li and Jihong Yu
Chemical Reviews 2014 Volume 114(Issue 14) pp:7268
Publication Date(Web):May 21, 2014
DOI:10.1021/cr500010r
Co-reporter:Junbiao Wu, Chunyao Tao, Yi Li, Yan Yan, Jiyang Li and Jihong Yu
Chemical Science 2014 vol. 5(Issue 11) pp:4237-4241
Publication Date(Web):24 Jul 2014
DOI:10.1039/C4SC01396D
X-ray-induced photochromic materials are promising candidates for X-ray detection. An effective strategy to synthesize photochromic materials is the incorporation of photochromic methylviologen (MV) into inorganic open frameworks. It is of great interest to adjust the photochromic behaviour of MV-based materials using designed synthesis of novel anionic open frameworks. A new multifunctional photo-sensitive material, MV-templated layered bimetal phosphate JU99, is presented. It possesses unique X-ray-induced photochromism at room temperature, as well as interesting photoluminescence and photovoltaic activity, all of which are reversible in response to X-ray irradiation. These properties make JU99 an excellent material for X-ray detection.
Co-reporter:Yuping Zhang, Dongdong Li, Yi Li and Jihong Yu
Chemical Science 2014 vol. 5(Issue 7) pp:2710-2716
Publication Date(Web):31 Mar 2014
DOI:10.1039/C4SC00721B
A novel class of tetraphenylethene (TPE) derivatives TPEM and TPEBM containing dicyanovinyl groups were synthesized, possessing remarkable dual properties of solvatochromism and aggregation-induced emission (AIE). The combination of the electron-donating TPE and the electron-accepting dicyanovinyl group endow both compounds with a prominent solvatochromic effect, with emissions strongly dependent on solvent polarity and tunable from blue to red by changing the solvent from apolar to polar. They are found to be useful as fluorescent indicators for the qualitative and quantitative detection of low-level water content in organic solvents, and the detection limit can be as low as 63 ppm and 109 ppm in THF, respectively. Meanwhile, TPEM and TPEBM demonstrate typical AIE features and emit green-yellow and orange light in their aggregated states, respectively. Based on the AIE feature of TPE and the nucleophilic addition of cyanide, both compounds can act as colorimetric and fluorescent sensors for highly sensitive and selective detection of CN− in aqueous media under the assistance of cetyltrimethylammonium bromide (CTAB). The low detection limit of 0.2 μM as well as a short sensing process of only 100 seconds promise their practical application for detecting cyanide in drinking water. Furthermore, the development of easy-to-prepare test papers provides a convenient and reliable approach to monitor CN− in daily applications without resorting to instrumental analysis.
Co-reporter:Dongyang Xi, Qiming Sun, Jun Xu, Minhyung Cho, Hae Sung Cho, Shunsuke Asahina, Yi Li, Feng Deng, Osamu Terasaki and Jihong Yu
Journal of Materials Chemistry A 2014 vol. 2(Issue 42) pp:17994-18004
Publication Date(Web):01 Sep 2014
DOI:10.1039/C4TA03030C
Silicoaluminophosphate zeolite SAPO-34 with CHA topology is known as one of the best catalysts for methanol-to-olefin (MTO) conversion. In this work, we demonstrate a facile one-step hydrothermal synthesis of hierarchically macroporous SAPO-34 through the etching effect of hydrofluoric acid. The highly crystalline hierarchically macroporous SAPO-34 is prepared as central-holed rhombohedral crystals with particle size of ca. 5–10 μm that comprise intracrystalline parallel macrochannels of ca. 100 nm. The formation of macroporous structures via in situ growth-etching can be directly imaged by SEM. Strikingly, a particular crystal configuration consisting of eight pyramidal parts has been first observed during the zeolite crystal growth process, which eventually grows to form a perfect rhombohedral shape. The HF etching effect is further elucidated by the analysis of changes of pH values as well as of solid and liquid compositions following the evolution of crystallization. The texture properties, chemical environments of framework atoms, and acidity of the synthesized SAPO-34 are characterized by N2 adsorption/desorption, MAS NMR and NH3-TPD measurements. The hierarchically macroporous SAPO-34 shows larger micropore volume, slightly stronger acid strength, and lower external surface acidity than its conventional counterpart synthesized without using HF. Consequently, the hierarchically macroporous SAPO-34 exhibits excellent MTO catalytic performance, showing much higher selectivity to ethylene and propylene as well as longer lifetime than the conventional counterpart. In comparison with previously reported methods for the generation of hierarchical porosity, this one-step HF-assisted in situ growth-etching synthetic route is simple, straightforward and cost-effective, which offers a new approach to prepare hierarchically porous zeolites with improved catalytic activity.
Co-reporter:Qiming Sun, Yanhang Ma, Ning Wang, Xu Li, Dongyang Xi, Jun Xu, Feng Deng, Kyung Byung Yoon, Peter Oleynikov, Osamu Terasaki and Jihong Yu
Journal of Materials Chemistry A 2014 vol. 2(Issue 42) pp:17828-17839
Publication Date(Web):27 Aug 2014
DOI:10.1039/C4TA03419H
Nanosheet-like silicoaluminophosphate (SAPO) molecular sieves SAPO-34 (CHA-type) and SAPO-18 (AEI-type) with different silicon contents were synthesized under hydrothermal conditions by using tetraethylammonium hydroxide as the template. Three-dimensional electron diffraction tomography (3D EDT) technique was applied for ab initio structure solutions. Electron microscopy observations confirmed the existence of defects, i.e., intergrowth of CHA- and AEI-type frameworks caused by the different stacking manners of double 6-ring layers, but the layers were highly coherent along c direction. Compositions, acidities, chemical environments, and texture properties of all the samples were characterized by ICP, EDS, NH3-TPD, MAS NMR, and N2 adsorption–desorption measurements. The catalytic performances of methanol-to-olefin (MTO) reactions over nano SAPO catalysts with different silicon contents were systematically studied. All of these catalysts showed excellent catalytic activity, among which SAPO-34 showed superior catalytic performance compared to SAPO-18. DFT calculations were utilized to study the different catalytic performance of CHA and AEI. Significantly to date, SAPO-34 with the lowest silicon content exhibited the longest catalyst lifetime and the lowest coking rate in the MTO reaction than any of the reported catalysts, tested under similar conditions. The straight 8-ring pore channel along the c direction provided the optimum diffusion pathway as well as the shortest diffusion length for reactant and generated olefins, thus significantly reduced the coking rate. This work demonstrates that a 3D EDT approach combined with TEM and EDS analysis from a single nanocrystal can provide a clear crystal structure, crystal orientation and compositional information of nanocrystals, which are useful for the better understanding of the catalytic performance of nanosized crystalline catalysts.
Co-reporter:Qiming Sun, Ning Wang, Dongyang Xi, Miao Yang and Jihong Yu
Chemical Communications 2014 vol. 50(Issue 49) pp:6502-6505
Publication Date(Web):30 Apr 2014
DOI:10.1039/C4CC02050B
Using an organosilane surfactant as the mesopore director, hierarchical porous silicoaluminophosphate SAPO-34 is obtained as an assembly of nanocrystallites intergrown into cubic micrometer-sized crystals, which show excellent performance in MTO reactions with a remarkably prolonged catalyst lifetime and enhanced selectivity of ethylene and propylene compared to the conventional microporous SAPO-34.
Co-reporter:Yanyan Wang, Yanjun Sun, Ying Mu, Chuanqi Zhang, Jiyang Li and Jihong Yu
Chemical Communications 2014 vol. 50(Issue 97) pp:15400-15403
Publication Date(Web):17 Oct 2014
DOI:10.1039/C4CC06319H
A facile organotemplate-free route has been developed to synthesize an aluminophosphate molecular sieve in an alkali metal-containing system under hydrothermal conditions. The as-prepared JU93 possesses AEN zeotype topology with small 8-ring pores, and its derivatives show ion conductivity and adsorption selectivity of CO2 over CH4.
Co-reporter:Libo Sun, Yongcun Zou, Zhiqiang Liang, Jihong Yu and Ruren Xu
Polymer Chemistry 2014 vol. 5(Issue 2) pp:471-478
Publication Date(Web):22 Aug 2013
DOI:10.1039/C3PY00980G
A series of luminescent microporous organic polymers (LMOPs) have been synthesized by a new synthetic methodology through the palladium catalyzed tandem Suzuki–Heck C–C coupling reactions of several aromatic halides with potassium vinyltrifluoroborate. These polymers are porous with the BET surface areas from 318 to 693 cm2 g−1. The formation of conjugated polymers with the incorporation of vinyl groups leads to the fluorescent properties, and the luminescence of LMOPs could be adjusted from blue to green by selecting the aromatic halides and alternating the ratio of monomers. The fluorescence quenching behaviors of these LMOPs by nitroaromatic analytes in ethanol are investigated. It is found that the fluorescence of the polymers can be effectively quenched by picric acid (PA).
Co-reporter:Chuanlong Miao, Dongdong Li, Yuping Zhang, Jihong Yu, Ruren Xu
Microporous and Mesoporous Materials 2014 Volume 196() pp:46-50
Publication Date(Web):15 September 2014
DOI:10.1016/j.micromeso.2014.04.049
•The materials combine the properties of AIE luminogen and porous materials.•The emission changed from 467 to 527 nm with increasing AIE molecules.•The obtained AIE functionalized nanoparticles show well dispersibility in water.•The materials can be used as an efficient fluorescent sensor.•The materials can be recycled by simply washed with proper solvents.The aggregation-induced emission (AIE) luminogen functionalized mesoporous silica nanoparticles (MSNs) were prepared via post-grafting 1,2-bis[4-(bromomethyl)phenyl]-1,2-diphenylethene (TPE-MB) on 3-aminopropyltriethoxysilane modified MSNs. The obtained materials combine the unique properties of the AIE luminogen and porous materials, and their emission wavelength can be changed from 467 to 527 nm by loading different amount of AIE molecules, showing an obvious red shift from blue light to yellow light. Such materials with well dispersibility in water are used as an efficient fluorescent sensor for the detection of explosives, including picric acid (PA), 4-nitrotoluene (4-NT), nitrobenzene (NB) in water. The obtained materials can be recycled by simply washing with proper solvents. The high sensitivity, increased chemical stability and recyclability of the AIE luminogen functionalized mesoporous silica nanoparticles promise that they can be used as an excellent fluorescence probe for future practical applications in explosives detection.AIE luminogen functionalized mesoporous silica nanoparticles with emission changing from blue to pale-yellow are an efficient and recyclable fluorescent sensor for explosives in water.
Co-reporter:Xu Li ; Qiming Sun ; Yi Li ; Ning Wang ; Junran Lu
The Journal of Physical Chemistry C 2014 Volume 118(Issue 43) pp:24935-24940
Publication Date(Web):October 2, 2014
DOI:10.1021/jp505696m
The confinement effect of zeolite cavities on the methanol-to-olefin (MTO) conversion is investigated through density functional theory calculations. According to the side-chain mechanism, we select several hydrocarbon pool (HP) intermediates that may exist during the MTO conversion process and optimize their structures within the cluster models of zeolite cavities cha, lev, and lta, respectively. The transition states during methylation, deprotonation, methyl shift, and olefin production are also located within these cavities. According to our results, all of the HP intermediates are stabilized in zeolite cavities, especially in cha and lta. Moreover, the cha cavity displays the lowest intrinsic free-energy barriers for all of the methylation and olefin-production steps, indicating its high MTO catalytic activity. We find that the differences in reaction barriers and reaction energies are highly related to the different confinement effects of zeolite cavities. In comparison with lev and lta, the cha cavity matches the dimensions of HP species very well, so it is able to provide the most suitable confinement to HP species. Our discovery will provide further understanding of the side-chain mechanism, which is important for finding new catalysts for MTO conversion.
Co-reporter:Chuanlong Miao, Dongdong Li, Yuping Zhang, Jihong Yu, Ruren Xu
Microporous and Mesoporous Materials 2014 200() pp: 281-286
Publication Date(Web):
DOI:10.1016/j.micromeso.2014.07.008
Co-reporter:Qiang Wen, Jiancheng Di, Yong Zhao, Yang Wang, Lei Jiang and Jihong Yu
Chemical Science 2013 vol. 4(Issue 12) pp:4378-4382
Publication Date(Web):16 Aug 2013
DOI:10.1039/C3SC51851E
Organic molecule pollution in industrial and agricultural sewage is a serious threat to the environment and human health. Adsorption membranes have proven to be good candidates for removing contaminations from wastewater efficiently and continuously. Inorganic porous materials possessing large surface area, and high chemical and thermal stability are excellent adsorbents for organic contaminants. However, a major shortfall of the inorganic porous membranes is that they are usually fragile. Here we demonstrate flexible SiO2–TiO2 composite porous nanofibrous membranes fabricated via electrospinning technique for efficient water purification. The composite membranes exhibit high adsorption capacity and permeability in the purification test with methylene blue solution based on their hierarchical porous structure and ultrafast wettability, and can be easily recycled by calcination. Such properties, integrated with the membrane fabrication process that is energy-efficient, low cost and easy to scale-up, will facilitate their practical application in the removal of organic pollutants.
Co-reporter:Qiang Wen, Jiancheng Di, Lei Jiang, Jihong Yu and Ruren Xu
Chemical Science 2013 vol. 4(Issue 2) pp:591-595
Publication Date(Web):23 Nov 2012
DOI:10.1039/C2SC21772D
Oil–water separations are helping with urgent issues due to increasing industrial oily wastewater, as well as frequent oil spill accidents. Membrane-based materials with special wettability are desired to separate oils from water. However, fabrication of energy-efficient and stable membranes that are suitable for practical oil–water separation remains challenging. Zeolite films have attracted intense research interest due to their unique pore character, excellent chemical, thermal and mechanical stability, etc. Here we first demonstrate zeolite-coated mesh films for gravity-driven oil–water separation. High separation efficiency of various oils can be achieved based on the excellent superhydrophilicity and underwater superoleophobicity of the zeolite surface. Flux and intrusion pressure are tunable by simply changing the pore size, dependent on the crystallization time of the zeolite crystals, of the zeolite meshes. More importantly, such films are corrosion-resistant in the presence of corrosive media, which gives them promise as candidates in practical applications of oil–water separation.
Co-reporter:Libo Sun, Hongzhu Xing, Zhiqiang Liang, Jihong Yu and Ruren Xu
Chemical Communications 2013 vol. 49(Issue 95) pp:11155-11157
Publication Date(Web):11 Jun 2013
DOI:10.1039/C3CC43383H
A zeolitic metal–organic framework with a SOD topology, (Et2NH2)[In(BCBAIP)]·4DEF·4EtOH (H4BCBAIP: 5-(bis(4-carboxybenzyl)amino)isophthalic acid) (1), has been constructed by a 4 + 4 synthetic strategy from tetrahedral organic building units and In3+ ions. Compound 1 could adsorb organic dyes and be used as a light-harvesting antenna.
