Co-reporter:Ya Chen, Bin Wang, Xiaoqing Wang, Lin-Hua Xie, Jinping Li, Yabo Xie, and Jian-Rong Li
ACS Applied Materials & Interfaces August 16, 2017 Volume 9(Issue 32) pp:27027-27027
Publication Date(Web):July 18, 2017
DOI:10.1021/acsami.7b07920
Copper(II)-paddlewheel-based metal–organic frameworks (CP-MOFs) represent a unique subclass of MOFs with highly predictable porous structures, facile syntheses, and functional open metal sites. However, the lack of high hydrolytic stability is an obstacle for CP-MOFs in many practical applications. In this work, we report a new CP-MOF, [Cu4(tdhb)] (BUT-155), which is constructed from a judiciously designed carboxylate ligand with high coordination connectivity (octatopic), abundant hydrophobic substituents (six methyl groups), and substituent constrained geometry (tetrahedral backbone), tdhb8– [H8tdhb = 3,3′,5,5′-tetrakis(3,5-dicarboxyphenyl)-2,2′,4,4′,6,6′-hexamethylbiphenyl)]. BUT-155 shows high porosity with a Brunauer–Emmett–Teller surface area of 2070 m2/g. Quite interestingly, this CP-MOF retains its structural integrity after being treated in water for 10 days at room temperature or in boiling water for 24 h. To the best of our knowledge, BUT-155 represents the first CP-MOF that is demonstrated to retain its structural integrity in boiling water. The high hydrolytic stability of BUT-155 allowed us to carry out adsorption studies of water vapor and aqueous organic pollutants on it. Water-vapor adsorption reveals a sigmoidal isotherm and a high uptake (46.7 wt %), which is highly reversible and regenerable. In addition, because of the availability of soft-acid-type open Cu(II) sites, BUT-155 shows a high performance for selective adsorption of soft-base-type aniline over water or phenol, and a naked-eye detectable color change for the MOF sample accompanies this. The adsorption selectivity and high adsorption capacity of aniline in BUT-155 are also well-interpreted by single-crystal structures of the water- and aniline-included phases of BUT-155.Keywords: aniline capture and detection; copper(II) paddlewheel; hydrolytic stability; octatopic ligand; water-vapor adsorption;
Co-reporter:Jian Zhou;Yibo Dou;Awu Zhou;Rui-Mei Guo;Min-Jian Zhao
Advanced Energy Materials 2017 Volume 7(Issue 12) pp:
Publication Date(Web):2017/06/01
DOI:10.1002/aenm.201602643
The ever-increasing demand for clean and renewable power sources has sparked intensive research on water splitting to produce hydrogen, in which the exploration of electrocatalysts is the central issue. Herein, a new strategy, metal–organic framework template-directed fabrication of hierarchically structured Co3O4@X (X = Co3O4, CoS, C, and CoP) electrocatalysts for efficient oxygen evolution reaction (OER) is developed, where Co3O4@X are derived from cobalt carbonatehydroxide@zeolitic-imidazolate-framework-67 (CCH@ZIF-67). Unique hierarchical structure and synergistic effect of resulting catalysts endow abundant exposed active sites, facile ion diffusion path, and improved conductivity, being favorable for improving catalytic activity of them. Consequently, these derivatives Co3O4@X reveal highly efficient electrocatalytic performance with long-term durability for the OER, much superior to previously reported cobalt-based catalysts as well as the Ir/C catalyst. Particularly, Co3O4@CoP exhibits the highest electrocatalytic capability with the lower overpotential of 238 mV at the current density of 10 mA cm−2. Furthermore, Co3O4@X can also efficiently catalyze other small molecules through electro-oxidation reaction (e.g., glycerol, methanol, or ethanol). It is expected that the strategy presented here can be extended to the fabrication of other composite electrode materials with hierarchical structures for more efficient water splitting.
Co-reporter:Ya Chen;Ling Wang;Yanan Zhai;Heyin Chen;Yibo Dou;Jianrong Li;Haoquan Zheng;Rui Cao
RSC Advances (2011-Present) 2017 vol. 7(Issue 51) pp:32310-32315
Publication Date(Web):2017/06/21
DOI:10.1039/C7RA04390B
A composite material of Pd–Ni nanoparticles supported on reduced graphene oxide (Pd–Ni/rGO) has been synthesised via an in situ reduction of PdO/Ni(OH)2 nanoparticles on GO. This Pd–Ni/rGO material is characterised by powder X-ray diffraction, transmission electron microscopy, scanning electron microscopy and X-ray photoelectron spectroscopy. The molar ratio of Pd/Ni in the alloy nanoparticles can be fine tuned by changing the starting ratio of Pd/Ni precursors during synthesis. The bimetallic Pd3Ni/rGO exhibits high catalytic activity, selectivity, and durability toward the hydrogen generation from hydrazine, while corresponding monometallic (Pd/rGO or Ni/rGO) counterparts are either inactive or poorly active under analogous reaction conditions.
Co-reporter:Yibo Dou;Jian Zhou;Awu Zhou;Zuoren Nie
Journal of Materials Chemistry A 2017 vol. 5(Issue 36) pp:19491-19498
Publication Date(Web):2017/09/19
DOI:10.1039/C7TA06443H
A strategy that visible-light responsive zeolitic-imidazolate-framework-67 (ZIF-67) encapsulates noble-metal sensitized semiconductors, ZnO@M (M = Au, Pt, and Ag) to fabricate composite catalysts for photoelectrochemical (PEC) water splitting is proposed. The obtained ZnO@M@ZIF-67 catalysts have good catalytic performance, particularly, the ZnO@Au@ZIF-67 exhibits quite improved photoconversion efficiency and photocurrent density, superior to most of the reported photoelectrode catalysts. This can be attributed to the wider solar spectra harvesting capability originating from visible-light responsive ZIF-67 and UV-light active ZnO. Simultaneously, their integration enables interfacial electrons in the ZIF-67 shell to easily transfer to the ZnO@Au core, providing good electron–hole separation. In addition, the porous ZIF-67 as a protective shell ensures structural robustness, while maintaining fast ion or gas bubble diffusion through its pores, accounting for stable and excellent PEC performance.
Co-reporter:Hao Wu;Fan Yang;Xiu-Liang Lv;Bin Wang;Yong-Zheng Zhang;Min-Jian Zhao
Journal of Materials Chemistry A 2017 vol. 5(Issue 28) pp:14525-14529
Publication Date(Web):2017/07/18
DOI:10.1039/C7TA03917D
A new porphyrinic metal–organic framework (MOF), [Co(DCDPP)]·5H2O, was designed and constructed by using a bifunctional ligand, 5,15-di(4-carboxylphenyl)-10,20-di(4-pyridyl)porphyrin (H2DCDPP). This MOF features a three-dimensional framework structure with open channels, surrounded by high-density non-coordinating carboxylic groups, and exhibits a high proton conductivity of 3.9 × 10−2 S cm−1 at 80 °C and 97% relative humidity, higher than most conductive MOFs. Moreover, it also shows excellent stability in boiling water and cyclic proton conduction.
