Shi-Lun Qiu

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Name: ShiLun Qiu; 裘式纶

Organization: Jilin University , China

Department: State Key Laboratory of Inorganic Synthesis and Preparative Chemistry

Title: Professor(PhD)

TOPICS

Analytical Chemistry

Chemicals
References

Amino-modified MIL-68(In) with enhanced hydrogen and carbon dioxide sorption enthalpy

Co-reporter:Lei Wu, Ming Xue, Shi-Lun Qiu, Gérald Chaplais, Angélique Simon-Masseron, Joël Patarin

Microporous and Mesoporous Materials 2012 Volume 157() pp:75-81

Publication Date(Web):15 July 2012

DOI:10.1016/j.micromeso.2011.12.034

The amino modified MIL-68(In), hereafter denoted by MIL-68(In)_NH2, has been obtained by self-assembling from 2-amino-terephthalic acid and indium nitrate hydrate. The characterization of the modified material based on powder X-ray diffraction analysis, IR spectroscopy, 1H NMR spectroscopy and TG analysis demonstrates that this porous coordination network possesses the Kagomé topology of MIL-68(In) with amino modified pores walls. The Brunauer–Emmett–Teller surface area of 1230 ± 24 m2 g−1 for MIL-68(In)_NH2 compared to 1028 ± 29 m2 g−1 for MIL-68(In) exhibits an surface area improvement of approximate 200 m2 g−1 within MIL-68(In)_NH2. Moreover, for both hybrids, the hydrogen and carbon dioxide sorption properties have been studied at 77 K and 87 K, and at 273 K and 298 K, respectively. The comparison of the corresponding results of MIL-68(In) shows that the presence of amino group can effectively enhance the adsorption enthalpy of H2 and CO2, whereas, slightly effect on the integral sorption amount. Besides, to our knowledge, it is the first time that the CO2 adsorption of MIL-68(In) sample are reported.Graphical abstractHighlights► An amino modified MIL-68(In) (named MIL-68(In)_NH2) has been synthesized. ► Surface area gain approximate 200 m2 g−1 within MIL-68(In)_NH2 compared to MIL-68(In). ► The adsorption enthalpy of H2 and CO2 is enhanced by the modification of amino groups into MIL-68(In).

Hydrothermal synthesis, structure, fluorescence property of a novel 3D metal-organic framework with high thermal stability

Co-reporter:Lei Wu;Ming Xue;Lin Huang;ShiLun Qiu

Science China Chemistry 2011 Volume 54( Issue 9) pp:

Publication Date(Web):2011 September

DOI:10.1007/s11426-011-4321-z

A novel 3D metal-organic framework (MOF) with remarkable thermal stability, Ni(BIC)2·2.5H2O (JUC-86) (HBIC = 1-H-benzimidazole-5-carboxylic acid and JUC = Jilin University China), has been synthesized under hydrothermal conditions. It crystallizes in tetragonal symmetry with P43212 space group. The 3D structure consists of channels assembled from triple helices with a 4.5 × 4.5 Å2 aperture, which are formed by the parallel alignment of three infinite helical chains. The thermogravimetric analysis (TGA) and powder X-ray diffractions (PXRD) indicate JUC-86 with high thermal stability (up to 350 °C).

Coordination Modulation Induced Synthesis of Nanoscale Eu1-xTbx-Metal-Organic Frameworks for Luminescent Thin Films

Co-reporter:Hailing Guo;Yongzhong Zhu;Shilun Qiu;Johannes A. Lercher;Hongjie Zhang

Advanced Materials 2010 Volume 22( Issue 37) pp:4190-4192

Publication Date(Web):

DOI:10.1002/adma.201000844

Facile fabrication of metal–organic framework films promoted by colloidal seeds on various substrates

Co-reporter:Xiaoqin Zou, Guangshan Zhu, Feng Zhang, Mingyi Guo and Shilun Qiu

CrystEngComm 2010 vol. 12(Issue 2) pp:352-354

Publication Date(Web):01 Oct 2009

DOI:10.1039/B912470E

With the aid of In(OH)(BDC) colloidal seeds, metal–organic framework films (In(OH)(BDC)) have been fabricated by a simple solvothermal reaction of 1,4-benzenedicarboxylic acid (H2BDC) and In(NO3)3·xH2O in DMF on various substrates with different surface conditions.

Molecular engineering for synthesizing novel structures of metal–organic frameworks with multifunctional properties

Co-reporter:Shilun Qiu, Guangshan Zhu

Coordination Chemistry Reviews 2009 Volume 253(23–24) pp:2891-2911

Publication Date(Web):December 2009

DOI:10.1016/j.ccr.2009.07.020

Metal–organic frameworks (MOFs) which are constructed from metal ions or metal ion clusters and bridging organic linkers, have recently emerged as an important family of porous materials due to their unique structural and functional properties. This review provides the molecular engineering for synthesizing novel MOF structures and summarizes their potential applications. In this review, we present the promotion of the synthesis chemistry in this area and introduce the general methods and the important factor of organic template in the synthesis process. To obtain MOFs with high porosity, three strategies will be introduced. We also discuss how to functionalize the MOFs from two directions: chiral frameworks and frameworks constructed from rare earth metals. The burgeoning area of MOF membranes will also be introduced. Most applications of MOFs are based on their ability to function as hosts. The potential applications including hydrogen storage and methane storage, molecular separation, catalysis, and sensor, are summarized. It is expected that MOFs will provide extraordinary advantages over traditional porous materials and have an important and permanent impact on the future of porous compounds.

Novel mesoporous silica spheres with ultra-large pore sizes and their application in protein separation

Co-reporter:Lihua Chen, Guangshan Zhu, Daliang Zhang, Hang Zhao, Mingyi Guo, Wei Shi and Shilun Qiu

Journal of Materials Chemistry A 2009 vol. 19(Issue 14) pp:2013-2017

Publication Date(Web):11 Feb 2009

DOI:10.1039/B818740A

A series of novel mesoporous silica materials with ultra-large pores (20 to 40 nm in size), interconnected channel structure, thick walls (15 to 20 nm), high hydrothermal stability and selective protein adsorption were synthesized via a new synthetic strategy. We used Brij-56 and Brij-97 as templates and ethyl acetate (EA) and dimethyl o-phthalate (DOP) as additives in a neutral pH system to afford three novel spherical mesoporous silica materials (denoted as B56-E-20, B56-D-33 and B97-D-40) having controllable, interconnected mesoscale channels with diameters of 20, 33 and 40 nm, respectively. The products have shown effective performance in size-selective adsorption of biomacromolecules, demonstrating great potentials in biomacromolecular separation. The molecular weight ranges of the proteins selectively adsorbed in B56-E-20, B56-D-33 and B97-D-40 are 50–55, 60–65 and 70–100 KDa, respectively. Moreover, the products show good hydrothermal stability and can maintain the mesostructure in boiling water over 5 days. This work has bridged the gap in the synthesis of ultra-large pore between mesoporous and macroporous biomaterials and their application in biomacromolecular separation.

Synthesis of a metal–organic framework film by direct conversion technique for VOCs sensing

Co-reporter:Xiaoqin Zou, Guangshan Zhu, Ian J. Hewitt, Fuxing Sun and Shilun Qiu

Dalton Transactions 2009 (Issue 16) pp:3009-3013

Publication Date(Web):10 Mar 2009

DOI:10.1039/B822248G

For the first time, a metal–organic framework Zn3(BTC)2 film has been successfully synthesized on the substrate of zinc wafer by a direct conversion technique. The obtained crystal densities and inter-growth of the film have been improved via the zinc wafer conversion method. The effect of synthesis conditions on the crystallization of Zn3(BTC)2 and activation of the substrate were determined to optimize the strategies for the synthesis of continuous and stable layers. The crystallization took place by converting the activated zinc layer on the substrate. The reaction between the substrate-generated zinc source and the H3BTC clear solution yielded the best inter-growth of crystals and formed a high-density coating. More interestingly, the fluorescence emission of the Zn3(BTC)2 film was found to be highly sensitive and selective sensing to dimethylamine among different VOCs. The fluorescence intensity decreased with increasing contents of dimethylamine in ethanol solution due to weak fluorescence quenching effect. This high-quality MOF film may find promising applications in sensors, especially in VOCs sensing.

A Series of Three-Dimensional Lanthanide Coordination Compounds with the Rutile Topology

Co-reporter:Xiaojun Zhao, Guangshan Zhu, Qianrong Fang, Ying Wang, Fuxing Sun and Shilun Qiu

Crystal Growth & Design 2009 Volume 9(Issue 2) pp:737

Publication Date(Web):December 12, 2008

DOI:10.1021/cg800204q

A series of three-dimensional lanthanide coordination compounds with rutile topology, M(CTC)(DMF)(H2O)·(DMF)(H2O) (M = Tb (1), Dy (2), Ho (3), Er (4), and Tm (5), CTC = cis,cis-1,3,5-cyclohexanetricarboxylic acid, DMF = N,N′-dimethylformamide), have been synthesized under mild conditions. They are isomorphous and crystallize in monoclinic symmetry with space group P21/n. The structure can be considered to be built up from metallic 6-connected and organic 3-connected building units with vertex symbol (4·4·4·4·64·64). These lanthanide coordination compounds possess 10.4 × 10.1 Å2 channels along the [100] direction, and 7.7 × 7.7 Å2 channels along the [011] and [01̅1] direction, respectively. The fluorescent, water, and methanol adsorption properties of these compounds are studied, and the results reveal that they could be potentially utilized as multifunctional materials.