Co-reporter:Dongdong Li, Chuanlong Miao, Xiaodan Wang, Xianghui Yu, Jihong Yu and Ruren Xu
Chemical Communications 2013 vol. 49(Issue 83) pp:9549-9551
Publication Date(Web):20 Aug 2013
DOI:10.1039/C3CC45041D
An aggregation-induced emission (AIE) probe, possessing a quaternary tetraphenylethene (TPEN) cation, was successfully intercalated into layered α-zirconium phosphate (α-ZrP) nanosheets by ion-exchange. The hybrid materials emit strong blue emissions in aqueous solution which can be used as an effective fluorescence label for HeLa cells.
Co-reporter:Yan Xu, Leifeng Liu, Daniel M. Chevrier, Junliang Sun, Peng Zhang, and Jihong Yu
Inorganic Chemistry 2013 Volume 52(Issue 18) pp:10238-10244
Publication Date(Web):February 12, 2013
DOI:10.1021/ic302705f
A new open-framework germanate, denoted as GeO-JU90, was prepared by the hydrothermal synthesis method using 1,5-bis(methylpyrrolidinium)pentane dihydroxide as the organic structure-directing agent (SDA). The structure of GeO-JU90 was determined from synchrotron X-ray powder diffraction (XRPD) data using the charge-flipping algorithm. It revealed a complicated framework structure containing 11 Ge atoms in the asymmetric unit. The framework is built of 7-connected Ge7 clusters and additional tetrahedral GeO3(OH) units forming a new three-dimensional interrupted framework with interesting 12 × 12 × 11-ring intersecting channels. The Ge K-edge extended X-ray absorption fine structure (EXAFS) analysis was performed to provide the local structural information around Ge atoms, giving rise to a first-shell contribution from about 4.2(2) O atoms at the average distance of 1.750(8) Å. The guest species in the channels were subsequently determined by the simulated annealing method from XRPD data combining with other characterization techniques, e.g., 13C NMR spectroscopy, infrared spectroscopy (FTIR), compositional analyses, and thermogravimetric analysis (TGA). Crystallographic data |(C15N2H32)(NH4)|[Ge11O21.5(OH)4], orthorhombic Ama2 (No. 40), a = 37.82959 Å, b = 15.24373 Å, c = 12.83659 Å, and Z = 8.
Co-reporter:Dongdong Li, Zhiqiang Liang, Jie Chen, Jihong Yu and Ruren Xu
Dalton Transactions 2013 vol. 42(Issue 27) pp:9877-9883
Publication Date(Web):22 Apr 2013
DOI:10.1039/C3DT50243K
A new type of organophosphonic acid, (4,4′-(1,2-diphenylethene-1,2-diyl)bis(4,1-phenylene))bis(methylene)diphosphonic acid (PATPE), based on tetraphenylethene has been prepared, and its ester derivative exhibits the characteristic property of aggregation-induced emission (AIE) in DMSO–H2O solution. The PATPE is then fabricated into hydroxyapatite by a one-pot condensation process to form hollow mesoporous nanocapsules of ellipsoidal morphology. The AIE luminogen-bridged hollow hydroxyapatite nanocapsules emit strong blue light under UV irradiation, which is further used for drug delivery using ibuprofen (IBU) as a model drug. The fluorescence intensity of the materials varies greatly with the loading and release of IBU, suggesting that the drug release process may be tracked in terms of the change of luminescence intensity. The biocompatibility of AIE luminogen functionalized material is also evaluated on HUH7 human hepatoma cells using the MTT assay. The low cytotoxicity of the materials reveals that the as-prepared multifunctional hydroxyapatite will be a new candidate for simultaneous drug delivery and cell imaging in potential bioapplications.
Co-reporter:Miao Yang, Xinjie Li, Jihong Yu, Jingran Zhu, Xiaoxia Liu, Genfu Chen and Yan Yan
Dalton Transactions 2013 vol. 42(Issue 18) pp:6298-6301
Publication Date(Web):15 Mar 2013
DOI:10.1039/C3DT50591J
A new chiral copper borophosphate, LiCu2[BP2O8(OH)2] (1), was crystallized from achiral inorganic raw materials in boric acid flux reaction. The structure features a 9-ring channel enclosed by triple right-handed helices. The bulk sample exhibits optical activity confirmed by circular dichroism (CD) spectra, indicating an interesting spontaneous resolution phenomenon.
Co-reporter:Xiaofang Wang, Jingxia Wang, Jiancheng Di, Jihong Yu, Lei Jiang
Microporous and Mesoporous Materials 2013 Volume 168() pp:121-125
Publication Date(Web):1 March 2013
DOI:10.1016/j.micromeso.2012.09.017
We report a photochemically tunable photonic crystals (PCs) system, based on azobenzene derivatives covalently grafted onto mesoporous silica photonic crystals (azo-MS-PCs), of which the reflectance at the stopband position can be modulated by alternating UV/Visible (UV/Vis) light irradiation. The stopband position of azo-MS-PCs was found to be dependent on the photoisomerization of azo ligands. The decreased effective refractive index of azo-MS-PCs at the cis-state under UV light irradiation led to a blue-shift of stopband position. Upon irradiation with Vis light, the stopband position was recovered after photoisomerization from the cis-state to the trans-state. The introduction of mesoporous silica matrix could not only enhance the grafting content, mechanical, chemical, and thermal stability of the responsive moieties, but also meet the steric demands of azo photoisomerization process. This work may open a new way to fabricate multi-functional PCs materials with the tunable band gap.Graphical abstractHighlights► High quality azo-modified mesoporous silica photonic crystals was fabricated. ► Azo derivatives were covalently attached to the mesoporous silica. ► The stopband position can be modulated by alternating UV/Vis light irradiation.
Co-reporter:Guoju Yang ; Yingxu Wei ; Shutao Xu ; Jingrun Chen ; Jinzhe Li ; Zhongmin Liu ; Jihong Yu ;Ruren Xu
The Journal of Physical Chemistry C 2013 Volume 117(Issue 16) pp:8214-8222
Publication Date(Web):March 25, 2013
DOI:10.1021/jp312857p
In this work, we systematically investigated the size effect of silicoaluminophosphate molecular sieve catalysts SAPO-34 on the catalytic performance of methanol-to-olefin (MTO) reactions. Four highly crystalline SAPO-34 molecular sieves with different crystallite sizes were synthesized under hydrothermal conditions carried out in conventional or microwave ovens with the same starting gel composition using TEAOH as the structure-directing agent. The as-prepared SAPO-34s have similar composition, and their average crystal size can be controlled between 20 nm and 8 μm. Textural properties and chemical environments of framework atoms as well as acid concentration were characterized by N2 adsorption and NMR measurements. The MTO reactions were carried out over these four SAPO-34 catalysts to study their catalytic performances dependent on the crystal size. The occurrence of catalyst deactivation varied considerably with the crystal size of SAPO-34s. Significantly, the nanosized catalysts, especially the sheetlike SAPO-34 catalyst with 20 nm thickness, exhibited the longest catalyst lifetime and lowest coking rate in MTO reactions. On the basis of the measurement of coke formation and the determination of retained coke species, a scheme is proposed to elucidate the reduction in coke deposition and consequently the remarkably enhanced lifetime on the nanosized SAPO-34 catalysts in methanol conversion.
Co-reporter:Dr. Yi Li; Jihong Yu; Ruren Xu
Angewandte Chemie 2013 Volume 125( Issue 6) pp:1717-1721
Publication Date(Web):
DOI:10.1002/ange.201206340
Co-reporter:Yan Xu;Dr. Yi Li;Dr. Yide Han;Dr. Xiaowei Song ; Jihong Yu
Angewandte Chemie 2013 Volume 125( Issue 21) pp:5611-5613
Publication Date(Web):
DOI:10.1002/ange.201300846
Co-reporter:Dr. Yi Li; Jihong Yu; Ruren Xu
Angewandte Chemie International Edition 2013 Volume 52( Issue 6) pp:1673-1677
Publication Date(Web):
DOI:10.1002/anie.201206340
Co-reporter:Yan Xu;Dr. Yi Li;Dr. Yide Han;Dr. Xiaowei Song ; Jihong Yu
Angewandte Chemie International Edition 2013 Volume 52( Issue 21) pp:5501-5503
Publication Date(Web):
DOI:10.1002/anie.201300846
Co-reporter:Zhuopeng Wang, Jihong Yu and Ruren Xu
Chemical Society Reviews 2012 vol. 41(Issue 5) pp:1729-1741
Publication Date(Web):22 Nov 2011
DOI:10.1039/C1CS15150A
Zeolites are an important class of materials which are widely used in industry as catalysts, adsorbents and ion-exchangers. Their superior properties are closely related to their unique porous framework structure, as well as composition and morphology. The ever-growing needs for zeolitic materials in applications inspire us to think of the rational synthesis of zeolites with desired structures and properties. However, rationalization of zeolitic materials remains one of the most challenging issues in the zeolite research field due to their unclear formation mechanism. Despite this, many efforts have been devoted to synthesize zeolites in a more rational way. In this tutorial review, first, we demonstrate how the geometrical characteristics of zeolite frameworks affect the catalytic performances of the resulting materials; then, we present recent advances in synthetic innovations to target materials, and we further highlight the developments in computer simulations toward ab initio design and synthesis; finally, the future perspective on the rational synthesis of zeolitic materials with desired functions and structures will be described.
Co-reporter:Dongdong Li, Jianzhao Liu, Ryan T. K. Kwok, Zhiqiang Liang, Ben Zhong Tang and Jihong Yu
Chemical Communications 2012 vol. 48(Issue 57) pp:7167-7169
Publication Date(Web):23 May 2012
DOI:10.1039/C2CC31890C
Mesoporous SBA-15 functionalized with aggregation-induced emission (AIE) luminogens serves as an efficient and recyclable fluorescent sensor for the detection of picric acid (PA), with a quenching constant of up to 2.5 × 105 M−1 in a water solution, presenting a new model for the supersensitive detection of explosives.
Co-reporter:Lang Shao, Yi Li, Jihong Yu, and Ruren Xu
Inorganic Chemistry 2012 Volume 51(Issue 1) pp:225-229
Publication Date(Web):December 7, 2011
DOI:10.1021/ic201515z
Two divalent-metal-containing aluminophosphates, (C5H14N2)[Co2Al4P6O24] and (C5H14N2)[Zn2Al4P6O24] (denoted as MAPO-CJ62; M = Co, Zn), have been hydrothermally synthesized by using N-methylpiperazine as the structure directing agent. Their structures are determined by single crystal X-ray diffraction and further characterized by powder X-ray diffraction, inductively coupled plasma, and thermogravimetric and diffuse reflectance spectroscopy analyses. Both of these two compounds exhibit a new zeolite framework topology. This new zeolite framework contains 1-dimensional 8-ring channels running along the [010] direction. All the metal and P atoms are tetrahedrally coordinated and alternately connected to each other through bridging O atoms. Inductively coupled plasma analysis shows that the molar ratio of M:Al in MAPO-CJ62 is 1:2. The M2+ ions in MAPO-CJ62 selectively occupy two of the three possible crystallographically distinct positions. A pure aluminophosphate analogue of MAPO-CJ62 without M2+-incorporation, denoted as AlPO-CJ62, has not been obtained in our experiment so far. The necessity of introducing M2+ ions and their ordered distribution in MAPO-CJ62 has been elucidated by analyzing the distortions of Al-centered tetrahedra in the hypothetical framework of AlPO-CJ62.
Co-reporter:Zhuo Liu, Xiaowei Song, Jiyang Li, Yi Li, Jihong Yu, and Ruren Xu
Inorganic Chemistry 2012 Volume 51(Issue 3) pp:1969-1974
Publication Date(Web):January 17, 2012
DOI:10.1021/ic2022903
Two novel heteroatom-containing aluminophosphate molecular sieves, |(C4NH12)4|[M4Al12P16O64] (denoted MAPO-CJ69, M = Co and Zn), have been solvothermally synthesized using diethylamine as the structure-directing agent. The framework of MAPO-CJ69 exhibits a new zeolite topology which is constructed by strict alternation of metal-centered (Al/M)O4 tetrahedra and PO4 tetrahedra to form a three-dimensional anionic [M4Al12(PO4)16]4– framework. The structure contains two intersecting 8-ring channels along the [010] and [001] directions, and the protonated diethylamine cations reside in the 8-ring channels to achieve charge neutrality. The structure of MAPO-CJ69 is composed of the 4-4- secondary building unit (SBU), which has been found in some known zeolites, such as AFR, SFO, ZON, OWE, etc. The structural relationships between these zeolites have been discussed.
Co-reporter:Xi Wang ; Yu Wang ; Qiong Liu ; Yi Li ; Jihong Yu ;Ruren Xu
Inorganic Chemistry 2012 Volume 51(Issue 8) pp:4779-4783
Publication Date(Web):March 28, 2012
DOI:10.1021/ic3005129
A family of novel 2D-layered lanthanide germanates K3[TbxEu1–xGe3O8(OH)2] (x = 1, 0.88, 0.67, 0; denoted as TbGeO-JU-87, Tb0.88Eu0.12GeO-JU-87, Tb0.67Eu0.33GeO-JU-87, and EuGeO-JU-87) were synthesized under mild hydrothermal conditions in a concentrated gel system. They are isostructural, as confirmed by the powder X-ray diffraction analysis. The single-crystal X-ray diffraction analysis of EuGeO-JU-87 reveals that it is a 2D-layered [EuGe3O8(OH)2]n3n– anionic framework, which is built up from GeO4H/GeO4 tetrahedra and EuO6 octahedra by sharing vertex O atoms. Charge neutrality is achieved by K+ ions located in the free void space. Interestingly, photoluminescence studies show that Tb0.88Eu0.12GeO-JU-87 and Tb0.67Eu0.33GeO-JU-87 exhibit a high Tb3+-to-Eu3+ energy-transfer efficiency and the TbxEu1–xGeO-JU-87 system displays tunable photoluminescent properties.
Co-reporter:Liqiu Tang, Xiaoyan Ren, A. Ken Inge, Tom Willhammar, Daniel Grüner, Jihong Yu, and Xiaodong Zou
Crystal Growth & Design 2012 Volume 12(Issue 7) pp:3714-3719
Publication Date(Web):June 22, 2012
DOI:10.1021/cg300519t
A novel open-framework silicogermanate SU-JU-14 (Stockholm University-Jilin University-Number 14), |NH3CH2CH2NH3|3[Ge6.40Si0.60O15(OH)]2[Ge0.73Si3.27O8], was synthesized by using ethylenediamine as the structure-directing agent under solvothermal conditions. Single-crystal structure analysis reveals that the crystal structure of SU-JU-14 consists of extended 24-ring channels built from [(Ge,Si)7O12O6/2(OH)]3– [(Ge,Si)7] clusters and unbranched zweier silica double chains [Ge0.73Si3.27O4O8/2]. Charge neutrality is achieved by diprotonated ethylenediamine guest molecules. The structure consists of stacking faults of layered arrays in two different configurations along the a-axis. SU-JU-14 was characterized by X-ray diffraction, X-ray energy dispersive spectroscopy, scanning electron microscopy, nuclear magnetic resonance, inductively coupled plasma, and thermogravimetric analyses. Crystallographic data: monoclinic, space group C2/c, and unit cell parameters: a = 35.625 (7) Å, b = 28.580 (6) Å, c = 10.403 (2) Å, and β = 98.30 (3)°.