Co-reporter:Yan Bai, Yibo Dou, Lin-Hua Xie, William Rutledge, Jian-Rong Li and Hong-Cai Zhou
Chemical Society Reviews 2016 vol. 45(Issue 8) pp:2327-2367
Publication Date(Web):17 Feb 2016
DOI:10.1039/C5CS00837A
Among the large family of metal–organic frameworks (MOFs), Zr-based MOFs, which exhibit rich structure types, outstanding stability, intriguing properties and functions, are foreseen as one of the most promising MOF materials for practical applications. Although this specific type of MOF is still in its early stage of development, significant progress has been made in recent years. Herein, advances in Zr-MOFs since 2008 are summarized and reviewed from three aspects: design and synthesis, structure, and applications. Four synthesis strategies implemented in building and/or modifying Zr-MOFs as well as their scale-up preparation under green and industrially feasible conditions are illustrated first. Zr-MOFs with various structural types are then classified and discussed in terms of different Zr-based secondary building units and organic ligands. Finally, applications of Zr-MOFs in catalysis, molecule adsorption and separation, drug delivery, and fluorescence sensing, and as porous carriers are highlighted. Such a review based on a specific type of MOF is expected to provide guidance for the in-depth investigation of MOFs towards practical applications.
Co-reporter:Yuxiu Sun;Fan Yang;Qi Wei;Naixin Wang;Xi Qin;Shaokang Zhang;Bin Wang;Zuoren Nie;Shulan Ji;Hui Yan
Advanced Materials 2016 Volume 28( Issue 12) pp:2374-2381
Publication Date(Web):
DOI:10.1002/adma.201505437
Co-reporter:Ying-Hu Kang; Xiao-Dan Liu; Ni Yan; Yao Jiang; Xiao-Qin Liu; Lin-Bing Sun
Journal of the American Chemical Society 2016 Volume 138(Issue 19) pp:6099-6102
Publication Date(Web):April 6, 2016
DOI:10.1021/jacs.6b01207
Metal–organic polyhedra (MOPs) have attracted great attention due to their intriguing structure. However, the applications of MOPs are severely hindered by two shortcomings, namely low dispersity and poor stability. Here we report the introduction of four MOPs (constructed from dicopper and carboxylates) to cavity-structured mesoporous silica SBA-16 via a double-solvent strategy to overcome both shortcomings simultaneously. By judicious design, the dimension of MOPs is just between the size of cavities and entrances of SBA-16, MOP molecules are thus confined in the cavities. This leads to the formation of isolated MOPs with unusual dispersion, making the active sites highly accessible. Hence, the adsorption capacity on carbon dioxide and propene as well as catalytic performance on ring opening are much superior to bulk MOPs. More importantly, the structure and catalytic activity of MOPs in confined cavities are well preserved after exposure to humid atmosphere, whereas those of bulk MOPs are degraded seriously.
Co-reporter:Xiu-Liang Lv, Kecheng Wang, Bin Wang, Jie Su, Xiaodong Zou, Yabo Xie, Jian-Rong LiHong-Cai Zhou
Journal of the American Chemical Society 2016 Volume 139(Issue 1) pp:211-217
Publication Date(Web):December 11, 2016
DOI:10.1021/jacs.6b09463
A base-resistant porphyrin metal–organic framework (MOF), namely PCN-602 has been constructed with 12-connected [Ni8(OH)4(H2O)2Pz12] (Pz = pyrazolate) cluster and a newly designed pyrazolate-based porphyrin ligand, 5,10,15,20-tetrakis(4-(pyrazolate-4-yl)phenyl)porphyrin under the guidance of the reticular synthesis strategy. Besides its robustness in hydroxide solution, PCN-602 also shows excellent stability in aqueous solutions of F–, CO32–, and PO43– ions. Interestingly, the Mn3+-porphyrinic PCN-602, as a recyclable MOF catalyst, presents high catalytic activity for the C–H bond halogenation reaction in a basic system, significantly outperforming its homogeneous counterpart. For the first time, a porphyrinic MOF was thus used as an efficient catalyst in a basic solution with coordinating anions, to the best of our knowledge.
Co-reporter:Bin Wang; Xiu-Liang Lv; Dawei Feng; Lin-Hua Xie; Jian Zhang; Ming Li; Yabo Xie; Jian-Rong Li;Hong-Cai Zhou
Journal of the American Chemical Society 2016 Volume 138(Issue 19) pp:6204-6216
Publication Date(Web):April 19, 2016
DOI:10.1021/jacs.6b01663
Antibiotics and organic explosives are among the main organic pollutants in wastewater; their detection and removal are quite important but challenging. As a new class of porous materials, metal–organic frameworks (MOFs) are considered as a promising platform for the sensing and adsorption applications. In this work, guided by a topological design approach, two stable isostructural Zr(IV)-based MOFs, Zr6O4(OH)8(H2O)4(CTTA)8/3 (BUT-12, H3CTTA = 5′-(4-carboxyphenyl)-2′,4′,6′-trimethyl-[1,1′:3′,1″-terphenyl]-4,4″-dicarboxylic acid) and Zr6O4(OH)8(H2O)4(TTNA)8/3 (BUT-13, H3TTNA = 6,6′,6″-(2,4,6-trimethylbenzene-1,3,5-triyl)tris(2-naphthoic acid)) with the the-a topological structure constructed by D4h 8-connected Zr6 clusters and D3h 3-connected linkers were designed and synthesized. The two MOFs are highly porous with the Brunauer–Emmett–Teller surface area of 3387 and 3948 m2 g–1, respectively. Particularly, BUT-13 features one of the most porous water-stable MOFs reported so far. Interestingly, these MOFs represent excellent fluorescent properties, which can be efficiently quenched by trace amounts of nitrofurazone (NZF) and nitrofurantoin (NFT) antibiotics as well as 2,4,6-trinitrophenol (TNP) and 4-nitrophenol (4-NP) organic explosives in water solution. They are responsive to NZF and TNP at parts per billion (ppb) levels, which are among the best performing luminescent MOF-based sensing materials. Simultaneously, both MOFs also display high adsorption abilities toward these organic molecules. It was demonstrated that the adsorption plays an important role in the preconcentration of analytes, which can further increase the fluorescent quenching efficiency. These results indicate that BUT-12 and -13 are favorable materials for the simultaneous selective detection and removal of specific antibiotics and organic explosives from water, being potentially useful in monitoring water quality and treating wastewater.
Co-reporter:Yibo Dou, Jian Zhou, Fan Yang, Min-Jian Zhao, Zuoren Nie and Jian-Rong Li
Journal of Materials Chemistry A 2016 vol. 4(Issue 32) pp:12526-12534
Publication Date(Web):12 Jul 2016
DOI:10.1039/C6TA04765C
CoAl-based layered-double-hydroxide@zeolitic-imidazolate-framework-67 (LDH@ZIF-67) was fabricated via a hydrothermal synthesis of LDH film on Ni substrate followed by the in situ growth of ZIF-67. Its derivatives, MMO@Co3O4, spinelle@C and LDH@CoS with hierarchical structures were obtained by the subsequent oxidation, carbonization and sulfurization of LDH@ZIF-67, respectively, which exhibit distinct specific capacitances of 692, 781 and 1205 F g−1 at a discharge current density of 1 A g−1. Interestingly, these derivatives retained hierarchical structures with large surface area, which ensures that the majority of exposed active species can participate in the charge–discharge process and thus effectively contribute to total capacitances. The synergistic effect from fast electronic transfer reduces reversible ion accumulation at the interface, which imparts LDH@ZIF-67 derivatives improved electrochemical activities, in contrast to conventional bulk MOF derivatives. In addition, it was found that the combination of the remarkable electrical conductivity of sulfides (compared with their oxide counterparts) and the strong electronic coupling between LDH and CoS can facilitate fast electron transfer. As a result, LDH@CoS exhibits an excellent specific energy of 44.5 W h kg−1 at a current density of 20 A g−1, as well as good capacitance retention of 88.5% after 2000 cycles. This work thus demonstrates a feasible strategy for the design and fabrication of LDH@MOF derived composites as SCs components, which is applicable in constructing other novel electrode materials with hierarchical structures for applications in energy storage systems.