Six Three-Dimensional Metal−Organic Frameworks with (3,4)-, (4,5)-, and (3,4,5)-Connected Nets Based on Mixed Ligands: Synthesis, Structures, and Adsorption Properties

Co-reporter:Ming Xue, Guangshan Zhu, Hong Ding, Lei Wu, Xiaojun Zhao, Zhao Jin and Shilun Qiu

Crystal Growth & Design 2009 Volume 9(Issue 3) pp:1481

Publication Date(Web):January 12, 2009

DOI:10.1021/cg8009546

Six new 3D metal−organic frameworks (MOFs) Cd2(3,4-PDC)2(μ2-hmt)(H2O)2·(DMF)2(H2O)2 (JUC-65), Zn4(3,4-PDC)4(μ2-hmt)(H2O)6·(DMA)4(H2O)5 (JUC-66), Cd2(3,4-PDC)2(bipy)2(H2O)2·(DMA)3(H2O)4 (JUC-67), Cd2(3,4-PDC)2(bipy)(DMF)(H2O)·(H2O)2 (JUC-68), Mn2(3,4-PDC)2(μ2-hmt)(H2O)2 (JUC-69), and Zn8(3,4-PDC)8(bipy)3(DMA)2·(DMA)8(H2O)8 (JUC-70) (3,4-H2PDC = pyridine-3,4-dicarboxylic acid, hmt = hexamethylenetramine, bipy = 4,4′-bipyridine, DMF = N,N′-dimethylformamide, DMA = N,N′-dimethylacetamide, and JUC = Jilin University China) have been synthesized via heterocoordination of unsymmetrical 3,4-H2PDC and transition metal ions (Cd2+, Zn2+, or Mn2+) to construct corrugated layers pillared by hmt or bipy ligands, which form various sizes and shapes of channels. Remarkably, from the topological point of view, JUC-65−68 exhibit three undocumented types of (3,4)-connected networks, JUC-69 exhibits a rare (4,5)-connected network, and JUC-70 possesses an unprecedented (3,4,5)-connected network. In addition, methanol adsorption isotherms of the activated JUC-65 and JUC-67 reveal type I behavior with approximately 87.7 mg/g and 124.8 mg/g at room temperature, respectively.

Synthesis and characterization of pure-silica-zeolite Beta low-k thin films

Co-reporter:Yanli Chen, Guangshan Zhu, Ye Peng, Hai Bi, Jing Feng, Shilun Qiu

Microporous and Mesoporous Materials 2009 Volume 123(1–3) pp:45-49

Publication Date(Web):1 July 2009

DOI:10.1016/j.micromeso.2009.03.022

A new reaction mixture with the addition of n-propyl alcohol into the all-silica TEAOH–TEOS–HF–H2O gel was presented for the first time to prepare continuous and compact pure-silica-zeolite (PSZ) Beta film on silicon wafer. n-Propyl alcohol was used to produce much homogeneous reaction mixture as well as accelerate the crystallization of Beta nanocrystals. In addition, by utilizing the secondary growth method the PSZ Beta film was much thinner (3.5 μm) and the synthesis time can further decrease to 36 h. X-ray diffraction, scanning electron microscopy, ICP–AES and ellipsometry were used to characterize the PSZ Beta film. After calcination the PSZ Beta film exhibited the ultra-low dielectric constant and dielectric loss of 2.07 and 0.096 at 1 MHz, and the elastic modulus and hardness of 45 and 1.8 GPa, respectively. The PSZ Beta film with ultra-low dielectric constant, high thermally and mechanically stability would make them very promising low dielectric constant materials as insulating films in microelectronic.

Effective heavy metal removal through porous stainless-steel-net supported low siliceous zeolite ZSM-5 membrane

Co-reporter:Xiaoqin Zou, Guangshan Zhu, Hailing Guo, Xiaofei Jing, Diou Xu, Shilun Qiu

Microporous and Mesoporous Materials 2009 Volume 124(1–3) pp:70-75

Publication Date(Web):August–September 2009

DOI:10.1016/j.micromeso.2009.04.034

Removal of heavy metals is of great interest as drinkable water resources are dramatically declining in China. Most desalination techniques before are concentrated on polymeric membranes with laborious processes. To improve thermal, chemical and physical stability of these membranes, zeolite membranes appear to be optimal substitutes. The technique used here is reverse osmosis with the porous stainless-steel-net supported low siliceous zeolite ZSM-5 membrane (Si/Al = 20). The synthesized membrane is more compact, continuous and large-scaled, which shows high rejection rate (>99%), and the highly porous stainless-steel-net support and high hydrophilicity of the low siliceous zeolite ZSM-5 membrane make the flux increased a lot. Zn2+, Cd2+, Hg2+, Cu2+, Pb2+ and Cr3+ heavy metal cations were investigated. The synthesized low siliceous ZSM-5 membrane (Si/Al = 20) was characterized by X-ray Diffraction, Leica optics micrographs, field emission scanning electron microscopy and inductively coupled plasma atomic emission spectrometer.

Synthesis and characterization of (h0l) oriented high-silica zeolite beta membrane

Co-reporter:Yanli Chen, Guangshan Zhu, Ye Peng, Xiangdong Yao, Shilun Qiu

Microporous and Mesoporous Materials 2009 Volume 124(1–3) pp:8-14

Publication Date(Web):August–September 2009

DOI:10.1016/j.micromeso.2009.04.012

The (h0l) oriented high-silica zeolite beta membrane was prepared with improved method in fluoride media. Dealuminated zeolite beta nanocrystals used as seeds were preliminary deposited on support, and then the seeded supports were vertically placed in autoclaves for hydrothermal synthesis. After the secondary growth of seeded supports at 413 K for 2 days, zeolite membranes were characterized by X-ray diffraction and scanning electron microscopy to determine their morphology and preferred orientation. Zeolite beta membranes with a thickness of intergrown crystal layer around 2 μm were prepared and the crystals with typical truncated square bipyramidal morphology were packed tightly with their pyramidal (h0l) face perpendicular to the plane of membrane. In addition, ICP-AES chemical analysis was utilized to confirm the composition of seeds and membrane, and the Si/Al molar ratio of zeolite beta membrane was around 5000. The (00l) and randomly orientated zeolite beta membranes were also prepared by changing the composition of starting synthesis gel and pH value. A competitive growth model was proposed to explain the formation of oriented membranes. The (h0l) oriented high-silica zeolite beta membrane with few cracks exhibited higher pervaporation flux.

A rare 3D lanthanide metal–organic framework with the rutile topology: Synthesis, structure and properties

Co-reporter:Xiao-Jun Zhao, Teng Ben, Ming Xue, Guang-Shan Zhu, Qian-Rong Fang, Shi-Lun Qiu

Journal of Molecular Structure 2009 Volume 931(1–3) pp:25-30

Publication Date(Web):14 August 2009

DOI:10.1016/j.molstruc.2009.05.027

A 3D lanthanide metal–organic framework (MOF) with the rutile topology, Yb(CTC)(DMF)·(H2O)2 (JUC-57) (CTC = cis, cis-1, 3, 5-cyclohexanetricarboxylic acid, DMF = N, N′-dimethylformamide, and JUC = Jilin University China), have been synthesized under mild conditions. It crystallizes in monoclinic symmetry with space group P21/n. The structure can be considered to be built up from six-connected inorganic and three-connected organic Secondary Building Units (SBUs) with the rutile topology, Schläfli symbol of which is (42·610·83)(4·62)2. This lanthanide MOF possesses 11.8 × 6.9 Å2 channels along the [1 0 0] direction, and 6.8 × 6.1 Å2 channels along the [0 1 1] and [0 1 −1] direction, respectively. The fluorescent and magnetic properties of JUC-57 are characterized and the result reveals that it could be potentially utilized as the multifunctional material.

Polymer−Mesoporous Silica Materials Templated with an Oppositely Charged Surfactant/Polymer System for Drug Delivery

Co-reporter:Huiming Lin, Guangshan Zhu, Jiaojiao Xing, Bo Gao and Shilun Qiu

Langmuir 2009 Volume 25(Issue 17) pp:10159-10164

Publication Date(Web):June 24, 2009

DOI:10.1021/la900910h

In this paper, polymer−mesoporous silica nanoparticles have been synthesized by a dual-template technology. Cationic polymer quaternized poly[bis(2-chloroethyl)ether-alt-1,3-bis[3-(dimethylamino)propyl]urea] (PEPU) and anionic surfactant sodium dodecyl sulfate (SDS) were used to form a homogeneous comicelle system to induce mesoporous silica spherical nanoparticles with diameters of 50−180 nm. The formation mechanism was studied by transmission electron microscopy (TEM), which suggested that PEPU played a cotemplate role in the synthesis process, and no mesoporous structure was generated without it. After removing the anionic surfactant, SDS, by an ion-exchange method, the cationic polymer−mesoporous silica nanoparticles were obtained. Using the materials as the host and ibuprofen (IBU)/captopril (CapH2) as the model drugs, the system revealed well-sustained release profiles.

Synthesis, crystal structure and properties of inorganic-organic hybrid polymers based on 8-hydroxylquinoline-5-sulfonic acid

Co-reporter:Ying Wang;Ming Xue;JiaNing Xu;GuangShan Zhu

Science China Chemistry 2009 Volume 52( Issue 10) pp:1602-1608

Publication Date(Web):2009 October

DOI:10.1007/s11426-009-0234-5

Two new inorganic-organic hybrid polymers, Mn(QS)(H2O) (1) and Co(QS)(H2O)2 (2) (H2QS=8-hydroxylquinoline-5-sulfonic acid), based on 8-hydroxylquinoline-5-sulfonate ligand, have been synthesized under solvothermal conditions and their structures were solved by single-crystal X-ray diffraction analysis. Compound 1 is a three-dimensional open framework with rutile topology structure, and compound 2 is a three-dimensional supramolecular structure. These compounds were characterized by powder XRD, infrared spectroscopy, thermogravimetric analysis, fluorescence properties and magnetism properties.