Co-reporter:Xinguang Zhao;Tingting Yan;Kai Wang;Yan Yan;Bo Zou;Ruren Xu
European Journal of Inorganic Chemistry 2012 Volume 2012( Issue 15) pp:2527-2532
Publication Date(Web):
DOI:10.1002/ejic.201200200
Abstract
The europium germanate NaEu3(GeO4)2(OH)2 was prepared under mild hydrothermal conditions. In situ synchrotron X-ray diffraction analysis and photoluminescence spectroscopic measurement in a diamond anvil cell (DAC) under high pressure were performed to study its structural stability as well as the luminescent properties of the Eu3+ ions. The synchrotron X-ray diffraction analysis revealed that the structure of NaEu3(GeO4)2(OH)2 was stable under pressure that ranged from 1 atm to 20 GPa with only a little distortion, and the unit-cell compression occurred more readily along the a axis than along the c axis. When the pressure was reduced to ambient pressure, the distortion and the unit cell recovered to the original state. Photoluminescence spectroscopic studies under high pressure showed that the redshift of the 5D0 7FJ (J = 0, 1, 2) transitions and the pressure imposed on the sample had a good linear relationship. Also, the intensity of the red emission lines was independent of the pressure in the range from 9 to about 20 GPa.
Co-reporter:Kun Qian, Jiyang Li, Jiuxing Jiang, Zhiqiang Liang, Jihong Yu, Ruren Xu
Microporous and Mesoporous Materials 2012 Volume 164() pp:88-92
Publication Date(Web):1 December 2012
DOI:10.1016/j.micromeso.2012.06.036
The chiral zeolite germanosilicate ITQ-37 has been prepared by using a new achiral organic structure-directing agent 3′,4′-dihydro-1′H-spiro[isoindoline-2,2′-isoquinolin]-2-ium (denoted as OSDA-1). The crystallization field diagram and the influence of synthetic factors on the synthesis of ITQ-37, such as crystallization temperature, crystallization time, source materials, and water amount have been studied. The as-synthesized samples have been characterized by XRD, ICP, CHN, TG, TEM, DLS, NMR, N2 adsorption and NH3-TPD analysis. The results indicate that the as-synthesized ITQ-37 is a pure phase, and the particle size is of ca. 200 nm. The OSDA-1 cations remain intact in the final product and the framework structure of ITQ-37 maintains up to 500 °C after the removal of OSDA. In addition, Al atoms can be introduced into the framework of germanosilicate ITQ-37 with the Al/(Si + Ge) molar ratio of ca. 1/160–1/80, forming Al-ITQ-37 mainly with weak acid sites.Graphical abstractHighlights► ITQ-37 has been synthesized by using an achiral OSDA. ► The crystallization field diagram of ITQ-37 has been investigated. ► The influence of synthetic factors has been studied in detail. ► The particle size of as-prepared ITQ-37 is ca. 200 nm. ► Al atoms are introduced that leads to mainly weak acid sites.
Co-reporter:Xinguang Zhao;Kai Wang;Tingting Yan;Yan Yan;Bo Zou;Ruren Xu
Chinese Journal of Chemistry 2012 Volume 30( Issue 9) pp:2066-2072
Publication Date(Web):
DOI:10.1002/cjoc.201200583
Abstract
The crystalline solid europium germanate NaEuGeO4 was prepared under hydrothermal conditions. The in-situ photoluminescence spectroscopic measurement and the synchrotron X-ray diffraction analysis in a diamond anvil cell (DAC) under high pressure were performed to study the pressure-induced phase transition of NaEuGeO4 as well as changes of the luminescent properties of Eu3+ ions. Photoluminescence spectroscopic studies revealed that a phase transition occurred at a pressure range of 6.5–10 GPa and the high-pressure phase of NaEuGeO4 (NaEuGeO4-HP) was still stable when the pressure raised up to about 20 GPa. As the pressure was released, the spectra returned to the original state, revealing that the pressure-induced phase transition is a completely reversible process. The synchrotron X-ray diffraction analysis demonstrated that the structure of NaEuGeO4 transformed to an unidentified phase NaEuGeO4-HP at a pressure higher than 10 GPa, and the phase transition is reversible. This result is consisted with that obtained by photoluminescence spectra analysis.
Co-reporter:Xi Wang, Jiyang Li, Yide Han, Yi Li, Jihong Yu, and Ruren Xu
Chemistry of Materials 2011 Volume 23(Issue 11) pp:2842
Publication Date(Web):May 17, 2011
DOI:10.1021/cm200104t
Na8CeSi6O18 and Na8Ce0.73Ti0.27Si6O18 (denoted CeSiO-CJ11A and CeTiSiO-CJ11B, respectively) were the first successful examples of Ce4+ and Ce4+/Ti4+ mixed silicates synthesized under mild hydrothermal conditions at 503 K. Their isostructure is confirmed by the powder X-ray diffraction (XRD) analysis. The single-crystal XRD analysis of CeSiO-CJ11A reveals that its structure is comprised of [Si6O18]n12n– cyclosilicate anions that are linked via CeO6 octahedra, giving rise to a three-dimensional (3D) framework that contains 6-membered ring channels delimited by the SiO4 tetrahedra and CeO6 octahedra along the [101]-direction. Charge neutrality is achieved by Na+ ions located in the channels. Interestingly, the surface photovoltage (SPV) and transient photovoltage (TPV) studies of CeSiTiO-CJ11B show that it exhibits n-type semiconductor characteristics and a slow recombination process.Keywords: cerium; cyclosilicates; hydrothermal synthesis; photovoltaic property; titanium;
Co-reporter:Jiuxing Jiang, Yan Xu, Peng Cheng, Qiming Sun, Jihong Yu, Avelino Corma, and Ruren Xu
Chemistry of Materials 2011 Volume 23(Issue 21) pp:4709
Publication Date(Web):October 12, 2011
DOI:10.1021/cm201221z
Seven isoindoline-based organic structure directing agents (OSDAs) with increasing sizes have been prepared and each applied in a high throughput (HT) design of 33 × 5 experiments by varying the synthesis parameters such as Si/Ge, Al(B)/(Si+Ge), F–/(Si+Ge), and H2O/(Si+Ge). Among the 945 experiments, 395 lead to crystalline zeolite products, corresponding to eight zeolites, i.e., Beta (3D 12 × 12 × 12 ring), ITQ-7 (3D 12 × 12 × 12 ring), ITQ-17 (3D 12 × 12 × 12 ring), ITQ-15 (2D 14 × 12 ring), ITQ-21 (3D 12 × 12 × 12 ring), ITQ-37(3D 30 ring), ITQ-43 (3D 28 × 12 × 12 ring), and ITQ-44 (3D 18 × 12 × 12 ring). Most of the crystalline phases obtained (85.8%, 339 of 395) are Beta, ITQ-7, ITQ-17, and intergrowths of ITQ-7 and ITQ-17, which have been named as “Default Structures” here. It has been found that concentrated gels and high Ge/Si ratio favor the formation of low framework density structures. When the OSDAs are relatively small, only “Default Structures” can be obtained, while if the size of OSDA increases above a certain dimension, extra-large pore zeolites such as ITQ-15, ITQ-37, ITQ-44, and ITQ-43 start to appear. The mesoporous chiral zeolite ITQ-37 has been successfully synthesized here with a much less costly achiral template than the one used originally. It has also been found that there is an intergrowth of ITQ-7 and ITQ-17 due to their closely correlated structures.Keywords: extra-large pore; high throughput; synthesis; template; zeolite;
Co-reporter:Jiancheng Di, Yong Zhao and Jihong Yu
Journal of Materials Chemistry A 2011 vol. 21(Issue 24) pp:8511-8520
Publication Date(Web):28 Apr 2011
DOI:10.1039/C1JM10512D
Molecular sieves, such as zeolites and mesoporous materials, have been widely used in the fields of catalysis, adsorption, ion-exchange, and are finding new applications in optics, electronics, magnetism, medicine, etc. Molecular sieves with different morphologies or aggregation states, such as spheres, films, and fibers have been prepared to fulfil the need for various applications. Electrospinning offers a simple and straightforward way for generating ultrafine fibers with diameter in the range of nanometres to micrometres from a variety of materials. In recent decades, electrospinning has been introduced to prepare molecular sieve fibers. In this review, fibrous molecular sieves including zeolite fibers, siliceous and nonsiliceous mesoporous fibers prepared by electrospinning are summarized, and their prominent applications in optics, adsorptions, catalysis, etc. are highlighted.
Co-reporter:Dongdong Li, Jihong Yu and Ruren Xu
Chemical Communications 2011 vol. 47(Issue 39) pp:11077-11079
Publication Date(Web):06 Sep 2011
DOI:10.1039/C1CC14064G
An aggregation-induced emission (AIE) luminogen, tetraphenylethene, has been successfully grafted onto mesoporous silica SBA-15 for the first time. The materials emit blue light upon UV irradiation, and are photostable for the ibuprofen (IBU) drug loading and release process, indicating their great potential for biomedical applications.
Co-reporter:Tan Su ; Hongzhu Xing ; Jin Xu ; Jihong Yu ;Ruren Xu
Inorganic Chemistry 2011 Volume 50(Issue 3) pp:1073-1078
Publication Date(Web):January 4, 2011
DOI:10.1021/ic101713y
Three new open-framework metal borophosphates, [Na6Co3B2P5O21Cl]·H2O (JIS-4), K5Mn2B2P5O19(OH)2 (JIS-5), (NH4)8[Co2B4P8O30(OH)4] (JIS-6), have been prepared under ionothermal conditions using ionic liquid 1-ethyl-3-methylimidazolium ([Emim]Br) as the solvent. They are the first examples of metalloborophosphate prepared by the ionothermal method. Their structures are determined by single-crystal X-ray diffraction. The 3-D open framework of JIS-4 is made of CoO5Cl octahedra, CoO5 square pyramids, and PO4 and BO4 tetrahedra forming 12-ring channels along the [010] direction. It is noted that JIS-4 is the first 3-D open-framework structure in the family of borophosphate with the B/P ratio of 2/5, which features a borophosphate cluster anionic partial structure. Such cluster anionic partial structures connect with MnO6 octahedra and MnO5 trigonal bipyramids resulting in the formation of the 2-D layer structure of JIS-5 with the same B/P ratio as JIS-4. The 2-D layer structure of JIS-6 belongs to the largest family of borophosphate with a B/P ratio of 1/2 which features a unique 1-D chain anionic partial structure. Crystal data for JIS-4, orthorhombic, Pnma, a = 14.0638(8) Å, b = 9.8813(7) Å, c = 14.0008(10) Å, V = 1945.7(2) Å3, and Z = 2; for JIS-5, monoclinic, P21/n, a = 14.4939(3) Å, b = 9.2539(3) Å, c = 14.8031(4) Å, β = 101.4600(10)°, V = 1945.88(9) Å3, and Z = 4. For JIS-6, triclinic, P1, a = 9.6928(3) Å, b = 9.8747(3) Å, c = 10.0125(2) Å, α = 62.057(2)°, β = 82.456(2)°, γ = 76.095(2)°, V = 821.60(4) Å3, and Z = 1.
Co-reporter:Weiting Yang, Jiyang Li, Tianyi Na, Jin Xu, Lei Wang, Jihong Yu and Ruren Xu
Dalton Transactions 2011 vol. 40(Issue 11) pp:2549-2554
Publication Date(Web):04 Feb 2011
DOI:10.1039/C0DT01475C
A new three-dimensional (3-D) open-framework manganese borophosphate, (NH4)6[Mn3B6P9O36(OH)3]·4H2O (denoted as MnBPO-CJ31), has been synthesized by using boric acid flux method. Its anionic framework structure is constructed by the connection of MnO6 octahedra and BO4, PO4 and PO3(OH) tetrahedra. It contains 12-ring channels along the [001] direction with a pore diameter of 7.1 Å. It is the first borophosphate featuring a 3-D anionic partial structure with a B/P ratio of 2/3 and an unprecedented fifteen mer tetrahedral fundamental building unit (FBU) [B6P9O36(OH)3] exists in this compound. NH4+ ions locate in the void space to balance the negative charge of the inorganic framework. The compound is further characterized by powder XRD, ICP, CHN, TGA and IR analyses. Magnetic study reveals that MnBPO-CJ31 shows interesting canted antiferromagnetic behaviour at low temperature.
Co-reporter:Yanan Guo, Xiaowei Song, Jiyang Li, Yi Li, Yide Han, Jihong Yu and Ruren Xu
Dalton Transactions 2011 vol. 40(Issue 36) pp:9289-9294
Publication Date(Web):11 Aug 2011
DOI:10.1039/C1DT10430F
Two heteroatom-containing open-framework aluminophosphates, (C3H4N2)2FeAl3P4O16 and (C3H4N2)2CrAl3P4O16 (denoted as MAPO-CJ50, M = Fe, Cr), have been synthesized by using imidazole as the template under solvothermal conditions. The structure of FeAPO-CJ50 is determined by single-crystal X-ray diffraction, and its analogous structure CrAPO-CJ50 is identified by powder X-ray diffraction. The 3-dimensional framework of MAPO-CJ50, constructed by MO4N2 octahedra, AlO4 tetrahedra, and PO4 tetrahedra, contains interconnecting 10- and 8-ring channels. Imidazole molecules are coordinated with framework M3+ ions and interact with each other through π–π stacking interactions in the channels. These two compounds show photoluminescent properties due to ligand-to-metal charge transfer. Magnetic measurements reveal that there are antiferromagnetic interactions between M3+ ions in the frameworks of FeAPO-CJ50 and CrAPO-CJ50.
Co-reporter:Jincheng Wang, Zhuopeng Wang, Song Guo, Jingyu Zhang, Yang Song, Xiaoming Dong, Xiaonan Wang, Jihong Yu
Microporous and Mesoporous Materials 2011 Volume 146(1–3) pp:216-222
Publication Date(Web):December 2011
DOI:10.1016/j.micromeso.2011.04.005
To reduce the incidence of peri-implant infections, zeolite coatings on titanium alloy surface have been prepared and their antibacterial as well as anti-adhesive properties were studied. Continuous zeolite A thin films of 1–4 μm thickness were coated onto titanium alloy surface through in situ crystallization method under hydrothermal conditions. Small amount of silver ions (ca. 2 wt.%) was incorporated into the zeolite layer by an ion-exchange process to provide antibacterial activity. X-ray powder diffraction (XRPD), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), contact angle measurement and scratch test were employed to characterize the coating surfaces. The antibacterial activity of silver incorporated zeolite coatings against methicillin-resistant Staphylococcus aureus (MRSA) evaluated in vitro showed that bacterial proliferation was significantly inhibited both in the culture medium surrounding the material and on the material surface. Moreover, the superhydrophilic nature of zeolite coating provides additional anti-adhesive property to the material surface. The results of in vitro cytotoxic assessment showed that both the zeolite coatings and silver-containing zeolite coatings have good biocompatibility. The antibacterial and anti-adhesive zeolite coatings will have potential application in orthopedic implants.Graphical abstractWe report a silver-exchanged zeolite coating on titanium alloy surface, and demonstrate that its excellent antibacterial and anti-adhesive properties can be of utility to reduce implant-associated infections.Highlights► An Ag-zeolite coating on titanium alloy surface was prepared. ► The antibacterial activity of Ag-zeolite coatings for orthopedic use was evaluated. ► The Ag-containing zeolite coatings exhibit excellent antibacterial activities. ► Both the zeolite coatings and Ag-zeolite coatings have good biocompatibility.
