Engineering of Pore Geometry for Ultrahigh Capacity Methane Storage in Mesoporous Metal–Organic Frameworks

Liang, Cong‐Cong; Shi, Zhaolin; He, Chun‐Ting; Tan, Jing; Zhou, Hu-Die; Zhou, Huijuan; Lee, Yongjin; Zhang, Yue‐Biao

doi:10.1021/jacs.7b08347

Cited by 144 publications

(77 citation statements)

References 32 publications

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“…Multicomponent MOFs have emerging applications in catalysis, luminescence and gas storage . In order to form multicomponent MOFs judicious selection of the linkers is essential (Figure , Scheme S1) .…”

Section: Introductionmentioning

confidence: 99%

Enhancing Multicomponent Metal–Organic Frameworks for Low Pressure Liquid Organic Hydrogen Carrier Separations

et al. 2020

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The resurgence of interest in the hydrogen economy could hinge on the distribution of hydrogen in a safe and efficient manner. Whilst great progress has been made with cryogenic hydrogen storage or liquefied ammonia, liquid organic hydrogen carriers (LOHCs) remain attractive due to their lack of need for cryogenic temperatures or high pressures, most commonly a cycle between methylcyclohexane and toluene. Oxidation of methylcyclohexane to release hydrogen will be more efficient if the equilibrium limitations can be removed by separating the mixture. This report describes a family of six ternary and quaternary multicomponent metal–organic frameworks (MOFs) that contain the three‐dimensional cubane‐1,4‐dicarboxylate (cdc) ligand. Of these MOFs, the most promising is a quaternary MOF (CUB‐30), comprising cdc, 4,4′‐biphenyldicarboxylate (bpdc) and tritopic truxene linkers. Contrary to conventional wisdom that adsorptive interactions with larger, hydrocarbon guests are dominated by π–π interactions, here we report that contoured aliphatic pore environments can exhibit high selectivity and capacity for LOHC separations at low pressures. This is the first time, to the best of our knowledge, where selective adsorption for cyclohexane over benzene is witnessed, underlining the unique adsorptive behavior afforded by the unconventional cubane moiety.

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Section: Introductionmentioning

confidence: 99%

Enhancing Multicomponent Metal–Organic Frameworks for Low Pressure Liquid Organic Hydrogen Carrier Separations

et al. 2020

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“…As shown in Figure c, FDM‐8 delivered a total volumetric capacity of 215 cm 3 stp cm −3 at 80 bar and 298 K. This total volumetric capacity increased to 257 cm 3 stp cm −3 at 80 bar when the measurement was conducted at 273 K. The corresponding uptake value was 204 cm 3 stp cm −3 at 308 K. The near‐zero‐coverage isosteric heat of adsorption ( Q st ) was calculated to be 10.4 kJ mol −1 based on the isotherms at various temperatures (see Figures S39 and S42 and Table S6), which is comparable to the values of most carboxylate and azolate MOFs, but lower than those of copper(I)‐based MOFs with open metal sites . The Q st value slightly increased at high pressure, probably owing to CH 4 –CH 4 interactions at high gas loading . Considering the retention of a minimum inlet pressure of 5 bar, the methane volumetric capacity above this pressure, termed the working capacity, is more meaningful in practical operation settings .…”

Section: Figurementioning

confidence: 97%

Harnessing Bottom‐Up Self‐Assembly To Position Five Distinct Components in an Ordered Porous Framework