Amine-Templated Assembly of Metal–Organic Frameworks with Attractive Topologies

Co-reporter:Qianrong Fang, Guangshan Zhu, Ming Xue, Zhuopeng Wang, Jinyu Sun and Shilun Qiu

Crystal Growth & Design 2008 Volume 8(Issue 1) pp:319

Publication Date(Web):December 14, 2007

DOI:10.1021/cg070604f

Seven new metal–organic frameworks (MOFs) have been synthesized using different organic amines as templates: [Cd(HBTC)2]·2(HDETA)·4(H2O) (1) (BTC = 1,3,5-benzenetricarboxylate and DETA = diethylenetriamine), [Cd2(BTC)2(H2O)2]·2(HCHA)·2(EtOH)·2(H2O) (CHA = cyclohexylamine) (2), [Cd5(BTC)4Cl4]·4(HTEA)·2(H3O) (TEA = triethylamine) (3), [Cd3(BTC)3(H2O)]·(HTEA)·2(H3O) (4), [Zn(BTC)(H2O)]·(HTPA)·(H2O) (TPA = tri-n-propylamine) (5), [Cd(BTC)]·(HTPA)·(H2O) (6), and [Cd2(BTC)(HBTC)]·(HTBA)·(H2O) (TBA = tri-n-butylamine) (7). Topologically, the polymer 1 exhibits a two-dimensional (2D) Cd-HBTC network with (44) topology, which is a sql structure; the polymer 2 possesses a three-dimensional (3D) porous Cd-BTC framework with (4·62)2(42·610·83) topology, which is a contorted rutile structure; polymer 3 exhibits a 3D open Cd-BTC architecture with (62·82·102)2(62·84)(63)4 topology; polymer 4 is a 3D porous Cd-BTC network with new (4·62)2(42·64·86·103)(6·82)2(62·84)(62·84)2(62·8)2 topology; similar to 1, polymer 5 is a 2D Zn-BTC framework with (4·82) topology; interestingly, polymer 6 possesses a 3D porous Cd-BTC architecture with the same topology as 2; polymer 7 shows a 3D open Cd-BTC framework with (63)(65·10) topology. In addition to the structures of polymers 1–7, their thermal stabilities, ion exchange properties, and nonbonding interaction energies, including H-bonding and van der Waals, have also been studied. Remarkably, those organic amine cations reside in the interlayer or channel space, playing important roles such as templating, space-filling, and charge-balancing agents. These studies would facilitate the exploration of novel MOFs with charming molecular topologies and multifunctional properties.

Rational Design and Control of the Dimensions of Channels in a Series of 3D Pillared Metal−Organic Frameworks: Synthesis, Structures, Adsorption, and Luminescence Properties

Co-reporter:Ming Xue, Guangshan Zhu, Yujian Zhang, Qianrong Fang, Ian J. Hewitt and Shilun Qiu

Crystal Growth & Design 2008 Volume 8(Issue 2) pp:427

Publication Date(Web):January 1, 2008

DOI:10.1021/cg0701022

A systematic variation of diamine ligands, TED, Bipy, and Bpe [TED = triethylenediamine, Bipy = 4,4′-bipyridine, and Bpe = trans-bis(4-pyridyl)ethylene], pillaring 2-fold (6,3) layers constructed from metallic trinuclear SBUs and flexible CTC ligands gives rise to a series of porous metal−organic frameworks, Cd3(CTC)2(TED)(H2O)2·(H3O)2Cl2 (1), Cd3(CTC)2(Bipy)(DMF)2·(DMF)(H2O)2 (2), Cd3(CTC)2(Bpe)(DMF)2·(DMF)(H2O)2 (3), Zn3(CTC)2(Bipy)·(DMF)(H2O)2 (4), and Zn3(CTC)2(Bpe)·(DMF)(H2O)2 (5) (compounds 1–5 named JUC-34, JUC-44, JUC-45, JUC-46, JUC-47, respectively, JUC-Jilin University, China, CTC = cis,cis-1,3,5-cyclohexanetricarboxylate and DMF = N,N′-dimethylformamide). These open frameworks have been synthesized under mild conditions possessing three-dimensional connectivity with interconnecting pores and the same (43)2(46·618·84) topology. The water adsorption isotherms of these compounds show type Ι behavior with approximately 0.07, 0.10, 0.12, 0.17, and 0.19 mL/g pore volumes, respectively. Photoluminescence investigations reveal that they display strong emission in the blue/green regions.

Structure, Hydrogen Storage, and Luminescence Properties of Three 3D Metal−Organic Frameworks with NbO and PtS Topologies

Co-reporter:Ming Xue, Guangshan Zhu, Yangxue Li, Xiaojun Zhao, Zhao Jin, Enhua Kang and Shilun Qiu

Crystal Growth & Design 2008 Volume 8(Issue 7) pp:2478-2483

Publication Date(Web):June 7, 2008

DOI:10.1021/cg8001114

Three 3D multifunctional microporous metal−organic frameworks (MOFs), Cu2(ABTC)(H2O)2·(DMF)2(H2O) (JUC-62), Cd2(ABTC)(DMF)3·(DMF)2 (JUC-63), and Mn(H2ABTC)(DMF)2 (JUC-64) (H4ABTC = 3,3′,5,5′-azobenzenetetracarboxylic acid, DMF = N,N′-dimethylformamide, and JUC = Jilin University China) have been synthesized by self-assembly of a rigid tetra-carboxylate ligand H4ABTC and corresponding transition metal salts under mild conditions. X-ray crystallography reveals that their topologies are based on NbO (JUC-62) and PtS (JUC-63 and JUC-64) nets, constructed of 4-connected rectangular ABTC4− units with 4-connected square paddle-wheel Cu2(CO2)4(H2O)2 secondary building units (SBUs), tetrahedral bimetallic Cd2(CO2)4(DMF)3 SBUs, and tetrahedral monometallic Mn(CO2)4(DMF)3 SBUs, respectively. High-pressure hydrogen sorption of the activated JUC-62 reveals a type I profile at 77 K, which is saturated at 40 bar with a hydrogen uptake of about 4.71 wt%. Photoluminescence investigations reveal that JUC-62 and JUC-63 display strong main emission spectra peaks at 392 and 402 nm, respectively.

Fluorescence of postgrafting Rhodamine B in the mesopores of rodlike SBA-15

Co-reporter:Mina Guli, Yue Chen, Xiaotian Li, Guangshan Zhu, Shilun Qiu

Journal of Luminescence 2007 Volume 126(Issue 2) pp:723-727

Publication Date(Web):October 2007

DOI:10.1016/j.jlumin.2006.11.003

Rhodamine B (Rh B) has been grafted into the channels of rod-like mesoporous silica SBA-15, which had been modified by organic silane with terminal amino group in CHCl3 solvent. The investigations of UV–vis, photoluminescence, and FT-IR confirmed the existence of Rh B in the channels of RSBA-15 (rod-like SBA-15). The composites show strong fluorescence and obvious blue-shift at the yellow wave band compared with Rh B in CHCl3.

Zeolite P/NaX composite membrane for gas separation

Co-reporter:Xiaoju Yin, Guangshan Zhu, Zhengyang Wang, Nailin Yue, Shilun Qiu

Microporous and Mesoporous Materials 2007 Volume 105(1–2) pp:156-162

Publication Date(Web):15 September 2007

DOI:10.1016/j.micromeso.2007.06.028

A stainless-steel-net-supported zeolite P/NaX composite membrane was synthesized by a secondary growth method. The zeolite P membrane covered the zeolite NaX membrane, which closely integrated with the stainless-steel-net support and showed high permeability and selectivity in H2/N2 and H2/CO2 separation in both single and mixture gases. The morphologies of these membranes have been studied using with both optical microscopy and scanning electron microscopy (SEM), and the effect of the zeolite type on the permeation property was discussed.

Mesoporous Metal–Organic Framework with Rare etb Topology for Hydrogen Storage and Dye Assembly

Co-reporter:Qian-Rong Fang Dr.;Guang-Shan Zhu ;Zhao Jin;Yan-Yan Ji Dr.;Jun-Wei Ye Dr.;Ming Xue Dr.;Hua Yang Dr.;Yue Wang

Angewandte Chemie 2007 Volume 119(Issue 35) pp:

Publication Date(Web):25 JUL 2007

DOI:10.1002/ange.200700537

Mehr Löcher als ein Schweizer Käse: Ein metall-organisches Gerüst mit den bisher größten 1D-hexagonalen Nanoröhren-artigen Kanälen (24.5×27.9 Å) und seltener etb-Topologie (siehe Bild) hat gute Fluoreszenzeigenschaften und nimmt beachtliche Mengen Wasserstoff auf. Auch Moleküle des Farbstoffs Rh6G wurden eingelagert; das Produkt zeigte eine vorteilhafte temperaturabhängige Lumineszenz.

Mesoporous Metal–Organic Framework with Rare etb Topology for Hydrogen Storage and Dye Assembly

Co-reporter:Qian-Rong Fang Dr.;Guang-Shan Zhu ;Zhao Jin;Yan-Yan Ji Dr.;Jun-Wei Ye Dr.;Ming Xue Dr.;Hua Yang Dr.;Yue Wang

Angewandte Chemie International Edition 2007 Volume 46(Issue 35) pp:

Publication Date(Web):25 JUL 2007

DOI:10.1002/anie.200700537

More holes than Swiss cheese: A new MOF with the largest reported 1D hexagonal nanotube-like channels of 24.5 Å×27.9 Å and rare etb topology has been synthesized (see picture). It exhibits good fluorescence properties and substantial hydrogen uptake. For the first time, the compound was assembled with Rh6G dye molecules, and the product showed favorable temperature-dependent luminescent properties.

Epitaxial growth of highly-oriented AlPO4-5 molecular sieve films for microlaser systems

Co-reporter:Rui Xu, Guangshan Zhu, Xiaoju Yin, Xin Wan and Shilun Qiu

Journal of Materials Chemistry A 2006 vol. 16(Issue 22) pp:2200-2204

Publication Date(Web):18 Apr 2006

DOI:10.1039/B516305F

For the first time highly-oriented AlPO4-5 molecular sieve films have been achieved on millimeter-sized AlPO4-5 single crystal substrates by epitaxial growth. The orientation of the molecular sieve films can be adjusted via changing the basal faces of the substrate crystal. Furthermore, a laser dye has been successfully encapsulated within such molecular sieve films by in situ crystallization. The controlled orientation of the dye-loaded molecular sieve films and the size around the optical wavelength of the microcrystals in the film may find promising applications in optics, especially in microlaser systems.

A lanthanide metal–organic framework with high thermal stability and available Lewis-acid metal sites

Co-reporter:Xiaodan Guo, Guangshan Zhu, Zhongyue Li, Fuxing Sun, Zhenghong Yang and Shilun Qiu

Chemical Communications 2006 (Issue 30) pp:3172-3174

Publication Date(Web):21 Jun 2006

DOI:10.1039/B605428E

A lanthanide metal–organic framework, Dy(BTC)(H2O)·DMF, with excellent thermal stability shows a high surface area, 655 m2 g−1, high hydrogen and carbon dioxide storage capability, and available Lewis-acid metal sites which could be anticipated to use in catalysis and metal-site specific chemical sensor.