Co-reporter:Jiancheng Di, Cong Zhang, Wenfu Yan, Xiaofang Wang, Jihong Yu, Ruren Xu
Microporous and Mesoporous Materials 2011 Volume 145(1–3) pp:104-107
Publication Date(Web):November 2011
DOI:10.1016/j.micromeso.2011.04.032
A new method for the fabrication of highly b-oriented silicalite-1 films is presented. With this method, the surface of the substrate of glass slides was modified with different surface coverage of Ti–OH groups by a surface sol–gel process, which enables layer-by-layer coating of a selected metal oxide on a hydroxyl-terminated surface. The modification of the glass substrate by the TiO2 layers greatly increased the density and the reactivity of the surface hydroxyl groups. After the insitu growth under normal synthetic conditions, highly b-oriented zeolite thin films were obtained. The resulting highly b-oriented zeolite thin films were further characterized by powder X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and scanning electron microscope (SEM). This method offers a general, facile, and straightforward approach to the preparation of various zeolite films under normal synthetic conditions.Graphical abstractHighlights► The surface sol–gel chemistry is introduced into the synthesis and preparation of zeolite films for the first time. ► The density and reactivity of the surface hydroxyl groups of substrate are greatly increased. ► The b-oriented silicalite-1 films were prepared on surface sol–gel process modified substrate via in situ crystallization. ► This method offers a straightforward approach to the preparation of various zeolite films under normal synthetic conditions.
Co-reporter:Weiting Yang, Jiyang Li, Jin Xu, Hongzhu Xing, Lei Wang, Jihong Yu, Ruren Xu
Solid State Sciences 2011 Volume 13(Issue 4) pp:757-761
Publication Date(Web):April 2011
DOI:10.1016/j.solidstatesciences.2010.04.007
Three new isostructural organo-templated transition metal borophosphates, (C3H12N2)[MnB2P3O12(OH)] (denoted MnBPO-CJ30), (C3H12N2)[FeB2P3O12(OH)] (denoted FeBPO-CJ30A) and (C4H12N2)[FeB2P3O12(OH)] (denoted FeBPO-CJ30B) were hydrothermally synthesized by using 1,2-diaminopropane and piperazine as the template, respectively. Single-crystal X-ray diffraction analyses reveal that the framework of MBPO-CJ30 (M = Mn, Fe) is constructed from the connection of infinite loop-branched borophosphate [B2P3O12(OH)4−] chains and MO6 octahedra, giving rise to three-dimensional (3-D) intersecting 8-, 8- and 9-ring channels along the [011], [011¯] and [100] directions, respectively. The negative charge of the framework is compensated by the diprotonated 1,2-diaminopropane or piperazine cations located in the 9-ring channels. These compounds are further characterized by powder X-ray diffraction, ICP, CHN, TGA, IR, and magnetic measurement. Structural analyses reveal that the organic amines that have the similar structure-directing ability but differing in size and shape have an influence on the crystal symmetry as well as the pore shapes of the 9-ring channels of these isostructures. Magnetic studies reveal that MnBPO-CJ30 exhibit antiferromagnetic behavior with weak ferromagnetic component to the magnetic interactions.
Co-reporter:Yide Han;Dr. Yi Li; Jihong Yu; Ruren Xu
Angewandte Chemie 2011 Volume 123( Issue 13) pp:3059-3061
Publication Date(Web):
DOI:10.1002/ange.201006500
Co-reporter:Yide Han;Dr. Yi Li; Jihong Yu; Ruren Xu
Angewandte Chemie International Edition 2011 Volume 50( Issue 13) pp:3003-3005
Publication Date(Web):
DOI:10.1002/anie.201006500
Co-reporter:Jihong Yu and Ruren Xu
Accounts of Chemical Research 2010 Volume 43(Issue 9) pp:1195
Publication Date(Web):June 24, 2010
DOI:10.1021/ar900293m
Since the first synthesis of zeolites in 1940s, these materials and related inorganic open-framework materials with regular nanoporous space have attracted considerable interest. Zeolites are important for catalysis, adsorption, and ion-exchange, and researchers are finding new applications for these materials in optics, electronics, sensors, and medicine. In particular, the petrochemical industry is interested in the synthesis of new zeolite catalysts with high catalytic activity and selectivity. Using hydrothermal, solvothermal, and the recently-developed ionothermal methods, researchers have prepared 194 types of zeolites and thousands of zeolite-related inorganic open-framework materials. However, their syntheses are based primarily on an empirical “trial-and-error” method. The rational synthesis of zeolitic inorganic open-framework materials, while targeting novel structures and functions, remains a formidable task. The challenge in rational synthesis lies in the unknown mechanism for their formation: the relationship between the synthetic parameters and structural characteristics of the products is not clear. In an effort to overcome these challenges, our group has built up a ZEOBANK, a database of zeolite structures and a database for their synthesis. ZEOBANK allows us to use data mining to find new methods for guiding the synthesis of zeolitic materials. In this Account, we describe our efforts to rationally synthesize zeolitic inorganic open-framework materials with desired structures and present computational methods for the design of these structures. In particular, we focus on the design of zeolites with desired pore geometries through constrained assembly of atoms around the predefined channels in the unit cell. Our approaches toward rational synthesis include the use of template to direct the structure, the use of heteroatoms as a framework substituent, and the use of computational data mining. Employing these strategies, we have developed innovative methods toward the synthesis of target structures with specific channel structures, such as extra-large pores and chiral channels. We expect that further data mining will increase the synthetic control for researchers interested in designing functional zeolitic materials.
Co-reporter:Xinguang Zhao ; Jiyang Li ; Peng Chen ; Yi Li ; Qingxin Chu ; Xiaoyang Liu ; Jihong Yu ;Ruren Xu
Inorganic Chemistry 2010 Volume 49(Issue 21) pp:9833-9838
Publication Date(Web):September 30, 2010
DOI:10.1021/ic1006154
Three new lanthanide silicates K1.25Gd1.25Si2.5O7.5 (denoted as GdSiO-CJ7), Cs3TbSi8O19·2H2O (denoted as TbSiO-CJ8), and Cs3DySi6O15 (denoted as DySiO-CJ9) were synthesized by using a high-temperature and high-pressure hydrothermal method. Their structures determined by single-crystal X-ray diffraction revealed anionic silicate chain, layer and framework, which are further connected with LnOn polyhedra to form novel lanthanide silicate frameworks. The structure of GdSiO-CJ7 consists of unbranched silicate chains [Si5O15]10- extending along the b axis, which are linked together by edge-sharing linked GdO6 and GdO8 chains along the c axis to form a 3-D framework with two types of 10-ring channels along the [010] and [001] directions, respectively. The structure of TbSiO-CJ8 consists of double 4,8-net sheets [Si8O19]6- built up from SiO4 tetrahedra, which are linked together via TbO6 octahedra to form a 3-D framework with 8-ring channels along the [100] and [010] directions. The structure of DySiO-CJ9 is based on a 3-D silicate framework [Si6O15]6- with 6-rings, where DyO6 octahedra are located between two adjacent 6-rings and connected with six Si atoms via O atoms. The photoluminescence photoluminescence properties of TbSiO-CJ8 and EuSiO-CJ8 were investigated.
Co-reporter:Hongzhu Xing, Yi Li, Tan Su, Jin Xu, Weiting Yang, Enbo Zhu, Jihong Yu and Ruren Xu
Dalton Transactions 2010 vol. 39(Issue 7) pp:1713-1715
Publication Date(Web):06 Jan 2010
DOI:10.1039/B919933K
We present the spontaneous crystallization of a new chiral open-framework borophosphate in an ionothermal system. Its structure contains a three-dimensional (3D) anionic framework with intersecting 12-ring channels formed by interweaving helical chains.
Co-reporter:Jiyang Li, Miao Qi, Jun Kong, Jianzhong Wang, Yan Yan, Weifeng Huo, Jihong Yu, Ruren Xu, Ying Xu
Microporous and Mesoporous Materials 2010 Volume 129(1–2) pp:251-255
Publication Date(Web):1 April 2010
DOI:10.1016/j.micromeso.2009.10.001
A better understanding of the relationship between the synthetic factors and the resulting structures is of great importance to rationalizing the synthesis of the target zeolitic materials. We present a computational study for predicting the formation of (6,12)-ring-containing microporous aluminophosphates (AlPOs), using a data classification approach. Through analyses of a database of AlPO synthesis with ca. 1600 reaction data, we identified a number of synthetic parameters such as three gel molar ratios of Al2O3, P2O5 and the organic amine template, as well as eleven parameters associated with the geometric and electronic characteristics of the templates deemed to be useful in distinguishing (6,12)-ring-containing AlPOs from the other AlPOs. Using these parameters, we have trained a support vector machine (SVM)-based classifier on a training dataset containing 360 (6,12)-ring-containing AlPOs and 1069 AlPOs without such rings. Analysis results revealed that the geometric size of the organic template, particularly the second longest distance of the template along with the gel molar ratios, has good predictive power for microporous aluminophosphates containing (6,12)-rings. This work demonstrates the general feasibility in establishing a relationship between the synthetic parameters and the structural features of the synthesized microporous materials, providing a useful guidance to the rational design and synthesis of such materials as well as other inorganic crystalline materials.
Co-reporter:Xi Wang, Jiyang Li, Guangmei Wang, Yide Han, Tan Su, Yi Li, Jihong Yu, Ruren Xu
Solid State Sciences 2010 Volume 12(Issue 4) pp:422-427
Publication Date(Web):April 2010
DOI:10.1016/j.solidstatesciences.2009.04.005
A family of microporous lanthanide silicates, K8Ln3Si12O32NO3·H2O (denoted LnSiO-CJ3, Ln = Eu, Tb, Gd, Sm), was synthesized under mild hydrothermal conditions at 503 K. The X-ray powder diffraction patterns of these compounds reveal that they are isostructural. The structure of EuSiO-CJ3 was determined by single-crystal X-ray diffraction analysis. It crystallizes in triclinic space group P-1 (No. 2) with a = 11.599(2) Å, b = 12.225(2) Å, c = 13.829(3) Å, α = 112.99(3)°, β = 92.05(3)°, γ = 90.57(3)°. The structure is based on [Si3O8]n4n− layers with 6-, 8-, 12-rings that are connected by EuO6 octahedra to form a 3-D framework with 8-ring channels along the [001] direction. Charge neutrality is achieved by the K+ and NO3− ions located in the channels. The framework of EuSiO-CJ3 shows good thermal stability, which can be stable up to 1273 K. Ion-exchange capacity of EuSiO-CJ3 was investigated by the exchange of NO3− ions with halide ions (F−, Cl−, Br−). The peaks in the emission spectra of LnSiO-CJ3 (Ln = Eu, Tb) belong to the characteristic transitions of Ln3+ (Ln = Eu, Tb) respectively. The lifetime measurements of LnSiO-CJ3 (Ln = Eu, Tb) suggest the presence of three Ln3+ (Ln = Eu, Tb) environments, which are consistent with the crystallographic results.A family of microporous lanthanide silicates: K8Ln3Si12O32NO3·H2O (Ln = Eu, Tb, Gd, Sm) was prepared under mild hydrothermal conditions at 503 K. Their structures are isostructural, consisting of [Si3O8]n4n− layers connected by EuO6 octahedra to form a 3-D framework with 8-ring channels along the [001] direction. The K+ and NO3−-ions are located in the void space. The compounds show good thermal stability, ion-exchange capacity and photoluminescent properties.
Co-reporter:Song Lin;Jiyang Li;Raj Pal Sharma;Ruren Xu
Topics in Catalysis 2010 Volume 53( Issue 19-20) pp:1304-1310
Publication Date(Web):2010 December
DOI:10.1007/s11244-010-9588-3
The crystal size and shape of the silicoaluminophosphate molecular sieve SAPO-34 have been effectively controlled in the reaction system of Al2O3–P2O5–SiO2–TEAOH–H2O under microwave radiations. Nano sheet-like SAPO-34 crystals are obtained when using colloidal silica as the silica source. When TEOS is used as the source of silica, homogeneous SAPO-34 crystals with a particle size of about 100 nm are formed, and the morphology of the crystals changes from uniform nano particles (~100 nm) to microspheres (~1.5 μm) by varying the H2O/Al2O3 molar ratio. To further investigate the morphology control of SAPO-34, the synthetic factors, such as the silica source, water content, crystallization time and aging time have been studied in detail.
Co-reporter:FangZheng Duan;JiYang Li;Wei Sun;Peng Chen
Science China Chemistry 2010 Volume 53( Issue 10) pp:2159-2163
Publication Date(Web):2010 October
DOI:10.1007/s11426-010-4100-2
A new aluminophosphate [Cu(en)2]0.5[Al3P3O12(OH)] (denoted as AlPO-CJ53; en = ethylenediamine) with zeotype AWO topology has been synthesized under hydrothermal conditions in which the self-assembled Cu(en)22+ cations in the reaction system act as the template. AlPO-CJ53 crystallizes in the monoclinic space group P21/n (No. 14) with a = 0.85547(11) nm, b = 1.7671(2) nm, c = 0.90500(12) nm, β = 107.725(2)°, V = 1.3031(3) nm3. Its framework consists of AlO4(OH)/AlO4 and PO4 units forming 8-ring channels along the c direction, where the copper complex cations Cu(en)22+ are located to neutralize the negative charges of the framework. AlPO-CJ53 transforms to AlPO4-25 with zeotype ATV upon calcination at 400 °C.
Co-reporter:Hongzhu Xing;Weiting Yang;Tan Su;Yi Li Dr.;Jin Xu;Takehito Nakano ;Ruren Xu
Angewandte Chemie International Edition 2010 Volume 49( Issue 13) pp:2328-2331
Publication Date(Web):
DOI:10.1002/anie.200906471
Co-reporter:Xiaoyan Ren ; Yi Li ; Qinhe Pan ; Jihong Yu ; Ruren Xu ;Ying Xu
Journal of the American Chemical Society 2009 Volume 131(Issue 40) pp:14128-14129
Publication Date(Web):May 28, 2009
DOI:10.1021/ja902413j
A novel germanate |C6N2H18|30[Ge9O18X4]6[Ge7O14X3]4[Ge7O14.42X2.58]8[GeX2]1.73 (X = OH, F) with 30-ring channels built from Ge7O14X3 (Ge7) and Ge9O18X4 (Ge9) clusters was obtained under solvothermal conditions. It has a mesoporous pore of 13.0 × 21.4 Å2, which represents the largest pore ring found in crystalline open-framework materials. The framework can be described as a 3-D net structure and viewed as introducing Ge7 and Ge9 clusters into the 4,8-heterocoordinated csq net.