Co-reporter:Jiong-Peng Zhao, Yabo Xie, Jian-Rong Li and Xian-He Bu
Dalton Transactions 2016 vol. 45(Issue 4) pp:1514-1524
Publication Date(Web):03 Dec 2015
DOI:10.1039/C5DT03667D
Low-temperature hydrothermal reactions of copper salts with NaN3 and structurally related pyridine-based ligands, 1-(4-pyridyl)pyridinium, 3-chloromethylpyridine, 4-benzylpyridine, and quinoline (L4), respectively, led to the formation of four new magnetic complexes, [Cu3(L1)2(N3)6]n (1), [Cu3(L2)2(N3)6]n (2), [Cu(L3)2(N3)2] (3), and [Cu(L4)(N3)2]n (4). In these complexes, L1, L2, and L3 are pyridine, 3-azidomethylpyridine, and 4-benzoylpyridine, being generated in situ by the decomposition, azido substitution, and oxidation reaction of the 1-(4-pyridyl)pyridinium, 3-chloromethylpyridine, and 4-benzylpyridine, respectively. 1 and 2 have similar structures being composed of double end-on azido-bridging planar [Cu3(L)2(N3)6] trinuclear units, which are further linked into a two-dimensional layer by the end-to-end azido bridges of themselves, along with their weak end-on coordination. It is interesting that the only slight differences of geometrical parameters in 1 and 2 have led to distinct magnetic interactions between the trinuclear units, where the former is antiferromagnetic but the latter is ferromagnetic, whereas 3 has a mono-nuclear core structure, which is further extended to a one-dimensional (1D) chain by weakly coordinated end-on azido bridges. 4 consists of unique 1D chains with double end-on azido bridge bonding distorted five-coordinated Cu(II) centers, and exhibits ferromagnetic intrachain interactions. In the structures of these complexes there also exist weak inter-layer or inter-chain hydrogen bonds, which should also be responsible for some magnetic behavior at low temperature. In addition, primary structural and magnetic comparisons and discussions have also been performed by combining other reported azido-Cu(II) systems with related pyridyl-based co-ligands. These results show that the selection of synthesis conditions and slight decoration of co-ligands (or geometric differences of them) have important influences on the structures and magnetic properties of resulting metal azido complexes.
Co-reporter:Bin Wang, Hui Yang, Ya-Bo Xie, Yi-Bo Dou, Min-Jian Zhao, Jian-Rong Li
Chinese Chemical Letters 2016 Volume 27(Issue 4) pp:502-506
Publication Date(Web):April 2016
DOI:10.1016/j.cclet.2015.12.034
Two new metal-organic frameworks (MOFs), [Cu2(H2O)2(BCPIA)] (BUT-20) and (Me2NH2)[In(BCPIA)] (BUT-21) were designed and synthesized through the solvothermal reaction between a newly created desymmetric 4-connected ligand, 5-(2,6-bis(4-carboxyphenyl)pyridin-4-yl)isophthalic acid (H4BCPIA) and Cu(NO3)2·2.5H2O or In(NO3)3·5H2O, respectively, and characterized by single-crystal and powder X-ray diffraction, thermogravimetric analysis, infrared spectroscopy, and elemental analysis. The two MOFs have three-dimensional structures, in which both the BCPIA4– ligand and metal-containing entities, Cu2(COO)4(H2O)2 and In(COO)4 act as 4-connected nodes. However, different linkage configurations of the two metal-containing nodes, quadrilateral Cu2(COO)4(H2O)2 and tetrahedral In(COO)4, lead to distinct structural networks of BUT-20 and -21, with Nbo and Unc topologies, respectively.Two metal-organic frameworks (MOFs) (BUT-20 and -21) based on a newly designed desymmetric 4-connected ligand, 5-(2,6-bis(4-carboxyphenyl)pyridin-4-yl)isophthalic acid (H4BCPIA) were designed and synthesized. Different linkage configurations of metal-containing nodes, Cu2(COO)4(H2O)2 and In(COO)4 in the two MOFs lead to distinct topologies of their structures.
Co-reporter:Tao He;Yong-Zheng Zhang;Bin Wang;Xiu-Liang Lv; Lin-Hua Xie; Jian-Rong Li
ChemPlusChem 2016 Volume 81( Issue 8) pp:864-871
Publication Date(Web):
DOI:10.1002/cplu.201600163
Abstract
A ZnII-based metal–organic framework (MOF), [Zn2(bdp-CHO)2]⋅(DMF)(CH3CN)(H2O)2 (BUT-31) is reported that was synthesized by the reaction between a newly designed aldehyde-tagged polypyrazole ligand 2,5-di(1H-pyrazol-4-yl)benzaldehyde (H2bdp-CHO) and a zinc salt. BUT-31 has a unique pillared layered framework structure with 3D intersecting channels approximately 3.4–5.4 Å in size. Powder X-ray diffraction and N2 adsorption experiments revealed that BUT-31 is rigid and permanently porous with the Brunauer–Emmett–Teller surface area of 926 m2 g−1. Notably, this MOF tolerates boiling water and even highly basic aqueous solution (4 m sodium hydroxide), although dilute acid gradually decomposes its framework. Owing the permanent porosity and chemical stability of BUT-31, covalent post-modification of the free aldehyde group exposed on the pore surface was accomplished by treating the MOF in a concentrated ammonia solution (25 %) at near room temperature, giving rise to an imine-functionalized analogue of BUT-31. Gas adsorption results show that the aldehyde- and imine-functionalized MOFs have high CO2 adsorption capacities, as well as CO2/N2 and CO2/CH4 adsorption selectivities.
Co-reporter:Kecheng Wang; Xiu-Liang Lv; Dawei Feng; Jian Li; Shuangming Chen; Junliang Sun; Li Song; Yabo Xie; Jian-Rong Li;Hong-Cai Zhou
Journal of the American Chemical Society 2015 Volume 138(Issue 3) pp:914-919
Publication Date(Web):December 30, 2015
DOI:10.1021/jacs.5b10881
Guided by a top-down topological analysis, a metal–organic framework (MOF) constructed by pyrazolate-based porphyrinic ligand, namely, PCN-601, has been rationally designed and synthesized, and it exhibits excellent stability in alkali solutions. It is, to the best of our knowledge, the first identified MOF that can retain its crystallinity and porosity in saturated sodium hydroxide solution (∼20 mol/L) at room temperature and 100 °C. This almost pushes base-resistance of porphyrinic MOFs (even if MOFs) to the limit in aqueous media and greatly extends the range of their potential applications. In this work, we also tried to interpret the stability of PCN-601 from both thermodynamic and kinetic perspectives.