Porous coordination polymers with zeolite topologies constructed from 4-connected building units

Co-reporter:Qian-Rong Fang, Guang-Shan Zhu, Ming Xue, Jin-Yu Sun and Shi-Lun Qiu

Dalton Transactions 2006 (Issue 20) pp:2399-2402

Publication Date(Web):13 Apr 2006

DOI:10.1039/B517400G

Two novel 3D coordination polymers, Cd(CTC)(H2O)·(H2PIP)0.5(H2O) (1) with zeolite ABW topology and Cd(CTC)·(HIPA) (2) with zeolite BCT topology, have been synthesized by constructing inorganic and organic 4-connected building units and using the organic bases as templates, and the frameworks of 1 and 2 not only expand the original structures of zeolites ABW and BCT, but also exhibit significant advantages over them in terms of thermal stability, ion exchange and adsorption.

Synthesis, Structure, and Magnetism of a Highly Thermally Stable Microporous Metal Organodiphosphonate with Reversible Dehydration/Rehydration Behavior

Co-reporter:Hua Li;Guang-shan Zhu;Xiao-dan Guo;Fu-xing Sun;Hao Ren;Yan Chen

European Journal of Inorganic Chemistry 2006 Volume 2006(Issue 20) pp:

Publication Date(Web):15 AUG 2006

DOI:10.1002/ejic.200600465

The synthesis and crystal structure of a novel organic–inorganic hybrid material Co₂(H₂O)₂[O₃PCH₂(C₆H₄)CH₂PO₃] is described. It crystallizes in the orthorhombic space group Pca2(1) [a = 9.6214(19), b = 5.6855(11), c = 21.725(4) Å, V = 1188.4(4) Å³], which consists of two-dimensional cobalt–oxygen inorganic layers pillared by p-xylylenediphosphonateto form a three-dimensional framework, which has 10.850 × 5.687 Å channels running along the b-axis. The material is exceptionally stable, even when heated up to 500 °C in air. More interestingly, the framework components display a reversible dehydration/rehydration behavior. There is an antiferromagnetic interaction between the cobalt ions. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)

The “Building-Block” Assembly of a [Ni12Mn6] Aggregate (Eur. J. Inorg. Chem. 10/2006)

Co-reporter:Gang Wu;Rodolphe Clérac;Wolfgang Wernsdorfer;Shilun Qiu;Christopher E. Anson;Ian J. Hewitt;Annie K. Powell

European Journal of Inorganic Chemistry 2006 Volume 2006(Issue 10) pp:

Publication Date(Web):9 MAY 2006

DOI:10.1002/ejic.200690020

The cover picture shows a mixed metal Mn₆Ni₁₂ compound that results when manganese(II) and nickel(II) percursor building blocks are allowed to self-assemble. The resulting structure contains a trigonal-prismatic central framework portion made up by linking six manganese(II) coordination compound precursors with meridionally arranged labile water ligands, which are replaced here by linking carboxylate units. This framework is decorated with three self-assembled nickel(II) acetate/methoxide cubane units. The overall structure is similar to a wind turbine having a hexanuclear manganese spindle with the nickel cubanes as blades. The synthetic strategy is a promising means for obtaining high-nuclearity heterometallic assemblies with interesting magnetic properties. Details of this work are described in the Short Communication by A. K. Powell et al. on p. 1927 ff.

The “Building-Block” Assembly of a [Ni12Mn6] Aggregate

Co-reporter:Gang Wu;Rodolphe Clérac;Wolfgang Wernsdorfer;Shilun Qiu;Christopher E. Anson;Ian J. Hewitt;Annie K. Powell

European Journal of Inorganic Chemistry 2006 Volume 2006(Issue 10) pp:

Publication Date(Web):4 APR 2006

DOI:10.1002/ejic.200600144

Reaction of Mn^II(bdoa)(H₂O)₃ with Ni(CH₃COO)₂·3H₂O in methanol gives a heterometallic cluster, [Ni₁₂Mn₆(bdoa)₆(O₂CMe)₁₂(μ₃-OMe)₁₂(MeOH)₁₂]·21MeOH, which was structurally characterised by single-crystal X-ray diffraction and possesses three self-assembled tetranuclear nickel cubes connected by a Mn^II₆(bdoa)₆(CH₃COO)₃ subunit. The magnetic properties were studied in detail and indicate that the compound possesses a high density of spin states with small energy gaps between them. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)

Controlled release of Captopril by regulating the pore size and morphology of ordered mesoporous silica

Co-reporter:Fengyu Qu, Guangshan Zhu, Shiying Huang, Shougui Li, Jinyu Sun, Daliang Zhang, Shilun Qiu

Microporous and Mesoporous Materials 2006 Volume 92(1–3) pp:1-9

Publication Date(Web):20 June 2006

DOI:10.1016/j.micromeso.2005.12.004

In order to control the release of water-soluble drug Captopril (CapH2), a series of mesoporous silica materials has been prepared, using three kinds of surfactants C16TAB, C12TAB, and EO20PO70EO20, respectively. It has been found that the loading amount of the drug was related to the BET surface area of the mesoporous silica. MCM-4116 with the highest surface area possesses the largest loading amount, which is up to 33.99 wt%. The loading and release kinetics (in vitro in simulated stomach fluid) showed that both of them were affected not only by the pore diameter but also by the morphologies of mesoporous silica materials. A rapid drug loading could be achieved either by enlarging pore sizes or by reducing particle sizes. And CapH2/SBA-15 delivery system with the largest pore diameter of 7.39 nm has exhibited the fastest release rate. While CapH2/MCM-4112 system with the smallest pore diameter of 1.65 nm and sphere morphology (120–250 nm in size) has a faster release rate than that of CapH2/MCM-4116 system with 2.17 nm pore diameter and rod-like morphology (ca. 20 μm in length). By comparing the release rate of CapH2/MCM-4116 in a simulated stomach fluid with that in the proximal intestine fluid, it was found that the release media played a key role on the drug delivery profiles.

In Situ Synthesis, Characterization of SiPMo-X, and Different Catalytic Properties of SiPMo-X and SiPW-X

Co-reporter:Chunfeng Shi;Runwei Wang;Guangshan Zhu;Shilun Qiu;Jun Long

European Journal of Inorganic Chemistry 2006 Volume 2006(Issue 15) pp:

Publication Date(Web):19 JUN 2006

DOI:10.1002/ejic.200600192

SBA-15 frameworks with encapsulated Keggin type heteropolyacids (HPAs) were synthesized in situ under strongly acidic conditions (pH < 0). During the hydrolysis of tetraethyl orthosilicate (TEOS), a P- and a Mo source were added into the initial sol–gel system to form Keggin type HPAs. The texture of the final products was studied by the N₂ adsorption–desorption isotherms and transmission electron microscopy (TEM), and their structure was systematically characterized by X-ray diffraction (XRD), UV/Vis diffuse reflectance- (DRS), infrared- (IR), and ³¹P magic angle spinning nuclear magnetic resonance (MAS NMR) spectroscopy. Characterization results suggest that the samples show very ordered hexagonal mesostructure, and the HPAs that are incorporated into the framework of meso-silica are insoluble during catalysis. Results of catalytic tests indicate that the materials demonstrated catalytic activity comparable with or even surpassing those of the bulk HPAs in catalytic tests implementing chemical reactions of bulky molecules (1,3,5-triisopropylbenzene cracking, esterification of benzoic acid with tert-butyl alcohol, and 2,3,6-trimethylphenol hydroxylation with H₂O₂). Additionally, some other properties, such as easy separation and stability when recycled, ensure their potential applications in the chemical industries. Here, we report not only the in situ synthesis and characterization of SiPMo-X, but also the difference in the catalytic properties of SiPMo-X and SiPW-X. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)

Drug Self-Templated Synthesis of Ibuprofen/Mesoporous Silica for Sustained Release

Co-reporter:Fengyu Qu;Guangshan Zhu;Huiming Lin;Jinyu Sun;Daliang Zhang;Shougui Li;Shilun Qiu

European Journal of Inorganic Chemistry 2006 Volume 2006(Issue 19) pp:

Publication Date(Web):18 AUG 2006

DOI:10.1002/ejic.200501035

The synthesis of Ibuprofen/mesoporous silica has been achieved by a drug self-templated one-step co-condensation process. The drug template of Ibuprofen, a co-template of 3-aminopropyltriethoxysilane (APTES), and tetraethoxysiliane (TEOS) were self-assembled into Ibuprofen/mesoporous silica in a neutral aqueous reaction system. This drug/mesoporous silica was characterized by powder XRD diffraction, FTIR spectroscopy, N₂ adsorption/desorption, TEM, and ²⁹Si/MAS and ¹³C/MAS NMR spectroscopy. The Ibuprofen/mesoporous silica system gives a well-sustained release profile. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)

Blue-shifting photoluminescence of Tris (8-hydroxyquinoline) aluminium encapsulated in the channel of functionalized mesoporous silica SBA-15

Co-reporter:Nan Li, Xiaotian Li, Wei Wang, Wangchang Geng, Shilun Qiu

Materials Chemistry and Physics 2006 Volume 100(Issue 1) pp:128-131

Publication Date(Web):10 November 2006

DOI:10.1016/j.matchemphys.2005.12.020

We describe the immobilization and photoluminescent properties of Tris (8-hydroxyquinoline) aluminium (Alq3) in the pores of mesoporous silica SBA-15 with amino functional group on the inner surface. Significant blue-shift in PL spectra of about 90 nm was observed and a possible amino group involved mechanism has been put forward.