Co-reporter:Weiting Yang, Jiyang Li, Qinhe Pan, Hongzhu Xing, Yan Chen, Jihong Yu and Ruren Xu
Journal of Materials Chemistry A 2009 vol. 19(Issue 26) pp:4523-4528
Publication Date(Web):15 May 2009
DOI:10.1039/B820130G
A new layered iron borophosphate (C4N3H16)(C4N3H15)0.5[Fe2B4P7O26(OH)4] (denoted FeBPO-CJ28), with a novel B/P ratio of 4/7 and mixed-valent iron(II, III) was prepared under mild hydrothermal conditions in the presence of diethylenetriamine (DETA) as the template. Its crystal structure was determined by single-crystal X-ray diffraction (triclinic, P (No. 2), a = 8.9568(3) Å, b = 9.8717(3) Å, c = 17.9905(5) Å, α = 102.510(2)°, β = 92.343(2)°, γ = 100.403(2)°, V = 1522.10(8) Å3, and Z = 2). The structure comprises unprecedented anionic double layers 2∞{[Fe2B4P7O26(OH)4]4−} with one-dimensional 8-ring channels along the [110] direction, which are made up of FeO6, BO4, PO4 and HPO4 polyhedral units. Such double layers parallel to the ab plane are connected by inter-layer hydrogen bonds forming the three-dimensional (3D) supramolecular open framework with pseudo 10-ring channels along the [110] direction. Protonated DETA cations locate in the 8-ring channels and pseudo 10-ring channels to compensate the negative charge of the anionic framework. The structure is featured by a new fundamental building unit (FBU) [B4P7O26(OH)4], which is the largest one of the borophosphate anionic partial structures. The compound is further characterized by powder XRD, ICP, CHN, TGA and Mössbauer spectroscopy analysis. The magnetic measurement reveals that FeBPO-CJ28 exhibits ferrimagnetic behavior below 9.6 K with a hysteresis loop at 2 K (HC = 2800 Oe, MR = 0.21 µB).
Co-reporter:Xiaowei Song, Jiyang Li, Yanan Guo, Qinhe Pan, Lin Gan, Jihong Yu and Ruren Xu
Inorganic Chemistry 2009 Volume 48(Issue 1) pp:198-203
Publication Date(Web):November 12, 2008
DOI:10.1021/ic801405e
Three transitional-metal-substituted aluminophosphate molecular sieves, |(C3N2H5)8|[M8Al16P24O96] (denoted MAPO-LAU, M = Co, Mn, Zn), have been synthesized under solvothermal conditions in the presence of imidazole as the structure-directing agent. Their structures are determined by single-crystal X-ray diffraction and further characterized by powder X-ray diffraction, inductively coupled plasma, thermogravimetric, and diffuse reflectance spectroscopy (UV−vis) analyses. The structure of MAPO-LAU is based on the strict alternation of MO4/AlO4 tetrahedra and PO4 tetrahedra through vertex oxygen atoms. Their frameworks are analogous to the zeotype LAU structure in which 33% of the aluminum sites are replaced by transitional-metal ions. The protonated imidazole cations resided in the 10-ring channels. These compounds show photoluminescent properties due to the existence of imidazole molecules in the structures. Magnetic measurements reveal that there is very weak antiferromagnetic interaction among the metal centers of MnAPO-LAU.
Co-reporter:Dayong Tian, Wenfu Yan, Zhouxiang Wang, Yanyan Wang, Zhibin Li, Jihong Yu and Ruren Xu
Crystal Growth & Design 2009 Volume 9(Issue 3) pp:1411
Publication Date(Web):January 12, 2009
DOI:10.1021/cg800683m
The core−shell molecular sieve composite comprised of Cr3+ substituted AlPO4-5 (Cr-AFI) as core and Ti4+ substituted AlPO4-5 (Ti-AFI) as shell was prepared via solvothermal epitaxial growth. The presynthesized tabletlike Cr-AFI crystals were dispersed in the reaction system of Al(OPri)3-H3PO4-TEA-(C4H9O)4Ti-H2O-pEG (polyethylene glycol) followed by solvothermal treatment at 170 °C. The sheetlike Ti-AFI microcrystals were epitaxially grown on the surface of the presynthesized tabletlike Cr-AFI core crystals. The growth process of the Ti-AFI microcrystals on the surface of core of Cr-AFI crystal was studied in detail by scanning electron microscopy characterization. The results demonstrate that the Ti-AFI microcrystals nucleate preferentially on the (100) basal face of the Cr-AFI core crystals. The N2 adsorption analysis shows that the channel systems of the core and shell have good communication, which may provide a good mass transport pathway for the catalytic reaction. The core−shell composite of Ti-/Cr-AFI makes it possible to combine two catalytic sites in one catalyst, which may benefit some special catalysis reactions.
Co-reporter:Xiaoxin Chen, Wenfu Yan, Xuejing Cao, Jihong Yu, Ruren Xu
Microporous and Mesoporous Materials 2009 Volume 119(1–3) pp:217-222
Publication Date(Web):1 March 2009
DOI:10.1016/j.micromeso.2008.10.015
A new method was developed to finely tune the aspect ratios of silicalite-1 (Si-MFI) crystals. This method involved the utilization of co-solvent of diols and the microwave heating of a reaction system of TEOS–TPAOH–H2O–Diol with the molar ratio of SiO2:TPAOH:EtOH:Diol:H2O = 1.0:0.357:4.0:x:y, where x = 6–9, y = 21.55–45.55. The diols included the ethylene glycol (EG), diethylene glycol (DEG), triethylene glycol (TEG), and tetraethylene glycol (tEG). Under microwave radiation the Si-MFI crystals with tunable sizes, shapes, and aspect ratios were crystallized. An excellent linear correlation between the aspect ratio of the Si-MFI crystals and the “concentration” of the C/OH, denoted as CC/OH, where C/OH is the ratio of the number of carbon and hydroxyl of the diols of the co-solvent, was observed. On the basis of this linear relationship, the aspect ratios of the well defined Si-MFI crystals could be effectively tuned. The possible mechanism on how the co-solvent of diols affects the growth kinetics of the Si-MFI crystals is discussed. The resulting products were further characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM).
Co-reporter:Fangzheng Duan, Jiyang Li, Peng Chen, Jihong Yu, Ruren Xu
Microporous and Mesoporous Materials 2009 Volume 126(1–2) pp:26-31
Publication Date(Web):November 2009
DOI:10.1016/j.micromeso.2009.05.015
In an attempt to synthesize microporous materials with respect to green chemistry, we investigate the syntheses of cobalt-substituted aluminophosphate molecular sieves by a low-cost approach through recycling waste mother-liquors of two layered aluminophosphates Mu-4 and AlPO-IM prepared in the Al(iPrO)3–H3PO4–Tem–TEG system (Tem: diethylamine or imidazole, TEG: triethylene glycol). A Co-substituted aluminophosphate [C8H24N2][Al8Co2P10O40] (denoted CoAPO-CJ51) was obtained with the addition of Co2+ ions into the mother-liquor of Mu-4. Its structure is analogous to zeotype GIS with 20% occupancy by Co2+ ions in the metal site, and the protonated diethylamine molecules are located in the 8-ring channels. Co-substituted aluminophosphate [C3H5N2][Al2CoP3O12] (denoted CoAPO-CJ52) was obtained with the addition of Co2+ ions into the mother-liquor of AlPO-IM. Its structure is analogous to zeotype LAU with 33.3% occupancy by Co2+ ions in the metal site, and the protonated imidazole molecules are located in the 10-ring channels. Both compounds are characterized by single-crystal X-ray diffraction analysis, ICP and TG analyses.
Co-reporter:Xiaowei Song;Yi Li Dr.;Lin Gan;Zhuopeng Wang, ;Ruren Xu
Angewandte Chemie International Edition 2009 Volume 48( Issue 2) pp:314-317
Publication Date(Web):
DOI:10.1002/anie.200803578
Co-reporter:Xiaowei Song;Yi Li Dr.;Lin Gan;Zhuopeng Wang, ;Ruren Xu
Angewandte Chemie 2009 Volume 121( Issue 2) pp:320-323
Publication Date(Web):
DOI:10.1002/ange.200803578
Co-reporter:Jianan Zhang, Zhen Ma, Jian Jiao, Hongfeng Yin, Wenfu Yan, Edward W. Hagaman, Jihong Yu and Sheng Dai
Langmuir 2009 Volume 25(Issue 21) pp:12541-12549
Publication Date(Web):July 14, 2009
DOI:10.1021/la9017486
Metal phosphates have many applications in catalysis, separation, and proton conduction, but their small surface areas and/or constrained pore structures limit their utilization. Here, we report two new methods for the liquid-phase grafting of titanium phosphate onto mesoporous silica (SBA-15) surfaces: (1) alternate grafting of Ti(OPri)4 and then POCl3 and (2) one-pot grafting of titanium phosphate formed in situ by employing Ti(OPri)4 (a base) and POCl3 (an acid) as an appropriate “acid−base pair”. Both the size of mesopores and the content of titanium phosphate can be changed by increasing the number of modification cycles in a stepwise (or layer-by-layer) fashion. The obtained products were characterized by inductively coupled plasma optical emission spectroscopy, X-ray diffraction, N2 adsorption−desorption, transmission electron microscopy, 31P and 29Si magic-angle spinning NMR, and NH3 temperature-programmed desorption, and their performance in acid catalysis and metal ion adsorption was investigated. This work provides new methodologies for the general synthesis of supported metal phosphates with large surface areas, ordered nanoporous structures, and acid properties.
Co-reporter:Lang Zhao, Jiyang Li, Peng Chen, Guanghua Li, Jihong Yu and Ruren Xu
Chemistry of Materials 2008 Volume 20(Issue 1) pp:17
Publication Date(Web):December 8, 2007
DOI:10.1021/cm7021906
Co-reporter:Qinhe Pan, Jiyang Li, Xiaoyan Ren, Zhuopeng Wang, Guanghua Li, Jihong Yu and Ruren Xu
Chemistry of Materials 2008 Volume 20(Issue 2) pp:370
Publication Date(Web):January 15, 2008
DOI:10.1021/cm702439v
Co-reporter:Dayong Tian, Wenfu Yan, Xuejing Cao, Jihong Yu and Ruren Xu
Chemistry of Materials 2008 Volume 20(Issue 6) pp:2160
Publication Date(Web):March 4, 2008
DOI:10.1021/cm703317c
In this work, poly ethylene glycol (pEG) was used as a cosolvent to control the morphology of transition metal substituted aluminophosphate molecular sieve AlPO4-5 (AFI) crystals in the solvothermal reaction system of Al(OPri)3-H3PO4-TEA-Me-H2O-pEG (Me = Cr, Ti, Fe, V). In the presence of pEG molecules, the growth rate of the Me-AFI crystals along c-direction was significantly inhibited. With the increase of the volume ratio of pEG/H2O, the aspect ratio of hexagonal prismlike Cr-AFI crystals was gradually decreased and the tabletlike crystals were obtained. Further increasing the volume ratio of pEG/H2O resulted in the novel flowerlike morphology for Cr3+- and Fe3+-substituted AFI crystals and kiwi-fruit-like morphology for Ti4+ and V5+ substituted AFI crystals. Our studies revealed that the existence of pEG molecules and the isomorphic substitution of Al or P are important for the formation of these specific morphologies.
Co-reporter:Jiancheng Di, Hongyan Chen, Xiaofang Wang, Yong Zhao, Lei Jiang, Jihong Yu and Ruren Xu
Chemistry of Materials 2008 Volume 20(Issue 11) pp:3543
Publication Date(Web):May 9, 2008
DOI:10.1021/cm8006809
Co-reporter:Hongzhu Xing, Jiyang Li, Wenfu Yan, Peng Chen, Zhao Jin, Jihong Yu, Sheng Dai and Ruren Xu
Chemistry of Materials 2008 Volume 20(Issue 13) pp:4179
Publication Date(Web):June 4, 2008
DOI:10.1021/cm800701x
Co-reporter:Weiting Yang, Jiyang Li, Qinhe Pan, Zhao Jin, Jihong Yu and Ruren Xu
Chemistry of Materials 2008 Volume 20(Issue 15) pp:4900
Publication Date(Web):July 1, 2008
DOI:10.1021/cm8000283
A new three-dimensional (3-D) open-framework vanadium (IV) borophosphate, Na2[VB3P2O12(OH)]·2.92H2O (denoted as VBPO-CJ27), has been synthesized by using boric acid flux method. Single-crystal structure analysis reveals that its structure is constructed by the connection of VO6 octahedra, PO4 and BO4 tetrahedra, and BO2(OH) trigonal planes to form a 3-D anionic framework containing intersecting 8-, 12-, and 16-ring channels. Charge neutrality is achieved by Na+ ions, and the guest water molecules locate in the void space of the open framework. To the best of our knowledge, it is the first borophosphate with extra-large 16-ring openings. Interestingly, its structure features unprecedented 128166 super cavities. The compound is further characterized by SEM, powder XRD, ICP, TGA, and IR analyses. Its magnetic property and ion-exchange capacity are also studied. The magnetic measurement reveals that VBPO-CJ27 is paramagnetic. Ion-exchange studies show that Na+ ions can be partially exchanged by NH4+ ions.
Co-reporter:Jihong Yu and Ruren Xu
Journal of Materials Chemistry A 2008 vol. 18(Issue 34) pp:4021-4030
Publication Date(Web):17 Jun 2008
DOI:10.1039/B804136A
Chiral zeolitic materials are of both fundamental and practical interest because they can combine both shape selectivity and enantioselectivity, which are desirable for asymmetric catalysis and separation. However, the synthesis of such materials remains a significant challenge in the field of zeolite science. This feature article will focus on a family of four-connected zeolite frameworks and related inorganic open frameworks with fascinating chiral structural features, aiming to provide an insight into the origin of chirality in these structures. Some approaches to the design of chiral zeolite frameworks, as well as synthesis routes and challenges to the chiral zeolitic materials are also discussed.
Co-reporter:Jiyang Li, Li Li, Jing Liang, Peng Chen, Jihong Yu, Ying Xu and Ruren Xu
Crystal Growth & Design 2008 Volume 8(Issue 7) pp:2318-2323
Publication Date(Web):May 24, 2008
DOI:10.1021/cg701080u
The rational selection of the templating agents or structure-directing agents (SDAs) is important for the designed synthesis of open-framework materials with specific channel structures. By utilizing organic amines that are predicted by computer simulations as the templates or SDAs, such as cyclohexylamine (CHA), cyclopentylamine (CPA), and n-propylamine, three new open-framework zinc phosphites, including (C6H14N)2[Zn3(HPO3)4] (ZnHPO-CJ2), (C5H12N)2[Zn3(HPO3)4] (ZnHPO-CJ3), and (C3H10N)2[Zn3(HPO3)4] (ZnHPO-CJ4), have been hydrothermally prepared with desired extra-large 24-ring channels analogous to (C4NH12)2[Zn3(HPO3)4] (ZnHPO-CJ1). Their structures are characterized by single-crystal and powder X-ray diffraction, inductively coupled plasma (ICP), IR, and thermogravimetric analyses. These organic amines predicted based on nonbonding interactions of host–guest show good matching in the space and charge density with the host inorganic framework. As with ZnHPO-CJ1 and other known extra-large micropore materials with high framework charge density, the 24-rings of these compounds are assembled around multiple small amines, exemplifying the cooperative templating mechanism of multiple small organic cations in the formation of extra-large micropore open-framework materials. This work demonstrates a useful strategy toward the template-designed synthesis of microporous materials with extra-large micropores.