Co-reporter:Yi Han, Shunan Sheng, Fan Yang, Yabo Xie, Minjian Zhao and Jian-Rong Li
Journal of Materials Chemistry A 2015 vol. 3(Issue 24) pp:12804-12809
Publication Date(Web):26 May 2015
DOI:10.1039/C5TA00963D
A new metal–organic framework, {[(CH3)2NH2][Co2NaL2(CH3COO)2]·xS}n (BUT-51, H2L = 5-(pyridine-4-yl)isophthalic acid) with two types of nanotubular channels, was synthesized and used in dye adsorption. It was found that cationic dyes, including Methylene Blue (MB), Acridine Red (AR) and Acriflavine Hydrochloride (AH), can be rapidly adsorbed by BUT-51, but larger Methylene Violet (MV) and anionic Methyl Orange (MO), as well as neutral Solvent Yellow 2 (SY2), can hardly be adsorbed. These results imply that the adsorption behaviour of BUT-51 with the cationic dyes follows not only a charge- but also size- and shape-exclusive effect. Surprisingly, BUT-51 also preferentially adsorbs (or separates) AH from MB and AR, respectively, in their mixed acetone solution, probably due to the coordination between AH and Co2+ in its framework. Furthermore, AH uptake can change the porosity and framework stability of BUT-51 to give a robust partner.
Co-reporter:Xiuling Zhang, Yong-Zheng Zhang, Da-Shuai Zhang, Baoyong Zhu and Jian-Rong Li
Dalton Transactions 2015 vol. 44(Issue 35) pp:15697-15702
Publication Date(Web):24 Jul 2015
DOI:10.1039/C5DT01770J
By the solvothermal reaction of a triangular ligand, 2,4,6-tris-(4-carboxyphenoxy)-1,3,5-triazine (H3tcpt) with Zn(NO3)2·6H2O in N,N′-dimethylacetamide/acetonitrile/H2O (v/v/v = 1:1:1) mixed solvents, a two-fold, interpenetrated, three-dimensional (3D), porous metal–organic framework, [Zn2(tcpt)OH]·solvents (1·solvents), with a rare, paddlewheel secondary building unit (SBU), Zn2(COO)3, was synthesized and characterized. It was found that a single 3D structure of 1 forms when two-dimensional layers, which are constructed by tcpt3− bonding with the paddlewheel SBUs, are linked by –OH groups along the axial sites of the SBUs. Compared with the reported Zn(II)-based partners with this ligand, synthesis conditions, particularly the solvents used, clearly played a key role in the formation of different SBUs, thereby resulting in distinct MOFs with the same ligand. In particular, 1 features good water and thermal stability and can withstand acidic aqueous solutions with pH values ranging from 5 to 12. In addition, 1 displays good adsorption ability towards H2 (2.21 wt% at 77 K and 1 atm) and can selectively adsorb CO2 from CH4 and N2, in spite of its relatively low void volume (36.8%), suggesting potential applications in gas storage and separation.
Co-reporter:Ya-Bo Xie, Lei Gan, E. Carolina Sañudo, Haiyang Zheng, Jiongpeng Zhao, Minjian Zhao, Bin Wang and Jian-Rong Li
CrystEngComm 2015 vol. 17(Issue 22) pp:4136-4142
Publication Date(Web):22 Apr 2015
DOI:10.1039/C5CE00531K
As the first example of using a parent tetrazole and an azide together in preparing magnetic complexes, two novel tetrazolate–azido-bridged Cu(II) coordination polymers, [Cu(tz)(N3)]n (1) and [Cu(tz)(N3)(NH3)2]n (2) (tz = tetrazolate), have been synthesized through the reaction of Htz, CuCl2, and NaN3 under hydrothermal conditions and in ammonia solution at room temperature, respectively. Single crystal X-ray structure analysis reveals that the two complexes possess distinct three-dimensional (3D) framework structures and can be topologically described as a 3-connected srs (SrSi2)-type net and a 4-connected cds (CdSO4)-type net, respectively. Both tetrazolate and azide groups also have different linkage modes in the two complexes. 1 contains end-on (EO) type azide bridges and 3-connected tetrazolate, while 2 possess end-to-end (EE) azide linkers and 2-coordinated tetrazolate. Magnetic measurements indicate that antiferrimagnetic interactions dominate between Cu(II) ions in the two complexes with the corresponding magnetic coupling constant being J = −41.0 cm−1 in 1 and J = −8.62 cm−1 in 2.
Co-reporter:Fan Yang, Hongliang Huang, Xiayan Wang, Fan Li, Yuhan Gong, Chongli Zhong, and Jian-Rong Li
Crystal Growth & Design 2015 Volume 15(Issue 12) pp:5827
Publication Date(Web):November 16, 2015
DOI:10.1021/acs.cgd.5b01190
Pursuing new proton-conducting materials has become a key issue to improve the performance of proton exchange membrane fuel cells for clean energy. As newly emerging materials, metal–organic frameworks (MOFs) have been attracting wide attention in this regard. Herein, using stable UiO-66 as a platform, through the modification of different functional groups of −SO3H, −2COOH, −NH2, and −Br in ligands, we explore the strategy to tune the proton conductivities of MOFs. With the highly acidic and strong hydrophilic functional groups −SO3H and −COOH, UiO-66-SO3H and UiO-66-2COOH show quite high proton conductivities of 0.34 × 10–2 and 0.10 × 10–2 S cm–1 at 303 K and ∼97% relative humidity, respectively while the −NH2, −H, and −Br represent comparatively low conductivities under the same conditions. Furthermore, water molecules adsorbed in the pores are proved to contribute greatly to the proton conductivities of these MOFs. Thermogravimetry-mass spectrometry (TG-MS) and molecular simulations are then used to analyze the interactions between the water molecules and MOFs. TG-MS analyses show two water molecule loss processes in UiO-66-SO3H and UiO-66-2COOH, but one in UiO-66-NH2, UiO-66, and UiO-66-Br during heating, which indicates the stronger affinity of −SO3H and −COOH functionalized UiO-66 toward water molecules than those with −NH2 and −Br, as well as UiO-66 itself. The isosteric heats (−Qst) of water adsorption and radial distribution functions (RDFs) in these MOFs are also evaluated by molecular simulations. It was found that UiO-66-SO3H and UiO-66-2COOH have higher −Qst of 86.50 and 52.10 kJ mol–1, whereas UiO-66-NH2, UiO-66, and UiO-66-Br have lower ones, 34.03, 19.04, and 36.36 kJ mol–1, respectively. The RDFs reveal the formation of hydrogen-bonding networks in UiO-66-SO3H, UiO-66-2COOH, UiO-66-NH2, and UiO-66, but not in UiO-66-Br.
Co-reporter:Jiong-Peng Zhao, Cui Zhao, Wei-Chao Song, Lei Wang, Yabo Xie, Jian-Rong Li and Xian-He Bu
Dalton Transactions 2015 vol. 44(Issue 22) pp:10289-10296
Publication Date(Web):22 Apr 2015
DOI:10.1039/C5DT00568J
The structure and magnetism of three cobalt(II)–azide complexes, [Co(N3)2(bepy)2]n (1), [Co2(N3)4(vipy)4]n (2), and [Co(N3)2(bipy)]n (3) were tuned by three structurally related 4-substituent pyridines, 4-benzylpyridine (bepy), 4-vinyl pyridine (vipy), and 4,4′-bipyridine (bipy) as co-ligands in solvothermal reactions. With flexible benzyl as a substituent group of the pyridine co-ligand, a one-dimensional (1D) complex 1 with double end-to-end (EE) azide-bridging Co(II) chain is formed. While using a rigid but small vinyl group as the substituent, a distinct Co(II)–azide chain with alternate double end-on (EO) and double EE azide bridges was obtained. Finally, when another pyridine group was used instead of the substituent incapable of coordinating in 1 and 2, a bipyridine, it gave rise to a chiral complex 3 with a three-dimensional (3D) diamondoid Co(II)–azide framework further reinforced by the bipy ligand. Magnetic studies indicate antiferromagnetic interactions between the Co(II) ions in the three complexes, but interestingly, weak antiferromagnetism origin of spin canting exists in 3 at low temperatures.