A controlled release of ibuprofen by systematically tailoring the morphology of mesoporous silica materials

Co-reporter:Fengyu Qu, Guangshan Zhu, Huiming Lin, Weiwei Zhang, Jinyu Sun, Shougui Li, Shilun Qiu

Journal of Solid State Chemistry 2006 Volume 179(Issue 7) pp:2027-2035

Publication Date(Web):July 2006

DOI:10.1016/j.jssc.2006.04.002

A series of mesoporous silica materials with similar pore sizes, different morphologies and variable pore geometries were prepared systematically. In order to control drug release, ibuprofen was employed as a model drug and the influence of morphology and pore geometry of mesoporous silica on drug release profiles was extensively studied. The mesoporous silica and drug-loaded samples were characterized by X-ray diffraction, Fourier transform IR spectroscopy, N2 adsorption and desorption, scanning electron microscopy, and transmission electron microscopy. It was found that the drug-loading amount was directly correlated to the Brunauer–Emmett–Teller surface area, pore geometry, and pore volume; while the drug release profiles could be controlled by tailoring the morphologies of mesoporous silica carriers.The release of ibuprofen is controlled by tailoring the morphologies of mesoporous silica. The mesoporous silica and drug-loaded samples are characterized by powder X-ray diffraction, Fourier transform IR spectroscopy, N2 adsorption and desorption, scanning electron microscopy, and transmission electron microscopy. The drug-loading amount is directly correlated to the Brunauer–Emmett–Teller surface area, pore geometry, and pore volume; while the drug release profiles can be controlled by tailoring the morphologies of mesoporous silica carriers.

Solvothermal synthesis and removal capacity for hydrogen chloride gas of Zn(OH)(NO3) with a rare (10,3)-d net

Co-reporter:Jinyu Sun, Yaming Zhou, Zhenxia Chen, Guangshan Zhu, Qianrong Fang, Rongjing Yang, Shilun Qiu, Dongyuan Zhao

Journal of Solid State Chemistry 2006 Volume 179(Issue 4) pp:1230-1236

Publication Date(Web):April 2006

DOI:10.1016/j.jssc.2006.01.039

A basic zinc nitrate, [Zn(OH)(NO3)]n with a novel framework reported herein is prepared by solvothermal synthesis, and holds a rare three-dimensional (10,3)-d net called by Wells. It crystallizes in orthorhombic, space group, Pna21 (No. 33), a=9.148(3)Å, b=7.596(3)Å, c=5.500(2)Å, Z=4Z=4, V=382.2(2)Å3, ρcalcd=2.509Mg/m3, μ=6.290mm-1, 3.49<θ<27.513.49<θ<27.51, T=293K, R1=0.029R1=0.029, wR2=0.0773wR2=0.0773 for 697 (I>2σ(I)I>2σ(I)) of 1728 [R(int)=0.0246R(int)=0.0246] unique reflections and 59 parameters. GOF=1.073. Interestingly this basic zinc nitrate, [Zn(OH)(NO3)]n behaves well at removal capacity for hydrogen chloride gas, 20.3 g HCl/100 g, and its framework is not destroyed yet. This adsorption character may be useful for the removal of toxic gases in the environment.A paradigm of 10,3-d net.

Humidity sensitivity of polypyrrole and polypyrrole/SBA-15 host–guest composite materials

Co-reporter:Nan Li;Tong Zhang;Xiaotian Li;Shilun Qiu;Wei Wang;Wangchang Geng

Journal of Applied Polymer Science 2006 Volume 102(Issue 4) pp:3301-3305

Publication Date(Web):29 AUG 2006

DOI:10.1002/app.24769

Polypyrrole (PPY) and PPY/SBA-15 host–guest composite materials have been prepared using chemical synthesis route and characterized by XRD, IR, N₂ adsorption–desorption isotherms, and SEM. The humidity sensitive properties (HSP) of this kind of materials have been studied by analyzing the variation curve of impedance as a function of relative humidity. It was found that the PPY/SBA-15 host–guest composites materials exhibit better HSP than that of the corresponding pure PPY. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3301–3305, 2006

Effective Controlled Release of Captopril by Silylation of Mesoporous MCM-41

Co-reporter:Guangshan Zhu;Shougui Li;Shiying Huang;Fengyu Qu;Shilun Qiu

ChemPhysChem 2006 Volume 7(Issue 2) pp:400-406

Publication Date(Web):13 JAN 2006

DOI:10.1002/cphc.200500294

The release of the water-soluble drug Captopril is controlled by tailoring the surface properties of mesoporous silica via stepwise silylation. The degree of silylation is manipulated by adjusting the initial concentration of silylanizing reagent (trimethylchlorosilane, TMCS). The silylanized and drug-loaded samples are characterized by powder X-ray diffraction, Fourier transform IR spectroscopy, N₂ adsorption and desorption,²⁹Si cross-polarization magic angle spinning NMR spectroscopy, and transmission electron microscopy. The drug-loading amount is correlated to the Brunauer–Emmett–Teller surface area and surface hydrophilicity/hydrophobicity of the mesoporous silica material, while drug release profiles can be controlled by tailoring the surface properties and pore size.

Microporous Metal–Organic Framework Constructed from Heptanuclear Zinc Carboxylate Secondary Building Units

Co-reporter:Qian-Rong Fang Dr.;Guang-Shan Zhu ;Ming Xue Dr.;Qing-Lin Zhang Dr.;Jin-Yu Sun Dr.;Xiao-Dan Guo Dr. ;Shi-Tao Xu Dr.;Ping Wang ;De-Jun Wang ;Yen Wei

Chemistry - A European Journal 2006 Volume 12(Issue 14) pp:

Publication Date(Web):3 MAR 2006

DOI:10.1002/chem.200500963

A novel, three-dimensional, noninterpenetrating microporous metal–organic framework (MOF), [Zn₇O₂(pda)₅(H₂O)₂]⋅5 DMF⋅4 EtOH⋅ 6 H₂O (1) (H₂PDA=p-phenylenediacrylic acid, DMF=N,N-dimethylformamide, EtOH=ethanol), was synthesized by constructing heptanuclear zinc carboxylate secondary building units (SBUs) and by using rigid and linear aromatic carboxylate ligands, PDA. The X-ray crystallographic data reveals that the seven zinc centers of 1 are held together with ten carboxylate groups of the PDA ligands and four water molecules to form a heptametallic SBU, Zn₇O₄(CO₂)₁₀, with dimensions of 9.8×9.8×13.8 Å³. Furthermore, the heptametallic SBUs are interconnected by PDA acting as linkers, thereby generating an extended network with a three-dimensional, noninterpenetrating, intersecting large-channel system with spacing of about 17.3 Å. As a microporous framework, polymer 1 shows adsorption behavior that is favorable towards H₂O and CH₃OH, and substantial H₂ uptake. In terms of the heptanuclear zinc carboxylate SBUs, polymer 1 exhibits interesting photoelectronic properties, which would facilitate the exploration of new types of semiconducting materials, especially among MOFs containing multinuclear metal carboxylate SBUs.

Hierarchical Growth of Large-Scale Ordered Zeolite Silicalite-1 Membranes with High Permeability and Selectivity for Recycling CO2

Co-reporter:Hailing Guo;Guangshan Zhu ;Hua Li;Xiaoqin Zou;Xiaoju Yin;Weishen Yang ;Shilun Qiu ;Ruren Xu

Angewandte Chemie International Edition 2006 Volume 45(Issue 42) pp:

Publication Date(Web):2 OCT 2006

DOI:10.1002/anie.200602308

Another fine mesh you've got me into: A stainless-steel-net-imbedded silicalite-1 membrane (MFI film) is synthesized by a hydrothermal method. A hierarchical growth mechanism of the membrane formation is deduced. The MFI film has high thermal and mechanical stability, large-scale order, and exhibits high permeation flux and excellent permeation selectivity for CO₂ (see scheme).

A Multifunctional Metal–Organic Open Framework with a bcu Topology Constructed from Undecanuclear Clusters

Co-reporter:Qian-Rong Fang Dr.;Guang-Shan Zhu ;Zhao Jin;Ming Xue Dr.;Xiao Wei Dr.;De-Jun Wang

Angewandte Chemie International Edition 2006 Volume 45(Issue 37) pp:

Publication Date(Web):27 JUL 2006

DOI:10.1002/anie.200601668

Flexible ligands afford large pores: A novel metal–organic framework constructed from cadmium carboxylate cluster secondary building units and formic acid bridging molecules is reported (see picture). This highly porous material displays rare body-centered cubic topology, as well as good sorption characteristics and optoelectronic properties.

Hierarchical Growth of Large-Scale Ordered Zeolite Silicalite-1 Membranes with High Permeability and Selectivity for Recycling CO2

Co-reporter:Hailing Guo;Guangshan Zhu ;Hua Li;Xiaoqin Zou;Xiaoju Yin;Weishen Yang ;Shilun Qiu ;Ruren Xu

Angewandte Chemie 2006 Volume 118(Issue 42) pp:

Publication Date(Web):2 OCT 2006

DOI:10.1002/ange.200602308

Ein wählerisches Sieb: Eine Silicalit-1-Membran, die in ein Edelstahlnetz eingebettet ist (MFI-Film), wird mit einem Hydrothermalverfahren hergestellt. Für die Membranbildung wird ein hierarchischer Wachstumsmechanismus abgeleitet. Der MFI-Film ist durch eine hohe thermische und mechanische Stabilität, eine großskalige Ordnung, einen hohen Gasdurchgang und eine ausgezeichnete Permeationsselektivität bezüglich CO₂ gekennzeichnet (siehe Schema).

A Multifunctional Metal–Organic Open Framework with a bcu Topology Constructed from Undecanuclear Clusters

Co-reporter:Qian-Rong Fang Dr.;Guang-Shan Zhu ;Zhao Jin;Ming Xue Dr.;Xiao Wei Dr.;De-Jun Wang

Angewandte Chemie 2006 Volume 118(Issue 37) pp:

Publication Date(Web):27 JUL 2006

DOI:10.1002/ange.200601668

Große Poren dank flexibler Liganden: Ein neuartiges metall-organisches Gerüst aus Cadmiumcarboxylat-Clustern als sekundären Baueinheiten und HCOOH als Brückengruppen wurde hergestellt (siehe Bild). Das poröse Material hat eine seltene innenzentrierte kubische Topologie und weist gute Sorptions- sowie optoelektronische Eigenschaften auf.