Co-reporter:Qinhe Pan;Jiyang Li Dr.;KirstenE. Christensen;Charlotte Bonneau Dr.;Xiaoyan Ren;Lei Shi Dr.;Junliang Sun Dr.;Xiaodong Zou ;Guanghua Li Dr. ;Ruren Xu
Angewandte Chemie International Edition 2008 Volume 47( Issue 41) pp:7868-7871
Publication Date(Web):
DOI:10.1002/anie.200801375
Co-reporter:Yi Li Dr. ;Ruren Xu ;Christian Baerlocher Dr.;LynneB. McCusker Dr.
Angewandte Chemie International Edition 2008 Volume 47( Issue 23) pp:4401-4405
Publication Date(Web):
DOI:10.1002/anie.200705175
Co-reporter:Yi Li Dr. ;Ruren Xu ;Christian Baerlocher Dr.;LynneB. McCusker Dr.
Angewandte Chemie 2008 Volume 120( Issue 23) pp:4473-4477
Publication Date(Web):
DOI:10.1002/ange.200705175
Co-reporter:Xiaoxin Chen, Wenfu Yan, Wanling Shen, Jihong Yu, Xuejing Cao, Ruren Xu
Microporous and Mesoporous Materials 2007 Volume 104(1–3) pp:296-304
Publication Date(Web):23 August 2007
DOI:10.1016/j.micromeso.2007.05.015
Morphology control of silicalite-1 (Si-MFI) crystals was achieved by employing microwave-assisted solvothermal synthesis in the reaction system TEOS–TPAOH-alcohol using dipolar alcohols as a co-solvent. The influences of various experimental parameters, such as dielectric parameters of the alcohols, aging time, and the amount of the alcohols in the reaction mixture on the morphology of the resulting Si-MFI crystals were investigated. Our studies show that self-stacked Si-MFI crystals could be prepared by using alcohols with low dielectric constants as a co-solvent with short aging time and high concentration in the reaction mixture under microwave radiation. The resulting products were further characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and 29Si MAS NMR analyses.
Co-reporter:Guangmei Wang, Wenfu Yan, Peng Chen, Xi Wang, Kun Qian, Tan Su, Jihong Yu
Microporous and Mesoporous Materials 2007 Volume 105(1–2) pp:58-64
Publication Date(Web):15 September 2007
DOI:10.1016/j.micromeso.2007.05.043
A new microporous sodium cerium silicate Na2.4CeSi6O15 · 2.6H2O containing mixed valence of CeIII/CeIV (denoted CeSiO-CJ2) was successfully synthesized under mild hydrothermal conditions. Its structure was determined by single-crystal X-ray diffraction (XRD) analysis, and characterized by SEM, powder XRD, ICP, TGA, and XPS analyses. CeSiO-CJ2 crystallizes in orthorhombic space group Cmm2 (No. 35) with a = 7.4165(15) Å, b = 30.966(6) Å, and c = 7.1539(14) Å, and Z = 4. It consists of flexuous [Si2O5]n2n- silicate layers that are connected by seven-coordinated Ce polyhedra to form a three dimensional (3D) open framework. There exist two different types of irregular 8-ring channels along [1 0 0] and 6-ring channels along [0 0 1] in which Na+ ions and water molecules reside. Magnetic measurement shows that CeSiO-CJ2 exhibits a Curie–Weiss behavior over the temperature range of 2–300 K with a Weiss constant θ of −5.34(1) K, and a Curie constant C of 0.12(7) K. The data of susceptibility show that there exists at least 31.2% trivalent Ce in CeSiO-CJ2 which is consistent with the XPS analysis. CeSiO-CJ2 exhibits a strong broad emission band containing two overlapped peaks centered at about 384 and 420 nm, respectively. Ion-exchange capacity of CeSiO-CJ2 was investigated by measuring the exchange amount of Na+ ions with various cations. Studies indicate that the Na+ ions can be nearly completely (97.2%) exchanged with NH4+ ions. The Na+ ionic conductivity measurement shows that its conductivity activation energy is 0.25 eV and that the conductivity at 573 K is 2.7 × 10−5 (Ω cm)−1.
Co-reporter:Zhiying Fan, Li Ren, Wenjing Zhang, Dongdong Li, Guoqing Zhao and Jihong Yu
Inorganic Chemistry Frontiers 2017 - vol. 4(Issue 5) pp:NaN839-839
Publication Date(Web):2017/02/27
DOI:10.1039/C7QI00046D
A multifunctional nanotheranostic system for imaging guided chemo- and photothermal synergistic therapy for cancer has been developed, in which the aggregation-induced emission (AIE) luminogen functionalised mesoporous silica nanoparticles (MSNs) act as anticancer drug carriers and biological imaging agents, and CuS nanoparticles attached to the silica nanosphere surface as the photothermal agent. The obtained nanocomposites (denoted as CFMSNs) exhibit a blue emission and have good biocompatibility, and can be used as an effective luminescent bioprobe for intracellular imaging. Furthermore, the nanoplatform can induce obvious thermal effects after the exposure to an 808 nm laser and serve as an effective pH-dependent NIR-responsive release system. More importantly, the combination of chemotherapy and photothermal therapy shows a better therapeutic effect than the individual therapies, thus demonstrating a synergistic action towards anticancer therapy.
Co-reporter:Shuting Du, Xiaoxin Chen, Qiming Sun, Ning Wang, Mingjun Jia, Valentin Valtchev and Jihong Yu
Chemical Communications 2016 - vol. 52(Issue 17) pp:NaN3583-3583
Publication Date(Web):2016/01/28
DOI:10.1039/C5CC10232D
Hierarchical TS-1 zeolites with secondary macropores have been successfully prepared by using two different fluoride-containing chemical etching post-treated routes. Hierarchical TS-1 zeolites exhibited a chemical composition similar to that of the parent material and showed remarkably enhanced catalytic activity in oxidative desulfurization reaction.
Co-reporter:Ying Mu, Yanyan Wang, Yi Li, Jiyang Li and Jihong Yu
Chemical Communications 2015 - vol. 51(Issue 11) pp:NaN2151-2151
Publication Date(Web):2014/12/15
DOI:10.1039/C4CC08964B
A new open-framework magnesium aluminophosphate MgAlP2O7(OH)(H2O)2 (denoted as JU102) has been hydrothermally synthesized by using an organotemplate-free synthetic route in the Al2O3–P2O5–MgO–H2O system. JU102 exhibits novel 4-connected zeolite-like topology with 8-ring channels. The existence of coordinated water and extensive H-bonds in the structure endows JU102 with unique proton conduction properties.
Co-reporter:Yanjun Sun, Yan Yan, Yanyan Wang, Yi Li, Jiyang Li and Jihong Yu
Chemical Communications 2015 - vol. 51(Issue 45) pp:NaN9319-9319
Publication Date(Web):2015/05/06
DOI:10.1039/C5CC03116H
A new open-framework aluminophosphate Na6[(AlPO4)8(OH)6]·8H2O (JU103) has been synthesized by utilization of the organotemplate-free synthetic route in alkali metal-containing system. The as-prepared JU103 possesses two-dimensional intersecting 8-ring channels. Sodium ions and water molecules in the channels facilitates JU103 excellent proton conductivity up to 3.59 × 10−3 S cm−1 (293 K, 98% RH).
Co-reporter:Dongdong Li, Chuanlong Miao, Xiaodan Wang, Xianghui Yu, Jihong Yu and Ruren Xu
Chemical Communications 2013 - vol. 49(Issue 83) pp:NaN9551-9551
Publication Date(Web):2013/08/20
DOI:10.1039/C3CC45041D
An aggregation-induced emission (AIE) probe, possessing a quaternary tetraphenylethene (TPEN) cation, was successfully intercalated into layered α-zirconium phosphate (α-ZrP) nanosheets by ion-exchange. The hybrid materials emit strong blue emissions in aqueous solution which can be used as an effective fluorescence label for HeLa cells.
Co-reporter:Dongdong Li, Yuping Zhang, Zhiying Fan and Jihong Yu
Chemical Communications 2015 - vol. 51(Issue 72) pp:NaN13833-13833
Publication Date(Web):2015/07/23
DOI:10.1039/C5CC05173H
Mesoporous silica nanoparticles functionalised with aggregation-induced emission (AIE) luminogen via a carbon–nitrogen double bond are fabricated into films by a dip-coating method. The as-made films can serve as efficient fluorescent sensors for the naked-eye detection of volatile acid gases by colour and emission changes, as well as for the detection of 2,4-dinitrotoluene vapours by fluorescence quenching.
Co-reporter:Dongyang Xi, Qiming Sun, Xiaoxin Chen, Ning Wang and Jihong Yu
Chemical Communications 2015 - vol. 51(Issue 60) pp:NaN11989-11989
Publication Date(Web):2015/06/19
DOI:10.1039/C5CC03904E
A facile and green route has been developed for the synthesis of hierarchical zeolite catalysts by recycling of waste mother-liquors. After three recycles of mother-liquors, the obtained hierarchical SAPO-34 zeolites retain high crystallinity, texture properties, and acidity, as well as excellent MTO catalytic performance as compared to the initially prepared catalysts.
Co-reporter:Qiming Sun, Ning Wang, Guanqi Guo and Jihong Yu
Chemical Communications 2015 - vol. 51(Issue 91) pp:NaN16400-16400
Publication Date(Web):2015/09/16
DOI:10.1039/C5CC07343J
Nano-sized SAPO-34 zeolites with high crystallinity are obtained in 10 minutes by fast heating the reaction gel in a stainless steel tubular reactor combined with the seed-assisted method, which show outstanding performance in methanol-to-olefin (MTO) reaction.
Co-reporter:Qiming Sun, Ning Wang, Dongyang Xi, Miao Yang and Jihong Yu
Chemical Communications 2014 - vol. 50(Issue 49) pp:NaN6505-6505
Publication Date(Web):2014/04/30
DOI:10.1039/C4CC02050B
Using an organosilane surfactant as the mesopore director, hierarchical porous silicoaluminophosphate SAPO-34 is obtained as an assembly of nanocrystallites intergrown into cubic micrometer-sized crystals, which show excellent performance in MTO reactions with a remarkably prolonged catalyst lifetime and enhanced selectivity of ethylene and propylene compared to the conventional microporous SAPO-34.
Co-reporter:Yanyan Wang, Yanjun Sun, Ying Mu, Chuanqi Zhang, Jiyang Li and Jihong Yu
Chemical Communications 2014 - vol. 50(Issue 97) pp:NaN15403-15403
Publication Date(Web):2014/10/17
DOI:10.1039/C4CC06319H
A facile organotemplate-free route has been developed to synthesize an aluminophosphate molecular sieve in an alkali metal-containing system under hydrothermal conditions. The as-prepared JU93 possesses AEN zeotype topology with small 8-ring pores, and its derivatives show ion conductivity and adsorption selectivity of CO2 over CH4.
Co-reporter:Dongdong Li, Jihong Yu and Ruren Xu
Chemical Communications 2011 - vol. 47(Issue 39) pp:NaN11079-11079
Publication Date(Web):2011/09/06
DOI:10.1039/C1CC14064G
An aggregation-induced emission (AIE) luminogen, tetraphenylethene, has been successfully grafted onto mesoporous silica SBA-15 for the first time. The materials emit blue light upon UV irradiation, and are photostable for the ibuprofen (IBU) drug loading and release process, indicating their great potential for biomedical applications.
Co-reporter:Yi Li and Jihong Yu
Chemical Science (2010-Present) 2016 - vol. 7(Issue 6) pp:
Publication Date(Web):
DOI:10.1039/C6SC00123H
Co-reporter:Ying Mu, Ning Wang, Zaicheng Sun, Jing Wang, Jiyang Li and Jihong Yu
Chemical Science (2010-Present) 2016 - vol. 7(Issue 6) pp:NaN3568-3568
Publication Date(Web):2016/02/12
DOI:10.1039/C6SC00085A
Hydrophilic N-doped carbogenic nanodots (denoted as CNDs) have been prepared from a N-methylpiperazine-templated zeolite precursor by calcination and NaOH treatment. The isolated CNDs exhibit tunable photoluminescence according to the concentration and pH value of aqueous dispersions of the CNDs. Fine-tuning of the fluorescence emission wavelength across the entire visible spectrum can be easily achieved by varying the concentration of the CND dispersions. Meanwhile, both the emission wavelength and intensity of the photoluminescence can be tuned by controlling the pH value of the CND dispersion. The pyrolysis of organic templates confined in nanoporous zeolites represents a new approach to controlling the optical properties of CNDs, which may open more opportunities in applications such as multimodal sensing and full-color displays.
Co-reporter:Dongdong Li, Yuping Zhang, Zhiying Fan, Jie Chen and Jihong Yu
Chemical Science (2010-Present) 2015 - vol. 6(Issue 11) pp:NaN6101-6101
Publication Date(Web):2015/07/20
DOI:10.1039/C5SC02044A
Aggregation-induced emission (AIE) and aggregation-caused quenching (ACQ) materials are important for various fluorescence-based applications but cannot easily collaborate because of their opposite luminescence behaviours. Here, we demonstrate a strategy to integrate AIE and ACQ chromophores in periodic mesoporous organosilicas (PMOs) for high-efficiency multicolour emission. Tetraphenylethene (TPE)-bridged AIE-PMOs are prepared as hosts to encapsulate ACQ dyes (e.g. RhB), which enables fine-tuning of ACQ@AIE-PMO emissions over the entire visible spectrum in the solid and film states. Significantly, high-quality white light is achieved with CIE coordinates of (0.32, 0.33) and a quantum yield of up to 49.6%. Because of their high stability and solution processability, the ACQ@AIE-PMOs can be applied in solid-state lighting and bioimaging. This design concept opens up new perspectives for developing high-performance luminescent materials by the combination of a wide variety of AIE and ACQ chromophores.