Co-reporter:Naixin Wang, Jida Liu, Jie Li, Jing Gao, Shulan Ji, Jian-Rong Li
Microporous and Mesoporous Materials 2015 Volume 201() pp:35-42
Publication Date(Web):1 January 2015
DOI:10.1016/j.micromeso.2014.09.010
•Modified silicalite-1 compatibility with PDMS by tuning its sizes and morphologies.•Improved silicalite-1 compatibility with PDMS through its functional modifications.•Optimized ethanol/water separation performance of PDMS hybrid membranes.The silicalite-1/PDMS hybrid membranes have been widely studied in alcohol perm-selective pervaporation separations. However, the poor compatibility between silicalite-1 particles and PDMS has already rebated the separation performance of these hybrid membranes. In this paper, two approaches were investigated to improve/tune the compatibility of the silicalite-1 particles and PDMS matrix. Firstly, silicalite-1 crystal particles with different sizes were synthesized. The effects of the particle size on the compatibility between silicalite-1 and PDMS were investigated. It was found that smaller silicalite-1 crystals (about 100 nm) have a better compatibility with PDMS matrix, thereby an enhanced separation performance of their hybrid membranes. Subsequently, the surface of silicalite-1 particles were modified through three kinds of silane coupling agents with different functional groups, which was confirmed to be feasible in increasing the compatibility with PDMS. In ethanol/water pervaporation separation, a higher selectivity was achieved in the PDMS hybrid membrane with TMDS-modified small silicalite-1 crystals. Moreover, silicalite-1 crystals provide many separate channels, so that the separation performance of the hybrid membrane has dramatically increased.
Co-reporter:Yi Han, Jian-Rong Li, Yabo Xie and Guangsheng Guo
Chemical Society Reviews 2014 vol. 43(Issue 16) pp:5952-5981
Publication Date(Web):24 Apr 2014
DOI:10.1039/C4CS00033A
Substitution reaction, as one of the most powerful and efficient chemical reactions, has been widely used in various syntheses, including those for the design and preparation of functional molecules or materials. In the past decade, a class of newly developed inorganic–organic hybrid materials, namely metal–organic materials (MOMs), has experienced a rapid development. MOMs are composed of metal-containing nodes connected by organic linkers through strong chemical bonds, and can be divided into metal–organic frameworks (MOFs) and metal–organic polygons/polyhedra (MOPs) with infinite and discrete structural features, respectively. Recent research has shown that the substitution reaction can be used as a new strategy in the synthesis and modification of MOFs and MOPs, particularly for pre-designed ones with desired structures and functions, which are usually difficult to access by a direct one-pot self-assembly synthetic approach. This review highlights the implementation of the substitution reaction in MOFs and MOPs. Examples of substitution reactions at metal ions, organic ligands, and free guest molecules of MOFs and MOPs are listed and analyzed. The changes or modifications in the structures and/or properties of these materials induced by the substitutions, as well as the nature of the associated reaction, are discussed, with the conclusion that the substitution reaction is really feasible and powerful in synthesizing and tailoring MOMs.
Co-reporter:Chong-Chen Wang, Jian-Rong Li, Xiu-Liang Lv, Yan-Qiu Zhang and Guangsheng Guo
Energy & Environmental Science 2014 vol. 7(Issue 9) pp:2831-2867
Publication Date(Web):17 Jul 2014
DOI:10.1039/C4EE01299B
Efficient removal of organic pollutants from wastewater has become a hot research topic due to its ecological and environmental importance. Traditional water treatment methods such as adsorption, coagulation, and membrane separation suffer from high operating costs, and even generate secondary pollutants. Photocatalysis on semiconductor catalysts (TiO2, ZnO, Fe2O3, CdS, GaP, and ZnS) has demonstrated efficiency in degrading a wide range of organic pollutants into biodegradable or less toxic organic compounds, as well as inorganic CO2, H2O, NO3−, PO43−, and halide ions. However, the difficult post-separation, easy agglomeration, and low solar energy conversion efficiency of these inorganic catalysts limit their large scale applications. Exploitation of new catalysts has been attracting great attention in the related research communities. In the past two decades, a class of newly-developed inorganic–organic hybrid porous materials, namely metal–organic frameworks (MOFs) has generated rapid development due to their versatile applications such as in catalysis and separation. Recent research has showed that these materials, acting as catalysts, are quite effective in the photocatalytic degradation of organic pollutants. This review highlights research progress in the application of MOFs in this area. The reported examples are collected and analyzed; and the reaction mechanism, the influence of various factors on the catalytic performance, the involved challenges, and the prospect are discussed and estimated. It is clear that MOFs have a bright future in photocatalysis for pollutant degradation.
Co-reporter:Jinhee Park ; Ying-Pin Chen ; Zachary Perry ; Jian-Rong Li ;Hong-Cai Zhou
Journal of the American Chemical Society 2014 Volume 136(Issue 48) pp:16895-16901
Publication Date(Web):November 10, 2014
DOI:10.1021/ja508822r
A series of molybdenum- and copper-based MOPs were synthesized through coordination-driven process of a bridging ligand (3,3′-PDBAD, L1) and dimetal paddlewheel clusters. Three conformers of the ligand exist with an ideal bridging angle between the two carboxylate groups of 0° (H2α-L1), 120° (H2β-L1), and of 90° (H2γ-L1), respectively. At ambient or lower temperature, H2L1 and Mo2(OAc)4 or Cu2(OAc)4 were crystallized into a molecular square with γ-L1 and Mo2/Cu2 units. With proper temperature elevation, not only the molecular square with γ-L1 but also a lantern-shaped cage with α-L1 formed simultaneously. Similar to how Watson–Crick pairs stabilize the helical structure of duplex DNA, the core–shell molecular assembly possesses favorable H-bonding interaction sites. This is dictated by the ligand conformation in the shell, coding for the formation and providing stabilization of the central lantern shaped core, which was not observed without this complementary interaction. On the basis of the crystallographic implications, a heterobimetallic cage was obtained through a postsynthetic metal ion metathesis, showing different reactivity of coordination bonds in the core and shell. As an innovative synthetic strategy, the site-selective metathesis broadens the structural diversity and properties of coordination assemblies.
Co-reporter:Cui Zhao, Naixin Wang, Lin Wang, Hongliang Huang, Rong Zhang, Fan Yang, Yabo Xie, Shulan Ji and Jian-Rong Li
Chemical Communications 2014 vol. 50(Issue 90) pp:13921-13923
Publication Date(Web):19 Sep 2014
DOI:10.1039/C4CC05279J
Hybrid membranes composed of porous metal–organic molecule nanocages as fillers embedded in a hyperbranched polymer (Boltorn W3000) were fabricated, which exhibit excellent pervaporation separation performances towards aromatic/aliphatic hydrocarbons. The unique nature of the molecule-based fillers and their good dispersion and compatibility in/with the polymer are responsible for the good membrane properties.