Stainless-Steel-Net-Supported Zeolite NaA Membrane with High Permeance and High Permselectivity of Oxygen over Nitrogen

Co-reporter:X. Yin;G. S. Zhu;W. Yang;Y. Li;G. Q. Zhu;R. Xu;J. Sun;S. Qiu;R. R. Xu

Advanced Materials 2005 Volume 17(Issue 16) pp:

Publication Date(Web):30 JUN 2005

DOI:10.1002/adma.200500270

A stainless-steel net is used to support a zeolite NaA membrane synthesized using a ‘seeded-growth' method. The zeolite and stainless-steel net are tightly integrated (see Figure), showing large-scale order and high mechanical stability. High oxygen permeance and high permselectivity for O₂ over N₂ (about 7) is demonstrated.

A chiral layered Co(II) coordination polymer with helical chains from achiral materials

Co-reporter:Ge Tian, Guangshan Zhu, Xiaoyu Yang, Qianrong Fang, Ming Xue, Jinyu Sun, Yan Wei and Shilun Qiu

Chemical Communications 2005 (Issue 11) pp:1396-1398

Publication Date(Web):26 Jan 2005

DOI:10.1039/B417184E

A layered coordination polymer Co(PDC)(H2O)2·H2O containing two helical chains was synthesized, and the resultant crystals were not racemic as evidenced by the observation of strong signals in vibrational circular dichroism (VCD) spectra.

Preparation of an ordered zeolite MFI film by epitaxial growth

Co-reporter:Jian Sun, Guangshan Zhu, Xiaoju Yin, Yue Chen, Yanjie Cui and Shilun Qiu

Chemical Communications 2005 (Issue 8) pp:1070-1072

Publication Date(Web):11 Jan 2005

DOI:10.1039/B416072J

An ordered zeolite MFI film has been prepared on the substrate of a {001} basal face of high-quality large silicalite-1 crystals by epitaxial growth.

Synthesis, Characterization, and Catalytic Properties of SiPW-X Mesoporous Silica with Heteropolyacid Encapsulated into Their Framework

Co-reporter:Chunfeng Shi;Runwei Wang;Guangshan Zhu;Shilun Qiu;Jun Long

European Journal of Inorganic Chemistry 2005 Volume 2005(Issue 23) pp:

Publication Date(Web):25 OCT 2005

DOI:10.1002/ejic.200500488

A series of SiPW-X mesoporous silica with Keggin-type heteropolyacids (HPAs) encapsulated into their framework have been synthesized under strong acidic conditions. During hydrolysis of tetraethyl orthosilicate (TEOS), Na₂HPO₄ (P source) and Na₂WO₄ (W Source) are added into the initial sol-gel system to form Keggin type HPAs. The final products have been intensively characterized by various techniques, such as XRD, TEM, N₂ adsorption isotherm analysis, and by IR, UV/Visible, and ³¹P Magic Angle Spinning (MAS) NMR spectroscopy. Characterization results suggest that samples with an HPA weight percent of 13.3–20.7 % show very ordered hexagonal mesostructures. In addition, HPAs incorporated in the mesosilica are insoluble during catalysis. Results of catalytic tests show that SiPW-X materials have catalytic activities that are comparable to bulk HPA in catalytic tests implementing chemical reactions of both small (cumene cracking and esterification of ethanol with acetic acid) and bulky (1,3,5-triisopropylbenzene cracking and esterification of benzoic acid with tert-butyl alcohol) molecules. It can be readily separated from the reaction system for reuse, which suggests the potential industrial application. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)

In situ synthesis of aluminophosphate microporous molecular sieve 8-hydroxyquinoline–AlPO4-5 with blue-emitting luminescence property

Co-reporter:Hua Li, Guangshan Zhu, Xiaodan Guo, Yi Li, Caijin Li, Shilun Qiu

Microporous and Mesoporous Materials 2005 Volume 85(Issue 3) pp:324-330

Publication Date(Web):7 November 2005

DOI:10.1016/j.micromeso.2005.07.002

Utilizing 8-hydroxyquinoline as a novel organic template, microporous aluminophosphate molecular sieve 8-hydroxyquinoline–AlPO4-5((C9H7NO)3 [Al12P12O48]) single crystals have been synthesized. The AFI type structure of the crystals has been identified by powder X-ray diffraction. TGA and C–H–N analysis results show there are three 8-hydroxyquinoline molecules per unit cell. The 27Al NMR indicates that quarter aluminum atoms located in the framework are distorted five-coordinated, with one-coordinated oxygen atom coming from 8-hydroxyquinoline. Two optimized configurations with the lowest energy were calculated from 12 possibilities of three aluminum atom in the framework per unit cell coordinated with three 8-hydroxyquinoline molecules. Due to the available restricted space of the micropore of AlPO4-5, the 1:1 stoichiometry Al–Q complex has been successfully achieved, which led to the strong luminescence property at room temperature and blue shift of 20 nm compared with the PL of traditional AlQ3.

Synthesis, characterization, and catalytic activities of mesostructured aluminophosphates assembled with preformed MFI zeolite nanoclusters

Co-reporter:Runwei Wang, Ling Xu, Lan Zhao, Bin Chu, Lei Hu, Chunfeng Shi, Guangshan Zhu, Shilun Qiu

Microporous and Mesoporous Materials 2005 Volume 83(1–3) pp:136-144

Publication Date(Web):1 September 2005

DOI:10.1016/j.micromeso.2005.04.004

Highly stable mesostructured heteroatom-substituted AlPOs (Al-JQW-5 and Ti-JQW-5) have been successfully synthesized by assembly of MFI zeolite nanoclusters with quaternary alkylammonium surfactants under alkaline conditions. Al-JQW-5 shows a stronger acidity than conventional SAPOs using TEOS as a silica source and Ti-JQW-5 exhibits high catalytic activities in both small molecular oxidation (phenol hydroxylation) and bulky molecular oxidation (2,3,6-trimethylphenol hydroxylation). These samples have also been characterized by X-ray diffraction, transmission electron microscopy, N2 adsorption, infrared, UV–visible spectroscopy, and a number of other techniques, and the local environment of Al, P and Si has been investigated by MAS NMR. The characterization results indicate that Al-JQW-5 and Ti-JQW-5 contain primary and secondary structural building units of MFI zeolite, which may be responsible for the stronger acidity or higher redox activities.

The fluorescence property of PNA encapsulated in the pores of oriented silicalite-1 film prepared on MSS

Co-reporter:Yue Chen, Xiaotian Li, Feifei Gao, Shilun Qiu

Materials Letters 2005 Volume 59(19–20) pp:2598-2600

Publication Date(Web):August 2005

DOI:10.1016/j.matlet.2005.02.089

Large-scale high-quality silicalite-1 films were prepared on monocrystal silica slice (MSS) by hydrothermal method. The films are b-oriented crystals perpendicular to the MSS substrate. Using such film as host material, PNA is encapsulated into the channels of the zeolite by physical vapor deposition. When pumped by 488 nm laser, PNA/silicalite-1 film showed strong fluorescence property.

A surface modification scheme for incorporation of nanocrystals in mesoporous silica matrix

Co-reporter:Lan Zhao, Guangshan Zhu, Daliang Zhang, Yue Chen, Shilun Qiu

Journal of Solid State Chemistry 2005 Volume 178(Issue 10) pp:2980-2986

Publication Date(Web):October 2005

DOI:10.1016/j.jssc.2005.06.040

A simple surface modification scheme is proposed to introduce various nanocrystals including oil-soluble Au nanocrystals, water-soluble Au nanocrystals and magnetic γ-Fe2O3 nanocrystals into mesoporous silica matrix. Disordered mesostructured cellular foam (MCF) and well-ordered FDU-12 were used as matrix materials. Surface modification of mesoporous silica with particular ligands enhanced the interaction between the matrix and nanocrystals, thereby facilitating the incorporation. High loading (up to 20% in weight) and uniform distribution of nanocrystals in mesopores were observed by transmission electron microscopy (TEM). The physical and chemical properties of nanocrystals were well maintained during this process. Moreover, the obtained composites were still highly porous with pore volume more than 1.0 cm3/g, as evidenced by N2 adsorption experiments.TEM micrograph of Au nanocrystals in FDU-12 functionalized with amine groups on inner pore surface

Ordered hexagonal mesoporous aluminosilicates synthesized using zeolite as precursor and the wall-thickness tuned by pH control

Co-reporter:Chunlei Wang, Guangshang Zhu, Tiecun Shang, Xiaohui Cai, Chengzhan Liu, Nan Li, Yuhong Wei, Jian Li, Weiwei Zhang, Shilun Qiu

Solid State Communications 2005 Volume 135(Issue 4) pp:257-259

Publication Date(Web):July 2005

DOI:10.1016/j.ssc.2005.04.025

High aluminium content mesoporous aluminosilicates MAS-X1 and MAS-X3 have been successfully synthesized using zeolite FAU-X as precursors and triblock copolymer pluronic P123 as structure directing agent. Samples have been characterized by XRD, TEM, nitrogen adsorption/desorption, 27Al MAS NMR, and ICP element analysis techniques. The salt, NaCl, which was introduced by dissolving the zeolite FAU-X, played an important role in the synthesis of high order sample. The secondary growth of the wall was considered to occur after the pH value had been increased up to five.

Rigid Nanoscopic Containers for Highly Dispersed, Stable Metal and Bimetal Nanoparticles with Both Size and Site Control

Co-reporter:Chunlei Wang Dr.;Guangshan Zhu;Jian Li;Xiaohui Cai;Yuhong Wei;Daliang Zhang;Shilun Qiu

Chemistry - A European Journal 2005 Volume 11(Issue 17) pp:

Publication Date(Web):23 JUN 2005

DOI:10.1002/chem.200500390

We demonstrate a novel strategy for the preparation of mesoporous silica-supported, highly dispersed, stable metal and bimetal nanoparticles with both size and site control. The supporting mesoporous silica, functionalized by polyaminoamine (PAMAM) dendrimers, is prepared by repeated Michael addition with methyl acrylates (MA) and amidation reaction with ethylenediamine (EDA), by using aminopropyl-functionalized mesoporous silica as the starting material. The encapsulation of metal nanoparticles within the dendrimer-propagated mesoporous silica is achieved by the chemical reduction of metal-salt-impregnated dendrimer–mesoporous silica by using aqueous hydrazine. The site control of the metal or bimetal nanoparticles is accomplished by the localization of inter- or intradendrimeric nanoparticles within the mesoporous silica tunnels. The size of the encapsulated nanoparticles is controlled by their confinement to the nanocavity of the dendrimer and the mesopore. For Cu and Pd, particles locate at the lining of mesoporous tunnels, and have diameters of less than 2.0 nm. For Pd/Pt, particles locate at the middle of mesoporous tunnels and have diameters in the range of 2.0–4.2 nm. The Pd and Pd/Pt nanoparticles are very stable in air, whereas the Cu nanoparticles are stable only in an inert atmosphere.