Co-reporter:Junbiao Wu, Chunyao Tao, Yi Li, Jiyang Li and Jihong Yu
Chemical Science (2010-Present) 2015 - vol. 6(Issue 5) pp:NaN2927-2927
Publication Date(Web):2015/03/05
DOI:10.1039/C5SC00291E
A novel zinc gallophosphate zeolitic material |(C12H14N2)4F1.33|[Ga13.33Zn6.67(PO4)20] (denoted as JU101) has been prepared by using in situ generated methyl viologen (MV) as the template. The framework of JU101 features two building units including an unprecedented fused d6r and a novel [412·64·82·102] cavity. The connection of these two building units forms a 3D intersecting pore system containing 8-rings along the [010] direction, and 10-rings along the [001] and [100] directions. The MV-templated JU101 zeolitic material offers a new type of electron transfer system, which endows the material with interesting photochromism, thermochromism, and tuneable photovoltaic activity in response to light and heating. Importantly, JU101 shows an extended photochromism range from UV to visible light, high thermal stability, as well as a long-lived charge-separated state for potential application in solar energy conversion.
Co-reporter:Qiang Wen, Jiancheng Di, Lei Jiang, Jihong Yu and Ruren Xu
Chemical Science (2010-Present) 2013 - vol. 4(Issue 2) pp:NaN595-595
Publication Date(Web):2012/11/23
DOI:10.1039/C2SC21772D
Oil–water separations are helping with urgent issues due to increasing industrial oily wastewater, as well as frequent oil spill accidents. Membrane-based materials with special wettability are desired to separate oils from water. However, fabrication of energy-efficient and stable membranes that are suitable for practical oil–water separation remains challenging. Zeolite films have attracted intense research interest due to their unique pore character, excellent chemical, thermal and mechanical stability, etc. Here we first demonstrate zeolite-coated mesh films for gravity-driven oil–water separation. High separation efficiency of various oils can be achieved based on the excellent superhydrophilicity and underwater superoleophobicity of the zeolite surface. Flux and intrusion pressure are tunable by simply changing the pore size, dependent on the crystallization time of the zeolite crystals, of the zeolite meshes. More importantly, such films are corrosion-resistant in the presence of corrosive media, which gives them promise as candidates in practical applications of oil–water separation.
Co-reporter:Zhuopeng Wang, Jihong Yu and Ruren Xu
Chemical Society Reviews 2012 - vol. 41(Issue 5) pp:NaN1741-1741
Publication Date(Web):2011/11/22
DOI:10.1039/C1CS15150A
Zeolites are an important class of materials which are widely used in industry as catalysts, adsorbents and ion-exchangers. Their superior properties are closely related to their unique porous framework structure, as well as composition and morphology. The ever-growing needs for zeolitic materials in applications inspire us to think of the rational synthesis of zeolites with desired structures and properties. However, rationalization of zeolitic materials remains one of the most challenging issues in the zeolite research field due to their unclear formation mechanism. Despite this, many efforts have been devoted to synthesize zeolites in a more rational way. In this tutorial review, first, we demonstrate how the geometrical characteristics of zeolite frameworks affect the catalytic performances of the resulting materials; then, we present recent advances in synthetic innovations to target materials, and we further highlight the developments in computer simulations toward ab initio design and synthesis; finally, the future perspective on the rational synthesis of zeolitic materials with desired functions and structures will be described.
Co-reporter:Jiyang Li, Avelino Corma and Jihong Yu
Chemical Society Reviews 2015 - vol. 44(Issue 20) pp:NaN7127-7127
Publication Date(Web):2015/03/05
DOI:10.1039/C5CS00023H
The search for new zeolites is of continuous interest in the field of zeolite science because of their widespread application in catalysis and adsorption–separation. To this end, considerable efforts have been devoted to the preparation of new zeolites with novel porous architectures and compositions. Taking account of the key factors governing the formation of zeolites (e.g., guest species, framework elements, construction processes, etc.), several synthetic strategies have been developed recently. These allow the discovery of many new zeolites with unprecedented structural features, such as hierarchical pores, odd-ring numbers (11-, 15-rings), extra-large pores (16-, 18-, 20-, 28-, and 30-rings), chiral pores, and extremely complex framework topologies, etc. In this review, we will present the advances in the synthesis of new zeolite structures in the last decade, which are achieved by utilization of the synthetic strategies based on pre-designed structure-directing agents, heteroatom substitution, and topotactic transformations.
Co-reporter:Miao Yang, Xinjie Li, Jihong Yu, Jingran Zhu, Xiaoxia Liu, Genfu Chen and Yan Yan
Dalton Transactions 2013 - vol. 42(Issue 18) pp:NaN6301-6301
Publication Date(Web):2013/03/15
DOI:10.1039/C3DT50591J
A new chiral copper borophosphate, LiCu2[BP2O8(OH)2] (1), was crystallized from achiral inorganic raw materials in boric acid flux reaction. The structure features a 9-ring channel enclosed by triple right-handed helices. The bulk sample exhibits optical activity confirmed by circular dichroism (CD) spectra, indicating an interesting spontaneous resolution phenomenon.
Co-reporter:Weiting Yang, Jiyang Li, Qinhe Pan, Hongzhu Xing, Yan Chen, Jihong Yu and Ruren Xu
Journal of Materials Chemistry A 2009 - vol. 19(Issue 26) pp:NaN4528-4528
Publication Date(Web):2009/05/15
DOI:10.1039/B820130G
A new layered iron borophosphate (C4N3H16)(C4N3H15)0.5[Fe2B4P7O26(OH)4] (denoted FeBPO-CJ28), with a novel B/P ratio of 4/7 and mixed-valent iron(II, III) was prepared under mild hydrothermal conditions in the presence of diethylenetriamine (DETA) as the template. Its crystal structure was determined by single-crystal X-ray diffraction (triclinic, P (No. 2), a = 8.9568(3) Å, b = 9.8717(3) Å, c = 17.9905(5) Å, α = 102.510(2)°, β = 92.343(2)°, γ = 100.403(2)°, V = 1522.10(8) Å3, and Z = 2). The structure comprises unprecedented anionic double layers 2∞{[Fe2B4P7O26(OH)4]4−} with one-dimensional 8-ring channels along the [110] direction, which are made up of FeO6, BO4, PO4 and HPO4 polyhedral units. Such double layers parallel to the ab plane are connected by inter-layer hydrogen bonds forming the three-dimensional (3D) supramolecular open framework with pseudo 10-ring channels along the [110] direction. Protonated DETA cations locate in the 8-ring channels and pseudo 10-ring channels to compensate the negative charge of the anionic framework. The structure is featured by a new fundamental building unit (FBU) [B4P7O26(OH)4], which is the largest one of the borophosphate anionic partial structures. The compound is further characterized by powder XRD, ICP, CHN, TGA and Mössbauer spectroscopy analysis. The magnetic measurement reveals that FeBPO-CJ28 exhibits ferrimagnetic behavior below 9.6 K with a hysteresis loop at 2 K (HC = 2800 Oe, MR = 0.21 µB).
Co-reporter:Jiancheng Di, Yong Zhao and Jihong Yu
Journal of Materials Chemistry A 2011 - vol. 21(Issue 24) pp:NaN8520-8520
Publication Date(Web):2011/04/28
DOI:10.1039/C1JM10512D
Molecular sieves, such as zeolites and mesoporous materials, have been widely used in the fields of catalysis, adsorption, ion-exchange, and are finding new applications in optics, electronics, magnetism, medicine, etc. Molecular sieves with different morphologies or aggregation states, such as spheres, films, and fibers have been prepared to fulfil the need for various applications. Electrospinning offers a simple and straightforward way for generating ultrafine fibers with diameter in the range of nanometres to micrometres from a variety of materials. In recent decades, electrospinning has been introduced to prepare molecular sieve fibers. In this review, fibrous molecular sieves including zeolite fibers, siliceous and nonsiliceous mesoporous fibers prepared by electrospinning are summarized, and their prominent applications in optics, adsorptions, catalysis, etc. are highlighted.
Co-reporter:Qiming Sun, Ning Wang, Guanqi Guo, Xiaoxin Chen and Jihong Yu
Journal of Materials Chemistry A 2015 - vol. 3(Issue 39) pp:NaN19789-19789
Publication Date(Web):2015/08/20
DOI:10.1039/C5TA04642D
Hierarchically porous zeolites with different levels of porosity have emerged as an important class of materials because of their enhanced mass transport and improved catalytic performance. Silicoaluminophosphate zeolite SAPO-34 is one of the best catalysts for methanol-to-olefin (MTO) conversion, but suffers from rapid deactivation due to the narrow 8-ring pore openings. To overcome this inherent diffusion bottleneck and improve the MTO performance, in this work, tri-level hierarchically porous SAPO-34 zeolite with intracrystalline micro–meso–macroporosity has been first synthesized by an Al-rich method coupled with the use of the polyethylene glycol 2000 polymer under hydrothermal conditions. The as-synthesized hierarchically porous SAPO-34 catalysts exhibit superior catalytic performance in the MTO reaction with about six times prolonged catalytic lifetime and nearly 5% improvement of selectivity for ethylene and propylene compared to the conventional microporous SAPO-34.
Co-reporter:Hongzhu Xing, Yi Li, Tan Su, Jin Xu, Weiting Yang, Enbo Zhu, Jihong Yu and Ruren Xu
Dalton Transactions 2010 - vol. 39(Issue 7) pp:NaN1715-1715
Publication Date(Web):2010/01/06
DOI:10.1039/B919933K
We present the spontaneous crystallization of a new chiral open-framework borophosphate in an ionothermal system. Its structure contains a three-dimensional (3D) anionic framework with intersecting 12-ring channels formed by interweaving helical chains.
Co-reporter:Yanan Guo, Xiaowei Song, Jiyang Li, Yi Li, Yide Han, Jihong Yu and Ruren Xu
Dalton Transactions 2011 - vol. 40(Issue 36) pp:NaN9294-9294
Publication Date(Web):2011/08/11
DOI:10.1039/C1DT10430F
Two heteroatom-containing open-framework aluminophosphates, (C3H4N2)2FeAl3P4O16 and (C3H4N2)2CrAl3P4O16 (denoted as MAPO-CJ50, M = Fe, Cr), have been synthesized by using imidazole as the template under solvothermal conditions. The structure of FeAPO-CJ50 is determined by single-crystal X-ray diffraction, and its analogous structure CrAPO-CJ50 is identified by powder X-ray diffraction. The 3-dimensional framework of MAPO-CJ50, constructed by MO4N2 octahedra, AlO4 tetrahedra, and PO4 tetrahedra, contains interconnecting 10- and 8-ring channels. Imidazole molecules are coordinated with framework M3+ ions and interact with each other through π–π stacking interactions in the channels. These two compounds show photoluminescent properties due to ligand-to-metal charge transfer. Magnetic measurements reveal that there are antiferromagnetic interactions between M3+ ions in the frameworks of FeAPO-CJ50 and CrAPO-CJ50.
Co-reporter:Dongdong Li, Zhiqiang Liang, Jie Chen, Jihong Yu and Ruren Xu
Dalton Transactions 2013 - vol. 42(Issue 27) pp:NaN9883-9883
Publication Date(Web):2013/04/22
DOI:10.1039/C3DT50243K
A new type of organophosphonic acid, (4,4′-(1,2-diphenylethene-1,2-diyl)bis(4,1-phenylene))bis(methylene)diphosphonic acid (PATPE), based on tetraphenylethene has been prepared, and its ester derivative exhibits the characteristic property of aggregation-induced emission (AIE) in DMSO–H2O solution. The PATPE is then fabricated into hydroxyapatite by a one-pot condensation process to form hollow mesoporous nanocapsules of ellipsoidal morphology. The AIE luminogen-bridged hollow hydroxyapatite nanocapsules emit strong blue light under UV irradiation, which is further used for drug delivery using ibuprofen (IBU) as a model drug. The fluorescence intensity of the materials varies greatly with the loading and release of IBU, suggesting that the drug release process may be tracked in terms of the change of luminescence intensity. The biocompatibility of AIE luminogen functionalized material is also evaluated on HUH7 human hepatoma cells using the MTT assay. The low cytotoxicity of the materials reveals that the as-prepared multifunctional hydroxyapatite will be a new candidate for simultaneous drug delivery and cell imaging in potential bioapplications.
Co-reporter:Bert M. Weckhuysen and Jihong Yu
Chemical Society Reviews 2015 - vol. 44(Issue 20) pp:NaN7024-7024
Publication Date(Web):2015/09/24
DOI:10.1039/C5CS90100F
A graphical abstract is available for this content
Co-reporter:Qiang Wen, Jiancheng Di, Yong Zhao, Yang Wang, Lei Jiang and Jihong Yu
Chemical Science (2010-Present) 2013 - vol. 4(Issue 12) pp:NaN4382-4382
Publication Date(Web):2013/08/16
DOI:10.1039/C3SC51851E
Organic molecule pollution in industrial and agricultural sewage is a serious threat to the environment and human health. Adsorption membranes have proven to be good candidates for removing contaminations from wastewater efficiently and continuously. Inorganic porous materials possessing large surface area, and high chemical and thermal stability are excellent adsorbents for organic contaminants. However, a major shortfall of the inorganic porous membranes is that they are usually fragile. Here we demonstrate flexible SiO2–TiO2 composite porous nanofibrous membranes fabricated via electrospinning technique for efficient water purification. The composite membranes exhibit high adsorption capacity and permeability in the purification test with methylene blue solution based on their hierarchical porous structure and ultrafast wettability, and can be easily recycled by calcination. Such properties, integrated with the membrane fabrication process that is energy-efficient, low cost and easy to scale-up, will facilitate their practical application in the removal of organic pollutants.
Co-reporter:Junbiao Wu, Chunyao Tao, Yi Li, Yan Yan, Jiyang Li and Jihong Yu
Chemical Science (2010-Present) 2014 - vol. 5(Issue 11) pp:NaN4241-4241
Publication Date(Web):2014/07/24
DOI:10.1039/C4SC01396D
X-ray-induced photochromic materials are promising candidates for X-ray detection. An effective strategy to synthesize photochromic materials is the incorporation of photochromic methylviologen (MV) into inorganic open frameworks. It is of great interest to adjust the photochromic behaviour of MV-based materials using designed synthesis of novel anionic open frameworks. A new multifunctional photo-sensitive material, MV-templated layered bimetal phosphate JU99, is presented. It possesses unique X-ray-induced photochromism at room temperature, as well as interesting photoluminescence and photovoltaic activity, all of which are reversible in response to X-ray irradiation. These properties make JU99 an excellent material for X-ray detection.
Co-reporter:Yuping Zhang, Dongdong Li, Yi Li and Jihong Yu
Chemical Science (2010-Present) 2014 - vol. 5(Issue 7) pp:NaN2716-2716
Publication Date(Web):2014/03/31
DOI:10.1039/C4SC00721B
A novel class of tetraphenylethene (TPE) derivatives TPEM and TPEBM containing dicyanovinyl groups were synthesized, possessing remarkable dual properties of solvatochromism and aggregation-induced emission (AIE). The combination of the electron-donating TPE and the electron-accepting dicyanovinyl group endow both compounds with a prominent solvatochromic effect, with emissions strongly dependent on solvent polarity and tunable from blue to red by changing the solvent from apolar to polar. They are found to be useful as fluorescent indicators for the qualitative and quantitative detection of low-level water content in organic solvents, and the detection limit can be as low as 63 ppm and 109 ppm in THF, respectively. Meanwhile, TPEM and TPEBM demonstrate typical AIE features and emit green-yellow and orange light in their aggregated states, respectively. Based on the AIE feature of TPE and the nucleophilic addition of cyanide, both compounds can act as colorimetric and fluorescent sensors for highly sensitive and selective detection of CN− in aqueous media under the assistance of cetyltrimethylammonium bromide (CTAB). The low detection limit of 0.2 μM as well as a short sensing process of only 100 seconds promise their practical application for detecting cyanide in drinking water. Furthermore, the development of easy-to-prepare test papers provides a convenient and reliable approach to monitor CN− in daily applications without resorting to instrumental analysis.