Co-reporter:Yabo Xie, Hui Yang, Zhiyong U. Wang, Yangyang Liu, Hong-Cai Zhou and Jian-Rong Li
Chemical Communications 2014 vol. 50(Issue 5) pp:563-565
Publication Date(Web):25 Nov 2013
DOI:10.1039/C3CC48089E
A new porous metal–organic framework (MOF) with three types of preserved polyhedral molecular building units, all of which have been observed in a series of isostructural MOFs constructed from highly symmetrical hexacarboxylic ligands, was formed even from a pre-designed related tetracarboxylic ligand with drastically reduced symmetry.
Co-reporter:Bin Wang, Hongliang Huang, Xiu-Liang Lv, Yabo Xie, Ming Li, and Jian-Rong Li
Inorganic Chemistry 2014 Volume 53(Issue 17) pp:9254-9259
Publication Date(Web):August 12, 2014
DOI:10.1021/ic5013473
Introducing functional groups into pores of metal–organic frameworks (MOFs) through ligand modification provides an efficacious approach for tuning gas adsorption and separation performances of this type of novel porous material. In this work, two UiO-67 analogues, [Zr6O4(OH)4(FDCA)6] (BUT-10) and [Zr6O4(OH)4(DTDAO)6] (BUT-11), with functionalized pore surfaces and high stability were synthesized from two functional ligands, 9-fluorenone-2,7-dicarboxylic acid (H2FDCA) and dibenzo[b,d]thiophene-3,7-dicarboxylic acid 5,5-dioxide (H2DTDAO), respectively, and structurally determined by single-crystal X-ray diffraction. Notwithstanding skeleton bend of the two ligands relative to the linear 4,4′-biphenyldicarboxylic acid in UiO-67, the two MOFs have structures similar to that of UiO-67, with only lowered symmetry in their frameworks. Attributed to these additional functional groups (carbonyl and sulfone, respectively) in the ligands, BUT-10 and -11 show enhanced CO2 adsorption and separation selectivities over N2 and CH4, in spite of decreased pore sizes and surface areas compared with UiO-67. At 298 K and 1 atm, the CO2 uptake is 22.9, 50.6, and 53.5 cm3/g, and the infinite dilution selectivities of CO2/CH4 are 2.7, 5.1, and 9.0 and those of CO2/N2 are 9.4, 18.6, and 31.5 for UiO-67, BUT-10, and BUT-11, respectively. The selectivities of CO2/CH4 and CO2/N2 are thus enhanced 1.9 and 2.0 times in BUT-10 and 3.3 and 3.4 times in BUT-11, respectively, on the basis of UiO-67. The adsorption mechanism of CO2 in BUT-11 has also been explored through computational simulations. The results show that CO2 molecules locate around the sulfone groups in pore surfaces of BUT-11, verifying at the molecular level that sulfone groups significantly increase the affinity toward CO2 molecules of the framework. This provides thus an efficient strategy for the design of CO2 capture materials.
Co-reporter:Yuxiu Sun, Rong Zhang, Cui Zhao, Naixin Wang, Yabo Xie and Jian-Rong Li
RSC Advances 2014 vol. 4(Issue 62) pp:33007-33012
Publication Date(Web):30 Jul 2014
DOI:10.1039/C4RA05182C
The ability to fabricate high-quality MOF-based membranes is critical and highly desired due to their outstanding performance in molecule separations and sensors. In this work, a water stable MOF, ZIF-8 is chosen as the typical example to validate a new self-modified counter diffusion assisted secondary growth method for the fabrication of inner skin tubular MOF membranes. The preparation route involves two main steps: counter diffusion for modifying the rough surface of industrial ceramic substrate (plugging pores in the ceramic tube) with homogenous ZIF-8 nanocrystals, and the secondary solvothermal growth for fabricating continuous ZIF-8 membranes on the inner surface of the tubular substrate. The ZIF-8 membranes prepared by this method are characterized in detail. The pre-modification process and the use of a low-reactivity growth solution containing zinc acetate favor the growth of dense ZIF-8 membrane in the solvothermal process.
Co-reporter:Rong Zhang; Shulan Ji;Dr. Naixin Wang;Lin Wang; Guojun Zhang
Angewandte Chemie International Edition 2014 Volume 53( Issue 37) pp:9775-9779
Publication Date(Web):
DOI:10.1002/anie.201403978
Abstract
Metal–organic frameworks (MOFs) have emerged as porous solids of a superior type for the fabrication of membranes. However, it is still challenging to prepare a uniformly dispersed robust MOF hybrid membrane. Herein, we propose a simple and powerful strategy, namely, coordination-driven in situ self-assembly, for the fabrication of MOF hybrid membranes. On the basis of the coordination interactions between metal ions and ligands and/or the functional groups of the organic polymer, this method was confirmed to be feasible for the production of a stable membrane with greatly improved MOF-particle dispersion in and compatibility with the polymer, thus providing outstanding separation ability. As an experimental proof of concept, a high-quality ZIF-8/PSS membrane was fabricated that showed excellent performance in the nanofiltration and separation of dyes from water.
Co-reporter:Rong Zhang; Shulan Ji;Dr. Naixin Wang;Lin Wang; Guojun Zhang
Angewandte Chemie 2014 Volume 126( Issue 37) pp:9933-9937
Publication Date(Web):
DOI:10.1002/ange.201403978
Abstract
Metal–organic frameworks (MOFs) have emerged as porous solids of a superior type for the fabrication of membranes. However, it is still challenging to prepare a uniformly dispersed robust MOF hybrid membrane. Herein, we propose a simple and powerful strategy, namely, coordination-driven in situ self-assembly, for the fabrication of MOF hybrid membranes. On the basis of the coordination interactions between metal ions and ligands and/or the functional groups of the organic polymer, this method was confirmed to be feasible for the production of a stable membrane with greatly improved MOF-particle dispersion in and compatibility with the polymer, thus providing outstanding separation ability. As an experimental proof of concept, a high-quality ZIF-8/PSS membrane was fabricated that showed excellent performance in the nanofiltration and separation of dyes from water.