A Metal–Organic Framework with the Zeolite MTN Topology Containing Large Cages of Volume 2.5 nm3

Co-reporter:Qianrong Fang;Guangshan Zhu ;Ming Xue;Jinyu Sun;Yen Wei ;Shilun Qiu ;Ruren Xu

Angewandte Chemie International Edition 2005 Volume 44(Issue 25) pp:

Publication Date(Web):29 APR 2005

DOI:10.1002/anie.200462260

If you look for holes, you will find them in a novel 3D metal–organic framework complex with zeolite MTN topology. The framework of [{Cd(H₂O)₃}₃₄(N₄C₆H₁₂)₁₇]Cl₆₈⋅46 H₂O⋅68 DMF greatly expands the original structure of MTN and contains large cages with a volume of about 2522 Å³ (see structure). MTN=zeolite socony mobil – thirty-nine, DMF=N,N-dimethylformamide.

A Metal–Organic Framework with the Zeolite MTN Topology Containing Large Cages of Volume 2.5 nm3

Co-reporter:Qianrong Fang;Guangshan Zhu ;Ming Xue;Jinyu Sun;Yen Wei ;Shilun Qiu ;Ruren Xu

Angewandte Chemie 2005 Volume 117(Issue 25) pp:

Publication Date(Web):29 APR 2005

DOI:10.1002/ange.200462260

Wer nach Löchern sucht, wird schnell fündig in einem neuartigen dreidimensionalen metall-organischen Koordinationspolymer mit Zeolith-MTN-Topologie. Das Netzwerk von [{Cd(H₂O)₃}₃₄(N₄C₆H₁₂)₁₇]Cl₆₈⋅46 H₂O⋅68 DMF ist gegenüber der ursprünglichen MTN-Struktur stark aufgeweitet: Es enthält große Hohlräume mit einem Volumen von ungefähr 2522 Å³ (siehe Strukturbild).

Influence of organic bases on constructing 3D photoluminescent open metal–organic polymeric frameworks

Co-reporter:Qianrong Fang, Guangshan Zhu, Ming Xue, Jinyu Sun, Ge Tian, Gang Wu and Shilun Qiu

Dalton Transactions 2004 (Issue 14) pp:2202-2207

Publication Date(Web):10 Jun 2004

DOI:10.1039/B402715A

Four three-dimensional non-interpenetrating open coordination frameworks constructed from the CTC ligand (CTC = cis,cis-1,3,5-cyclohexanetricarboxylate) coordinated to metal ions (Mn(II) and Cd(II)): Mn3(CTC)2(DMF)2 (1); Cd3(CTC)2(H2O)3·H2O (2); Cd3(CTC)2(4,4′-bpy)2(EG)2 (3); Cd3(CTC)2(μ2-hmt)(DMF) (C2H5OH)(H2O)·2H2O (4) (DMF = dimethylformamide and EG = ethylene glycol) have been synthesized by slow evaporation of DMF–C2H5OH–H2O solutions of M(II) (Mn(II) or Cd(II)) and CTC in the presence of the organic bases TEA (triethylamine), TEA, 4,4′-bpy (4,4′-bipyridine) and hmt (hexamethylenetetramine), respectively, and structurally characterized by X-ray crystallography. The polymer 1 constructed by CTC and Mn(II) exhibits a 3-D architecture with 5 × 9 Å channels; the polymer 2 formed by CTC and Cd(II) exists a 3-D extended framework with 9 × 9 Å channels; wave-like sheet subunits of the polymer 3 are upheld by 4,4′-bpy ligands resulting in a 3-D framework with 4 × 10 Å channels; two-fold alternate sheet subunits of the polymer 4 are interlinked by μ2-hmt ligands to form a novel 3-D architecture with 7 × 8 Å channels. Polymers 2–4 exhibit their strongest excitation peaks at 391, 390 and 394 nm, respectively, and their main strong emission peaks are at 543, 460 (with a shoulder peak at about 570 nm) and 557 nm, respectively.

Novel Supramolecular Frameworks Self-Assembled from One-Dimensional Polymeric Coordination Chains

Co-reporter:Xin Shi;Guangshan Zhu;Qianrong Fang;Gang Wu;Ge Tian;Renwei Wang;Daliang Zhang;Ming Xue;Shilun Qiu

European Journal of Inorganic Chemistry 2004 Volume 2004(Issue 1) pp:

Publication Date(Web):31 OCT 2003

DOI:10.1002/ejic.200300390

The novel supramolecular frameworks [Cd(BDC)(phen)(H₂O)]_n (2) and [Cd₂(HBTC)₂(phen)₂]₂_n·nCd(HBTC)(phen)₂ (3) have been synthesized by reaction of the metal source Cd(phen)₂(NO₃)₂ (1) with benzene-1,4-dicarboxylic acid (H₂BDC) and benzene-1,3,5-tricarboxylic acid (H₃BTC), respectively in a mixed solution of DMF/C₂H₅OH/H₂O. The three-dimensional supramolecular structure of 2 is constructed through hydrogen-bond and aromatic π−π interactions between adjacent metal-organic polymeric coordination chains. Conversely, interestingly, the supramolecular architecture 3 is formed by extending 1-D metal-organic polymeric coordination chains into a 3-D framework by hydrogen-bond interactions between polymeric coordination chains and metal-organic coordination complexes instead of by interchain hydrogen-bond interactions. Additionally, these three compounds exhibit strong fluorescence at room temperature in the solid state. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)

Synthesis, structure and fluorescence of a novel three-dimensional inorganic–organic hybrid polymer constructed from trimetallic clusters and mixed carboxylate ligands

Co-reporter:Qianrong Fang, Guangshan Zhu, Xin Shi, Gang Wu, Ge Tian, Runwei Wang, Shilun Qiu

Journal of Solid State Chemistry 2004 Volume 177(4–5) pp:1060-1066

Publication Date(Web):April–May 2004

DOI:10.1016/j.jssc.2003.10.013

A new inorganic–organic hybrid framework coordination polymer, Cd3(BDC)0.5(BTC)2(DMF)(H2O)·3DMF·H3O·H2O 1, in which two carboxylate ligands, 1,4-benzenedicarboxylic acid (H2BDC) and 1,3,5-benzenetricarboxylic acid (H3BTC), coordinate with cadmium ions, has been synthesized under mild conditions and its structure solved by single-crystal X-ray diffraction (XRD) analysis. Polymer 1 crystallizes in the monoclinic system, space group P21/c (No. 14) with a=15.750(3) Å, b=14.501(3) Å, c=19.363(4) Å, β=113.67(3)°, V=4050.4(14) Å3, Z=4, R1=0.0374 and wR2=0.1148. Its structure revealed that the nine vertices of the secondary building units are linked by benzene rings from both H3BTC and H2BDC ligands to form a 3D network with 10×10 Å channels along [001] direction. Complex 1 is characterized by inductively coupled plasma analysis, powder XRD, infrared spectroscopy and thermogravimetric analysis. Polymer 1 exhibits intense fluorescence at 358 and 377 nm with λexcitation=208 nm in the solid state at room temperature.

Electroless deposition of open-end Cu nanotube arrays

Co-reporter:Nan Li, Xiaotian Li, Xiaoju Yin, Wei Wang, Shilun Qiu

Solid State Communications 2004 Volume 132(Issue 12) pp:841-844

Publication Date(Web):December 2004

DOI:10.1016/j.ssc.2004.09.040

Cu nanotube arrays were fabricated by electroless deposition using porous anodic aluminium oxide membranes as templates. This was accomplished by a four-step procedure, i.e. pore-wall modification, polishing treatment, sensitization–activation and electroless deposition. The as-synthesized Cu nanotubes possess controllable inner diameter and open ends.

Zn2[(S)-O3PCH2NHC4H7CO2]2: A Homochiral 3D Zinc Phosphonate with Helical Channels

Co-reporter:Xin Shi Dr.;Guangshan Zhu Dr.;Shilun Qiu ;Kunlin Huang Dr.;Jihong Yu ;Ruren Xu

Angewandte Chemie 2004 Volume 116(Issue 47) pp:

Publication Date(Web):1 DEC 2004

DOI:10.1002/ange.200460724

Drei Arten von Kanälen zeichnen die Struktur der Titelverbindung aus (siehe Bild): rechts- (R) und linksgängige (L) helicale sowie achirale Kanäle (A). Die katalytisch aktiven Gruppen des 1-Phosphonomethylprolin-Liganden ragen ins Innere der Kanäle, sodass das Material möglicherweise als „Heterogen-Organokatalysator“ dienen kann.

Zn2[(S)-O3PCH2NHC4H7CO2]2: A Homochiral 3D Zinc Phosphonate with Helical Channels

Co-reporter:Xin Shi Dr.;Guangshan Zhu Dr.;Shilun Qiu ;Kunlin Huang Dr.;Jihong Yu ;Ruren Xu

Angewandte Chemie International Edition 2004 Volume 43(Issue 47) pp:

Publication Date(Web):1 DEC 2004

DOI:10.1002/anie.200460724

Three types of channel—right- (R) and left-handed (L) helical, and achiral (A)—alternate along the c axis in the structure of the title compound (see picture). The catalytically active groups of the 1-phosphonomethylproline ligands are directed into the channels, thus suggesting applications of this material in asymmetric catalysis.