Co-reporter:Dongdong Li, Jianzhao Liu, Ryan T. K. Kwok, Zhiqiang Liang, Ben Zhong Tang and Jihong Yu
Chemical Communications 2012 - vol. 48(Issue 57) pp:NaN7169-7169
Publication Date(Web):2012/05/23
DOI:10.1039/C2CC31890C
Mesoporous SBA-15 functionalized with aggregation-induced emission (AIE) luminogens serves as an efficient and recyclable fluorescent sensor for the detection of picric acid (PA), with a quenching constant of up to 2.5 × 105 M−1 in a water solution, presenting a new model for the supersensitive detection of explosives.
Co-reporter:Libo Sun, Hongzhu Xing, Zhiqiang Liang, Jihong Yu and Ruren Xu
Chemical Communications 2013 - vol. 49(Issue 95) pp:NaN11157-11157
Publication Date(Web):2013/06/11
DOI:10.1039/C3CC43383H
A zeolitic metal–organic framework with a SOD topology, (Et2NH2)[In(BCBAIP)]·4DEF·4EtOH (H4BCBAIP: 5-(bis(4-carboxybenzyl)amino)isophthalic acid) (1), has been constructed by a 4 + 4 synthetic strategy from tetrahedral organic building units and In3+ ions. Compound 1 could adsorb organic dyes and be used as a light-harvesting antenna.
Co-reporter:Shuting Du, Fen Li, Qiming Sun, Ning Wang, Mingjun Jia and Jihong Yu
Chemical Communications 2016 - vol. 52(Issue 16) pp:NaN3371-3371
Publication Date(Web):2016/01/22
DOI:10.1039/C5CC08441E
Hierarchical TS-1 zeolites with uniform intracrystalline mesopores have been successfully synthesized through the hydrothermal method by using the green and cheap surfactant Triton X-100 as the mesoporous template. The resultant materials exhibit remarkably enhanced catalytic activity in oxidative desulfurization reactions compared to the conventional TS-1 zeolite.
Co-reporter:Duo Wang, Jie Chen, Li Ren, Qinglan Li, Dongdong Li and Jihong Yu
Inorganic Chemistry Frontiers 2017 - vol. 4(Issue 3) pp:NaN472-472
Publication Date(Web):2017/01/03
DOI:10.1039/C6QI00488A
Aggregation-induced emission luminogens (AIEgens), tetraphenylethene, were post grafted onto mesoporous silica nanoparticles to form AIEgen-functionalised mesoporous materials. The obtained blue-emitting materials can serve as a fluorescence resonance energy transfer (FRET) donor for monitoring the release process of doxorubicin hydrochloride (DOX) as an acceptor by the change of the fluorescent signal, showing potential application in imaging-guided therapy.
Co-reporter:Junran Lu, Lin Li, Hongxiao Cao, Yi Li and Jihong Yu
Physical Chemistry Chemical Physics 2017 - vol. 19(Issue 2) pp:NaN1280-1280
Publication Date(Web):2016/12/06
DOI:10.1039/C6CP06217B
To boost function-led discovery of new zeolites with desired pores and properties, millions of hypothetical zeolite structures have been predicted via various computational approaches. It is now well accepted that most of these predicted structures are experimentally unrealisable under conventional synthetic conditions. Many structure evaluation criteria have been proposed to screen out unfeasible structures, among which the framework density–framework energy correlation criterion and the local interatomic distances criteria are the most frequently used. However, many hypothetical structures passing these criteria have been found unfeasible because of the existence of highly distorted framework rings. Here, we propose a new set of structure evaluation criteria to screen out such unfeasible structures. After optimising all existing zeolite structures as silica polymorphs, we find that the closest non-adjacent O⋯O distances in existing zeolite rings generally show a normal distribution. By comparing the closest non-adjacent O⋯O distances between existing and hypothetical zeolite structures, we are able to screen out many unfeasible hypothetical zeolite structures with distorted rings that are deemed feasible according to previous structure evaluation methods.
Co-reporter:Qiming Sun, Ning Wang, Risheng Bai, Xiaoxin Chen and Jihong Yu
Journal of Materials Chemistry A 2016 - vol. 4(Issue 39) pp:NaN14982-14982
Publication Date(Web):2016/09/13
DOI:10.1039/C6TA06613E
A facile and cost-effective strategy has been developed to synthesize nano-sized SAPO-34 zeolite catalysts with intracrystalline meso-macroporosity as well as high crystallinity and product yield via the seed-assisted method using triethylamine as the sole template. Significantly, compared to conventional micron-sized microporous SAPO-34 zeolites, the nano-sized hierarchical SAPO-34 zeolites show superior performance in the methanol-to-olefin (MTO) reaction with a 4-fold prolonged catalytic lifetime and remarkably improved selectivity for ethylene and propylene reaching up to 85.0%, which is among the highest catalytic performances in the MTO reaction ever reported under similar conditions.
Co-reporter:Shuting Du, Qiming Sun, Ning Wang, Xiaoxin Chen, Mingjun Jia and Jihong Yu
Journal of Materials Chemistry A 2017 - vol. 5(Issue 17) pp:NaN7998-7998
Publication Date(Web):2017/04/12
DOI:10.1039/C6TA10044A
In this work, we report a hydrothermal route to synthesize hierarchical TS-1 zeolites with abundant mesopores (5–40 nm) inside the zeolite crystals by using polydiallyldimethylammonium chloride (PDADMAC) as a mesopore-directing template. The textural parameters of the hierarchical TS-1 zeolites can be adjusted by changing the amount of PDADMAC in the synthesis system; in particular, a hierarchical TS-1C sample with abundant and uniform mesopores (around 10 nm) can be obtained by optimizing the amount of PDADMAC. The resultant hierarchical TS-1 zeolite exhibits excellent catalytic activity in the oxidation of bulky organosulfur compounds. Moreover, the hierarchical TS-1 catalysts possess high structural stability and can be easily recycled without any post treatment. This work demonstrates a facile route to synthesize hierarchical TS-1 zeolites with abundant intracrystalline mesopores by using a cheap and easily available mesoporous template, which will open new perspectives for the potential application of hierarchical TS-1 zeolites in catalytic oxidation of bulky organic compounds.
Co-reporter:Jihong Yu and Ruren Xu
Journal of Materials Chemistry A 2008 - vol. 18(Issue 34) pp:NaN4030-4030
Publication Date(Web):2008/06/17
DOI:10.1039/B804136A
Chiral zeolitic materials are of both fundamental and practical interest because they can combine both shape selectivity and enantioselectivity, which are desirable for asymmetric catalysis and separation. However, the synthesis of such materials remains a significant challenge in the field of zeolite science. This feature article will focus on a family of four-connected zeolite frameworks and related inorganic open frameworks with fascinating chiral structural features, aiming to provide an insight into the origin of chirality in these structures. Some approaches to the design of chiral zeolite frameworks, as well as synthesis routes and challenges to the chiral zeolitic materials are also discussed.
Co-reporter:Dongyang Xi, Qiming Sun, Jun Xu, Minhyung Cho, Hae Sung Cho, Shunsuke Asahina, Yi Li, Feng Deng, Osamu Terasaki and Jihong Yu
Journal of Materials Chemistry A 2014 - vol. 2(Issue 42) pp:NaN18004-18004
Publication Date(Web):2014/09/01
DOI:10.1039/C4TA03030C
Silicoaluminophosphate zeolite SAPO-34 with CHA topology is known as one of the best catalysts for methanol-to-olefin (MTO) conversion. In this work, we demonstrate a facile one-step hydrothermal synthesis of hierarchically macroporous SAPO-34 through the etching effect of hydrofluoric acid. The highly crystalline hierarchically macroporous SAPO-34 is prepared as central-holed rhombohedral crystals with particle size of ca. 5–10 μm that comprise intracrystalline parallel macrochannels of ca. 100 nm. The formation of macroporous structures via in situ growth-etching can be directly imaged by SEM. Strikingly, a particular crystal configuration consisting of eight pyramidal parts has been first observed during the zeolite crystal growth process, which eventually grows to form a perfect rhombohedral shape. The HF etching effect is further elucidated by the analysis of changes of pH values as well as of solid and liquid compositions following the evolution of crystallization. The texture properties, chemical environments of framework atoms, and acidity of the synthesized SAPO-34 are characterized by N2 adsorption/desorption, MAS NMR and NH3-TPD measurements. The hierarchically macroporous SAPO-34 shows larger micropore volume, slightly stronger acid strength, and lower external surface acidity than its conventional counterpart synthesized without using HF. Consequently, the hierarchically macroporous SAPO-34 exhibits excellent MTO catalytic performance, showing much higher selectivity to ethylene and propylene as well as longer lifetime than the conventional counterpart. In comparison with previously reported methods for the generation of hierarchical porosity, this one-step HF-assisted in situ growth-etching synthetic route is simple, straightforward and cost-effective, which offers a new approach to prepare hierarchically porous zeolites with improved catalytic activity.
Co-reporter:Qiming Sun, Yanhang Ma, Ning Wang, Xu Li, Dongyang Xi, Jun Xu, Feng Deng, Kyung Byung Yoon, Peter Oleynikov, Osamu Terasaki and Jihong Yu
Journal of Materials Chemistry A 2014 - vol. 2(Issue 42) pp:NaN17839-17839
Publication Date(Web):2014/08/27
DOI:10.1039/C4TA03419H
Nanosheet-like silicoaluminophosphate (SAPO) molecular sieves SAPO-34 (CHA-type) and SAPO-18 (AEI-type) with different silicon contents were synthesized under hydrothermal conditions by using tetraethylammonium hydroxide as the template. Three-dimensional electron diffraction tomography (3D EDT) technique was applied for ab initio structure solutions. Electron microscopy observations confirmed the existence of defects, i.e., intergrowth of CHA- and AEI-type frameworks caused by the different stacking manners of double 6-ring layers, but the layers were highly coherent along c direction. Compositions, acidities, chemical environments, and texture properties of all the samples were characterized by ICP, EDS, NH3-TPD, MAS NMR, and N2 adsorption–desorption measurements. The catalytic performances of methanol-to-olefin (MTO) reactions over nano SAPO catalysts with different silicon contents were systematically studied. All of these catalysts showed excellent catalytic activity, among which SAPO-34 showed superior catalytic performance compared to SAPO-18. DFT calculations were utilized to study the different catalytic performance of CHA and AEI. Significantly to date, SAPO-34 with the lowest silicon content exhibited the longest catalyst lifetime and the lowest coking rate in the MTO reaction than any of the reported catalysts, tested under similar conditions. The straight 8-ring pore channel along the c direction provided the optimum diffusion pathway as well as the shortest diffusion length for reactant and generated olefins, thus significantly reduced the coking rate. This work demonstrates that a 3D EDT approach combined with TEM and EDS analysis from a single nanocrystal can provide a clear crystal structure, crystal orientation and compositional information of nanocrystals, which are useful for the better understanding of the catalytic performance of nanosized crystalline catalysts.
Co-reporter:Weiting Yang, Jiyang Li, Tianyi Na, Jin Xu, Lei Wang, Jihong Yu and Ruren Xu
Dalton Transactions 2011 - vol. 40(Issue 11) pp:NaN2554-2554
Publication Date(Web):2011/02/04
DOI:10.1039/C0DT01475C
A new three-dimensional (3-D) open-framework manganese borophosphate, (NH4)6[Mn3B6P9O36(OH)3]·4H2O (denoted as MnBPO-CJ31), has been synthesized by using boric acid flux method. Its anionic framework structure is constructed by the connection of MnO6 octahedra and BO4, PO4 and PO3(OH) tetrahedra. It contains 12-ring channels along the [001] direction with a pore diameter of 7.1 Å. It is the first borophosphate featuring a 3-D anionic partial structure with a B/P ratio of 2/3 and an unprecedented fifteen mer tetrahedral fundamental building unit (FBU) [B6P9O36(OH)3] exists in this compound. NH4+ ions locate in the void space to balance the negative charge of the inorganic framework. The compound is further characterized by powder XRD, ICP, CHN, TGA and IR analyses. Magnetic study reveals that MnBPO-CJ31 shows interesting canted antiferromagnetic behaviour at low temperature.
![1,3-Benzenedicarboxylic acid, 5-[bis[(4-carboxyphenyl)methyl]amino]-](/data/chemimg/3716500/1492054-35-9.png)
![1,3-Benzenedicarboxylic acid, 5-[bis[(4-carboxyphenyl)methyl]amino]-](/data/chemimg/3716500/1492054-35-9_b.png)
![[1,1':3',1''-Terphenyl]-4,4''-dicarboxaldehyde, 5'-(4-formylphenyl)-](/data/chemimg/113700/118688-53-2.png)
![[1,1':3',1''-Terphenyl]-4,4''-dicarboxaldehyde, 5'-(4-formylphenyl)-](/data/chemimg/113700/118688-53-2_b.png)
![Benzene,[(1E)-2-methoxy-1-methylethenyl]-](http://img.cochemist.com/ccimg/59000/58966-09-9.png)
![Benzene,[(1E)-2-methoxy-1-methylethenyl]-](http://img.cochemist.com/ccimg/59000/58966-09-9_b.png)
![11-oxo-2,3,5,6,7,11-Hexahydro-1H-pyrano[2,3-f]pyrido[3,2,1-ij]quinoline-10-carboxylic acid](/data/chemimg/86700/55804-65-4.png)
![11-oxo-2,3,5,6,7,11-Hexahydro-1H-pyrano[2,3-f]pyrido[3,2,1-ij]quinoline-10-carboxylic acid](/data/chemimg/86700/55804-65-4_b.png)
![1,2-ETHANEDIAMINE, N-[(TRIETHOXYSILYL)METHYL]-](http://img.cochemist.com/ccimg/41600/41555-92-4.png)
![1,2-ETHANEDIAMINE, N-[(TRIETHOXYSILYL)METHYL]-](http://img.cochemist.com/ccimg/41600/41555-92-4_b.png)
![6-azoniaspiro[5.5]undecane;bromide](http://img.cochemist.com/ccimg/6300/6286-82-4.png)
![6-azoniaspiro[5.5]undecane;bromide](http://img.cochemist.com/ccimg/6300/6286-82-4_b.png)
![9-Oxabicyclo[6.1.0]nonane, (1R,8S)-rel-](http://img.cochemist.com/ccimg/5000/4925-71-7.png)
![9-Oxabicyclo[6.1.0]nonane, (1R,8S)-rel-](http://img.cochemist.com/ccimg/5000/4925-71-7_b.png)