Co-reporter:Meng Lan, Rui-Mei Guo, Yibo Dou, Jian Zhou, Awu Zhou, Jian-Rong Li
Nano Energy (March 2017) Volume 33() pp:
Publication Date(Web):March 2017
DOI:10.1016/j.nanoen.2017.01.046
•A bimetallic MOF directed strategy is proposed for fabricating Pt-doping heterojunctions.•Porous Pt-ZnO-Co3O4, Pt-ZnS-CoS, and Pt-Zn3P2-CoP heterojunction photocatalysts are made.•They exhibit excellent catalytic activity towards hydrogen generation from water splitting.Porous Pt-doping heterojunctions, Pt-ZnO-Co3O4, Pt-ZnS-CoS, and Pt-Zn3P2-CoP were fabricated by firstly the oxidation, sulfurization, and phosphorization of ZnCo-zeolitic-imidazolate-framework (ZnCo-ZIF) and then the doping of Pt nanoparticles. They exhibit excellent photocatalytic activity towards hydrogen generation from water splitting. These bimetallic metal-organic-framework (MOF) derivatives maintain the porous framework skeleton of ZnCo-ZIF precursor, there by significantly enhancing the light utilization and simultaneously affording abundant exposed catalytic active sites. Most importantly, suitable band matching and strong electron coupling in these heterojunctions are achieved by using the bimetallic MOF template, which facilitate the efficient electron-hole separation and transportation. In addition, Pt nanoparticles distributed on the porous heterojunctions as electron traps can offer rich redox active sites for the hydrogen generation. Correspondingly, the hydrogen generation rate of Pt-ZnO-Co3O4, Pt-ZnS-CoS, and Pt-Zn3P2-CoP was up to ~7.80, ~8.21, and ~9.15 mmol h−1 g−1, respectively, higher than those of respective ZIF-8 or ZIF-67-based derivatives. This work thus provides a new approach that using bimetallic MOF as template directs the fabrication of noble-metal doping heterojunctions to simultaneously enhance light absorption utilization, electro-hole separation, and transport, therefore promoting surface water oxidation reaction for efficient water splitting.A bimetallic MOF template approach is proposed to fabricate Pt-doping heterojunction photocatalysts for the hydrogen generation of water splitting. The obtained Pt-ZnO-Co3O4, Pt-ZnS-CoS, and Pt-Zn3P2-CoP catalysts from the oxidation, sulfurization, and phosphorization of bimetallic ZnCo-zeolitic-imidazolate-framework (ZnCo-ZIF), respectively followed by Pt-doping exhibit excellent hydrogen generation performance.
Co-reporter:Hao Wu, Fan Yang, Xiu-Liang Lv, Bin Wang, Yong-Zheng Zhang, Min-Jian Zhao and Jian-Rong Li
Journal of Materials Chemistry A 2017 - vol. 5(Issue 28) pp:NaN14529-14529
Publication Date(Web):2017/06/22
DOI:10.1039/C7TA03917D
A new porphyrinic metal–organic framework (MOF), [Co(DCDPP)]·5H2O, was designed and constructed by using a bifunctional ligand, 5,15-di(4-carboxylphenyl)-10,20-di(4-pyridyl)porphyrin (H2DCDPP). This MOF features a three-dimensional framework structure with open channels, surrounded by high-density non-coordinating carboxylic groups, and exhibits a high proton conductivity of 3.9 × 10−2 S cm−1 at 80 °C and 97% relative humidity, higher than most conductive MOFs. Moreover, it also shows excellent stability in boiling water and cyclic proton conduction.
Co-reporter:Cui Zhao, Naixin Wang, Lin Wang, Hongliang Huang, Rong Zhang, Fan Yang, Yabo Xie, Shulan Ji and Jian-Rong Li
Chemical Communications 2014 - vol. 50(Issue 90) pp:NaN13923-13923
Publication Date(Web):2014/09/19
DOI:10.1039/C4CC05279J
Hybrid membranes composed of porous metal–organic molecule nanocages as fillers embedded in a hyperbranched polymer (Boltorn W3000) were fabricated, which exhibit excellent pervaporation separation performances towards aromatic/aliphatic hydrocarbons. The unique nature of the molecule-based fillers and their good dispersion and compatibility in/with the polymer are responsible for the good membrane properties.
Co-reporter:Yabo Xie, Hui Yang, Zhiyong U. Wang, Yangyang Liu, Hong-Cai Zhou and Jian-Rong Li
Chemical Communications 2014 - vol. 50(Issue 5) pp:NaN565-565
Publication Date(Web):2013/11/25
DOI:10.1039/C3CC48089E
A new porous metal–organic framework (MOF) with three types of preserved polyhedral molecular building units, all of which have been observed in a series of isostructural MOFs constructed from highly symmetrical hexacarboxylic ligands, was formed even from a pre-designed related tetracarboxylic ligand with drastically reduced symmetry.
Co-reporter:Xiuling Zhang, Yong-Zheng Zhang, Da-Shuai Zhang, Baoyong Zhu and Jian-Rong Li
Dalton Transactions 2015 - vol. 44(Issue 35) pp:NaN15702-15702
Publication Date(Web):2015/07/24
DOI:10.1039/C5DT01770J
By the solvothermal reaction of a triangular ligand, 2,4,6-tris-(4-carboxyphenoxy)-1,3,5-triazine (H3tcpt) with Zn(NO3)2·6H2O in N,N′-dimethylacetamide/acetonitrile/H2O (v/v/v = 1:1:1) mixed solvents, a two-fold, interpenetrated, three-dimensional (3D), porous metal–organic framework, [Zn2(tcpt)OH]·solvents (1·solvents), with a rare, paddlewheel secondary building unit (SBU), Zn2(COO)3, was synthesized and characterized. It was found that a single 3D structure of 1 forms when two-dimensional layers, which are constructed by tcpt3− bonding with the paddlewheel SBUs, are linked by –OH groups along the axial sites of the SBUs. Compared with the reported Zn(II)-based partners with this ligand, synthesis conditions, particularly the solvents used, clearly played a key role in the formation of different SBUs, thereby resulting in distinct MOFs with the same ligand. In particular, 1 features good water and thermal stability and can withstand acidic aqueous solutions with pH values ranging from 5 to 12. In addition, 1 displays good adsorption ability towards H2 (2.21 wt% at 77 K and 1 atm) and can selectively adsorb CO2 from CH4 and N2, in spite of its relatively low void volume (36.8%), suggesting potential applications in gas storage and separation.
Co-reporter:Yi Han, Shunan Sheng, Fan Yang, Yabo Xie, Minjian Zhao and Jian-Rong Li
Journal of Materials Chemistry A 2015 - vol. 3(Issue 24) pp:NaN12809-12809
Publication Date(Web):2015/05/26
DOI:10.1039/C5TA00963D
A new metal–organic framework, {[(CH3)2NH2][Co2NaL2(CH3COO)2]·xS}n (BUT-51, H2L = 5-(pyridine-4-yl)isophthalic acid) with two types of nanotubular channels, was synthesized and used in dye adsorption. It was found that cationic dyes, including Methylene Blue (MB), Acridine Red (AR) and Acriflavine Hydrochloride (AH), can be rapidly adsorbed by BUT-51, but larger Methylene Violet (MV) and anionic Methyl Orange (MO), as well as neutral Solvent Yellow 2 (SY2), can hardly be adsorbed. These results imply that the adsorption behaviour of BUT-51 with the cationic dyes follows not only a charge- but also size- and shape-exclusive effect. Surprisingly, BUT-51 also preferentially adsorbs (or separates) AH from MB and AR, respectively, in their mixed acetone solution, probably due to the coordination between AH and Co2+ in its framework. Furthermore, AH uptake can change the porosity and framework stability of BUT-51 to give a robust partner.