The synthesis and characterization of a new 3-D inorganic–organic hybrid framework porous material Zn3(bbdc)3(4,4′-bpy)·2(DMF)·4(H2O)

Co-reporter:Qianrong Fang, Xin Shi, Gang Wu, Ge Tian, Guangshu Zhu, Runwei Wang, Shilun Qiu

Journal of Solid State Chemistry 2003 Volume 176(Issue 1) pp:1-4

Publication Date(Web):15 November 2003

DOI:10.1016/S0022-4596(03)00141-5

A new 3-D inorganic–organic hybrid framework microporous material Zn3(bbdc)3(4,4′-bpy)·2(DMF)·4(H2O) (1), which is constructed by coordination of zinc ions with 4,4′-bibenzene-dicarboxylic acid (H2bbdc) and 4,4′-bipyridine (4,4′-bpy), was obtained at mild synthesis condition. Crystallographic data for the compound (1), C58H54N4O18Zn3, orthorhombic, space group Pbcn, a=14. 532(3) Å, b=25.037(5) Å, c=18.184(4) Å, Z=4, V=6616(2) Å3.

Strongly Acidic and High-Temperature Hydrothermally Stable Mesoporous Aluminosilicates with Ordered Hexagonal Structure

Co-reporter:Zongtao Zhang Dr.;Yu Han;Lei Zhu;Runwei Wang;Yi Yu;Shilun Qiu ;Dongyuan Zhao ;Feng-Shou Xiao

Angewandte Chemie 2002 Volume 114(Issue 13) pp:

Publication Date(Web):1 JUL 2002

DOI:10.1002/1521-3757(20020703)114:13<2331::AID-ANGE2331>3.0.CO;2-V

Strongly Acidic and High-Temperature Hydrothermally Stable Mesoporous Aluminosilicates with Ordered Hexagonal Structure

Co-reporter:Zongtao Zhang Dr.;Yu Han;Lei Zhu;Runwei Wang;Yi Yu;Shilun Qiu ;Dongyuan Zhao ;Feng-Shou Xiao

Angewandte Chemie International Edition 2002 Volume 41(Issue 13) pp:

Publication Date(Web):1 JUL 2002

DOI:10.1002/1521-3773(20020703)41:13<2226::AID-ANIE2226>3.0.CO;2-5

Template-assisted self-assembly of macro–micro bifunctional porous materials

Co-reporter:Guangshan Zhu, Shilun Qiu, Feifei Gao, Dongsheng Li, Yafeng Li, Runwei Wang, Bo Gao, Binsong Li, Yanghong Guo, Ruren Xu, Zheng Liu and Osamu Terasaki

Journal of Materials Chemistry A 2001 vol. 11(Issue 6) pp:1687-1693

Publication Date(Web):10 Apr 2001

DOI:10.1039/B008801N

The preparation of macro–micro bifunctional porous materials has been accomplished by a well-controlled, vacuum-assisted technique. Monodisperse polystyrene latex spheres were ordered into close-packed arrays by slow sedimentation, allowing a high flux of water through the interstices between latex spheres. Zeolite LTA, FAU, LTL, BEA, MFI and Si-MFI nanocrystals, synthesized by hydrothermal procedures, permeated the interstices of latex spheres under the driving force of flowing water. After drying and calcination at 500°C, both the latex spheres and zeolite structure-directing molecules were removed, followed by the formation of products consisting of both crystalline micropores and periodic, interconnected networks of submicron macropores. XRD, SEM, TEM, IR, TG/DTA, ICP and N2 adsorption–desorption measurements were performed to monitor the preparation and to characterize the properties of the macro–micro bifunctional porous materials. The materials presented in this paper combine the benefits of both the micropore and macropore regimes. They could potentially improve the efficiency of both separation and catalysis of zeolites.

Application of logarithmic x-axis on adsorption isotherms to improve micropore analysis

Co-reporter:Xiaodan Guo, Yu Han, Yongcun Zou, Dongsheng Li, Jihong Yu, Shilun Qiu, Feng-Shou Xiao

Microporous and Mesoporous Materials 2001 Volume 42(2–3) pp:325-336

Publication Date(Web):February 2001

DOI:10.1016/S1387-1811(00)00341-3

The adsorption isotherms for N2 over zeolite samples with various structure types or various crystal sizes have been investigated systematically. It is interesting to note that the powder samples of zeolites with cavity structures show oscillation phenomena in their adsorption isotherms on logarithmic x-axis, but the samples without cavities do not show this phenomenon. With increase in the size of the zeolite crystals, the oscillation phenomenon becomes more remarkable. If crystals are large enough and have complex channel structures, even if they do not have cavities, they also exhibit a slight oscillation phenomenon. These results are very helpful to pre-determine which model should be applied for a new sample with an unknown structure, and to get more reliable data on its pore size distribution when Horvath–Kawazoe equation is used to calculate its pore size distribution.

A new layered aluminophosphate [Al2P4O16][C6H22N4][C2H10N2] with 4.12-net porous sheets

Co-reporter:Bo Wei, Jihong Yu, Zhan Shi, Shilun Qiu and Jiyang Li

Dalton Transactions 2000 (Issue 13) pp:1979-1980

Publication Date(Web):12 Jun 2000

DOI:10.1039/B003153O

Employing phenol, an aromatic and acidic organic solid, as the solvent, and triethylene tetramine as the template, a new two-dimensional layered aluminophosphate [Al2P4O16][C6H22N4][C2H10N2] has been solvothermally synthesized for the first time, which contains novel 4.12-net porous sheets.

Size-controlled synthesis of silicalite-1 single crystals in the presence of benzene-1,2-diol

Co-reporter:Changlu Shao, Xiaotian Li, Shilun Qiu, Feng-shou Xiao, Osamu Terasaki

Microporous and Mesoporous Materials 2000 Volume 39(1–2) pp:117-123

Publication Date(Web):September 2000

DOI:10.1016/S1387-1811(00)00183-9

By adding benzene-1,2-diol as a complex agent for silicon into the system: SiO2–TPABr–NaOH–R–H2O (R: benzene-1,2-diol), single crystals of zeolites silicalite-1 with different crystallite sizes ranging from 9×3×2 μm to 165×30×30 μm were obtained. Experimental results showed that crystals synthesized in the presence of benzene-1,2-diol have a much larger size and better morphology than those synthesized in the absence of benzene-1,2-diol, and their sizes were largely influenced by the content of benzene-1,2-diol in the reaction system. The role of benzene-1,2-diol in the hydrothermal reaction mixture has been characterized by 29Si-NMR, and it was shown that silicon–benzene-1,2-diol complex was formed in the reaction system, which was very important for the synthesis of large single crystals of zeolites.

Preparation, characterization, and optical properties of the host-guest nanocomposite material zeolite-silver iodide

Co-reporter:Qing-Zhou Zhai, Shilun Qiu, Feng-Shou Xiao, Zong-Tao Zhang, Chang-Lu Shao, Yu Han

Materials Research Bulletin 2000 Volume 35(Issue 1) pp:59-73

Publication Date(Web):January 2000

DOI:10.1016/S0025-5408(00)00193-8

Zeolites NaZSM-5 and NaY as hosts for producing nanoscale silver iodide guest were studied with the goal of investigating the optical properties of the prepared host-guest nanocomposite materials. The host-guest nanocomposite materials of NaY–AgI and (NaZSM-5)–AgI were prepared by a heat diffusion method. The nanocomposite materials prepared were characterized by X-ray diffraction (XRD), differential thermal analysis (DTA), X-ray photoelectric spectroscopy (XPS), and adsorption. The properties of the diffuse reflectance absorption spectra and the surface photovoltage spectra of the prepared nanocomposite materials were investigated. The quantum confinement effect of the channels of zeolites made the prepared host-guest nanocomposite materials show some interesting optical properties. This makes the investigated nanomaterials suitable for use as quantum electronic and optoelectric materials.

BN and Si nanostructures: preparation and visible photoluminescence properties

Co-reporter:Xiaotian Li, Changlu Shao, Shilun Qiu, Feng-Shou Xiao, Weitao Zheng, Osamu Terasaki

Materials Letters 2000 Volume 44(Issue 6) pp:341-346

Publication Date(Web):July 2000

DOI:10.1016/S0167-577X(00)00056-2

We report strong visible photoluminescence (PL) at room temperature from BN and Si nanometer-sized particles prepared through chemical vapor deposition (CVD) in the pores of zeolite NaY and ZSM-5. The samples were characterized by X-ray diffraction (XRD), thermogravimetry analyses (TG), and UV–Vis absorption. Analysis of PL spectra leads us to propose that the Si and BN nanometer-sized particles, a kind of quasi-direct-gap semiconductor transferred from indirect-gap materials by encapsulation method, are possible origins of the strong PL.

The role of pyrocatechol as a complex agent for silicon in the synthesis of large single crystals of silica-sodalite zeolite

Co-reporter:Changlu Shao, Xiaotian Li, Shilun Qiu, Feng-Shou Xiao

Microporous and Mesoporous Materials 1999 Volume 33(1–3) pp:215-222

Publication Date(Web):15 December 1999

DOI:10.1016/S1387-1811(99)00140-7

To investigate the role of a complex agent in synthesizing large single crystals of silica-sodalite, pyrocatechol was added as an additive to the system SiO2–NaOH–EG (EG=ethylene glycol). Experimental results showed that the crystals synthesized in the presence of pyrocatechol have much larger size and better morphology than those synthesized in the absence of pyrocatechol. The role of pyrocatechol in the hydrothermal reaction mixture was investigated by 29Si NMR, IR, and UV–vis spectroscopy, and it was shown that a silicon–pyrocatechol complex was formed in the reaction system.

Novel mesoporous silica spheres with ultra-large pore sizes and their application in protein separation

Co-reporter:Lihua Chen, Guangshan Zhu, Daliang Zhang, Hang Zhao, Mingyi Guo, Wei Shi and Shilun Qiu

Journal of Materials Chemistry A 2009 - vol. 19(Issue 14) pp:NaN2017-2017

Publication Date(Web):2009/02/11

DOI:10.1039/B818740A

Synthesis of a metal–organic framework film by direct conversion technique for VOCs sensing

Co-reporter:Xiaoqin Zou, Guangshan Zhu, Ian J. Hewitt, Fuxing Sun and Shilun Qiu

Dalton Transactions 2009(Issue 16) pp:NaN3013-3013

Publication Date(Web):2009/03/10

DOI:10.1039/B822248G