Co-reporter:Yibo Dou, Jian Zhou, Fan Yang, Min-Jian Zhao, Zuoren Nie and Jian-Rong Li
Journal of Materials Chemistry A 2016 - vol. 4(Issue 32) pp:NaN12534-12534
Publication Date(Web):2016/07/12
DOI:10.1039/C6TA04765C
CoAl-based layered-double-hydroxide@zeolitic-imidazolate-framework-67 (LDH@ZIF-67) was fabricated via a hydrothermal synthesis of LDH film on Ni substrate followed by the in situ growth of ZIF-67. Its derivatives, MMO@Co3O4, spinelle@C and LDH@CoS with hierarchical structures were obtained by the subsequent oxidation, carbonization and sulfurization of LDH@ZIF-67, respectively, which exhibit distinct specific capacitances of 692, 781 and 1205 F g−1 at a discharge current density of 1 A g−1. Interestingly, these derivatives retained hierarchical structures with large surface area, which ensures that the majority of exposed active species can participate in the charge–discharge process and thus effectively contribute to total capacitances. The synergistic effect from fast electronic transfer reduces reversible ion accumulation at the interface, which imparts LDH@ZIF-67 derivatives improved electrochemical activities, in contrast to conventional bulk MOF derivatives. In addition, it was found that the combination of the remarkable electrical conductivity of sulfides (compared with their oxide counterparts) and the strong electronic coupling between LDH and CoS can facilitate fast electron transfer. As a result, LDH@CoS exhibits an excellent specific energy of 44.5 W h kg−1 at a current density of 20 A g−1, as well as good capacitance retention of 88.5% after 2000 cycles. This work thus demonstrates a feasible strategy for the design and fabrication of LDH@MOF derived composites as SCs components, which is applicable in constructing other novel electrode materials with hierarchical structures for applications in energy storage systems.
Co-reporter:Jiong-Peng Zhao, Cui Zhao, Wei-Chao Song, Lei Wang, Yabo Xie, Jian-Rong Li and Xian-He Bu
Dalton Transactions 2015 - vol. 44(Issue 22) pp:NaN10296-10296
Publication Date(Web):2015/04/22
DOI:10.1039/C5DT00568J
The structure and magnetism of three cobalt(II)–azide complexes, [Co(N3)2(bepy)2]n (1), [Co2(N3)4(vipy)4]n (2), and [Co(N3)2(bipy)]n (3) were tuned by three structurally related 4-substituent pyridines, 4-benzylpyridine (bepy), 4-vinyl pyridine (vipy), and 4,4′-bipyridine (bipy) as co-ligands in solvothermal reactions. With flexible benzyl as a substituent group of the pyridine co-ligand, a one-dimensional (1D) complex 1 with double end-to-end (EE) azide-bridging Co(II) chain is formed. While using a rigid but small vinyl group as the substituent, a distinct Co(II)–azide chain with alternate double end-on (EO) and double EE azide bridges was obtained. Finally, when another pyridine group was used instead of the substituent incapable of coordinating in 1 and 2, a bipyridine, it gave rise to a chiral complex 3 with a three-dimensional (3D) diamondoid Co(II)–azide framework further reinforced by the bipy ligand. Magnetic studies indicate antiferromagnetic interactions between the Co(II) ions in the three complexes, but interestingly, weak antiferromagnetism origin of spin canting exists in 3 at low temperatures.
Co-reporter:Jiong-Peng Zhao, Yabo Xie, Jian-Rong Li and Xian-He Bu
Dalton Transactions 2016 - vol. 45(Issue 4) pp:NaN1524-1524
Publication Date(Web):2015/12/03
DOI:10.1039/C5DT03667D
Low-temperature hydrothermal reactions of copper salts with NaN3 and structurally related pyridine-based ligands, 1-(4-pyridyl)pyridinium, 3-chloromethylpyridine, 4-benzylpyridine, and quinoline (L4), respectively, led to the formation of four new magnetic complexes, [Cu3(L1)2(N3)6]n (1), [Cu3(L2)2(N3)6]n (2), [Cu(L3)2(N3)2] (3), and [Cu(L4)(N3)2]n (4). In these complexes, L1, L2, and L3 are pyridine, 3-azidomethylpyridine, and 4-benzoylpyridine, being generated in situ by the decomposition, azido substitution, and oxidation reaction of the 1-(4-pyridyl)pyridinium, 3-chloromethylpyridine, and 4-benzylpyridine, respectively. 1 and 2 have similar structures being composed of double end-on azido-bridging planar [Cu3(L)2(N3)6] trinuclear units, which are further linked into a two-dimensional layer by the end-to-end azido bridges of themselves, along with their weak end-on coordination. It is interesting that the only slight differences of geometrical parameters in 1 and 2 have led to distinct magnetic interactions between the trinuclear units, where the former is antiferromagnetic but the latter is ferromagnetic, whereas 3 has a mono-nuclear core structure, which is further extended to a one-dimensional (1D) chain by weakly coordinated end-on azido bridges. 4 consists of unique 1D chains with double end-on azido bridge bonding distorted five-coordinated Cu(II) centers, and exhibits ferromagnetic intrachain interactions. In the structures of these complexes there also exist weak inter-layer or inter-chain hydrogen bonds, which should also be responsible for some magnetic behavior at low temperature. In addition, primary structural and magnetic comparisons and discussions have also been performed by combining other reported azido-Cu(II) systems with related pyridyl-based co-ligands. These results show that the selection of synthesis conditions and slight decoration of co-ligands (or geometric differences of them) have important influences on the structures and magnetic properties of resulting metal azido complexes.
Co-reporter:Yan Bai, Yibo Dou, Lin-Hua Xie, William Rutledge, Jian-Rong Li and Hong-Cai Zhou
Chemical Society Reviews 2016 - vol. 45(Issue 8) pp:NaN2367-2367
Publication Date(Web):2016/02/17
DOI:10.1039/C5CS00837A
Among the large family of metal–organic frameworks (MOFs), Zr-based MOFs, which exhibit rich structure types, outstanding stability, intriguing properties and functions, are foreseen as one of the most promising MOF materials for practical applications. Although this specific type of MOF is still in its early stage of development, significant progress has been made in recent years. Herein, advances in Zr-MOFs since 2008 are summarized and reviewed from three aspects: design and synthesis, structure, and applications. Four synthesis strategies implemented in building and/or modifying Zr-MOFs as well as their scale-up preparation under green and industrially feasible conditions are illustrated first. Zr-MOFs with various structural types are then classified and discussed in terms of different Zr-based secondary building units and organic ligands. Finally, applications of Zr-MOFs in catalysis, molecule adsorption and separation, drug delivery, and fluorescence sensing, and as porous carriers are highlighted. Such a review based on a specific type of MOF is expected to provide guidance for the in-depth investigation of MOFs towards practical applications.
Co-reporter:Yi Han, Jian-Rong Li, Yabo Xie and Guangsheng Guo
Chemical Society Reviews 2014 - vol. 43(Issue 16) pp:NaN5981-5981
Publication Date(Web):2014/04/24
DOI:10.1039/C4CS00033A
Substitution reaction, as one of the most powerful and efficient chemical reactions, has been widely used in various syntheses, including those for the design and preparation of functional molecules or materials. In the past decade, a class of newly developed inorganic–organic hybrid materials, namely metal–organic materials (MOMs), has experienced a rapid development. MOMs are composed of metal-containing nodes connected by organic linkers through strong chemical bonds, and can be divided into metal–organic frameworks (MOFs) and metal–organic polygons/polyhedra (MOPs) with infinite and discrete structural features, respectively. Recent research has shown that the substitution reaction can be used as a new strategy in the synthesis and modification of MOFs and MOPs, particularly for pre-designed ones with desired structures and functions, which are usually difficult to access by a direct one-pot self-assembly synthetic approach. This review highlights the implementation of the substitution reaction in MOFs and MOPs. Examples of substitution reactions at metal ions, organic ligands, and free guest molecules of MOFs and MOPs are listed and analyzed. The changes or modifications in the structures and/or properties of these materials induced by the substitutions, as well as the nature of the associated reaction, are discussed, with the conclusion that the substitution reaction is really feasible and powerful in synthesizing and tailoring MOMs.
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