Diestel

Shi

et al. 2019

Angewandte Chemie

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Positioning adiverse set of building blocks in awelldefined arraye nables cooperativity amongst them and the systematic programming of functional properties.T he extension of this concept to porous metal-organic frameworks (MOFs) is challenging since the installation of multiple components in aw ell-ordered framework requires careful design of the lattice topology,j udicious selection of building blocks,a nd precise control of the crystallization parameters. Herein, we report how we met these challenges to prepare the first quinary MOF structure,F DM-8, by bottom-up selfassembly from two metals,Z n II and Cu I ,a nd three distinct carboxylate-and pyrazolate-based linkers.Withasurface area of 3643 m 2 g À1 ,F DM-8 contains hierarchical pores and shows outstanding methane-storage capacity at high pressure.F urthermore,functional groups introduced on the linkers became compartmentalized in predetermined arrays in the pores of the FDM-8 framework.One distinction between synthetic materials and their natural counterparts is their level of structural complexity. Synthetic materials are typically constructed from asmall set of structural units,which places an inherent limitation on their composition and architecture.T he contrast with biological materials,such as DNAand proteins,which are composed of multiple building blocks,isstartling. Owing to acombination of structural complexity and order,s uch biomolecules are capable of sophisticated functions.W hereas conventional synthetic materials lack complexity,t he functionality of biomaterials has inspired attempts to synthesize architectures that position ab road set of building blocks in aw ell-defined array.One prominent example is the design and realization of multicomponent metal-organic frameworks (MOFs). [1] The assembly of these materials relies on the combination of multiple metal clusters and organic linkers.T hese building blocks are distinguished from one another by their coordination preferences (metals) or symmetries and metric parameters (linkers). In this way,they can be positioned in specific positions in the growing lattice,w hich mitigates against randomness and disorder. By drawing on the isoreticular principle, [2] functional groups can be placed on the organic linkers that do not interfere with framework assembly. Accordingly,specific functional groups in proximity generate precisely controlled pore environments.P ores that are programmed in this way lead to designer functions,including enhanced gas storage [3] and cooperative catalysis. [4] Theg eneration of single crystals with multiple components directly from solution becomes increasingly difficult as the number of building blocks is increased because the selfassembly process requires ac ollection of simultaneous interactions to be manipulated in ac ooperative manner.I n the case of MOFs,t he formation of alternative products is fatal, since the purification of crystalline products is virtually impossible.Todate,the number of discrete molecules that can be cocrystallized to occupy inequivalent p...

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“…As ar esult, 3D_ICOF_5 is the most likely configuration in ICOFs,w hich is in line with the energy calculation of the ICOFs. To evaluate the CH 4 adsorption capacity on 3D_ ICOFs, the comparison of the CH 4 uptakes with several porous classical materials (including COF-5, [3] ZIF-8, [52] UMCM-1, [53] IRMOF-1, [54] ST-2 [55] ), as well as two ionic materials [5,20] is displayed in Figure 7. We choose the COF-5, ZIF-8, UMCM-1, IRMOF-1, and ST-2 for comparison because they are wellknown classic porous materials with excellent gas adsorption/ separation properties, and are often used as benchmarks.…”

Section: Gas Uptakes In 3d_icofsmentioning

confidence: 99%

Theoretical Investigation of the Topology of Spiroborate‐Linked Ionic Covalent Organic Frameworks (ICOFs)

Zhang

Guan

et al. 2019

Chemistry A European J

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A novel type of ionic covalent organic framework (ICOF) with a spiroborate linkage has been recently designed and synthesized by Zhang and co‐workers (Ionic Covalent Organic Frameworks with Spiroborate Linkage, Angew. Chem. Int. Ed. 2016, 55, 1737–1741). The spiroborate‐linked ICOFs exhibit high Brunauer–Emmett–Teller (BET) surface areas and significant amounts of H2 and CH4 uptakes, combined with excellent thermal and chemical stabilities. Inspired by the novel properties of ICOFs, with the aim of gaining better understanding of the structure of such spiroborate‐linked ICOFs, a series of potential 3D network configurations of ICOFs connected with tetrahedral [BO4]− nodes were proposed, assuming the [BO4]− node in spiroborate segments takes a tetrahedral configuration. These ICOFs, in terms of 2D and 3D topology through torsional energy of the [BO4]− fragment, pore‐size distribution, total energy of the framework, and gas adsorption properties were compared and systematically investigated by density functional theory calculations, molecular mechanics, and well‐established Grand canonical Monte Carlo simulations. The results indicate that spiroborate‐linked ICOFs are likely a mixture of various topologies. Among these architectures, the five‐fold interpenetrating model shows the lowest energy and reasonable gas uptakes, therefore, it is considered to be the most possible structure. More importantly, the five‐fold interpenetrating model, showing high CH4 uptakes compared with several classic porous materials, represents a promising CH4 storage material.

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Engineering of Pore Geometry for Ultrahigh Capacity Methane Storage in Mesoporous Metal–Organic Frameworks

Cited by 144 publications

References 32 publications

Enhancing Multicomponent Metal–Organic Frameworks for Low Pressure Liquid Organic Hydrogen Carrier Separations

Enhancing Multicomponent Metal–Organic Frameworks for Low Pressure Liquid Organic Hydrogen Carrier Separations

Harnessing Bottom‐Up Self‐Assembly To Position Five Distinct Components in an Ordered Porous Framework

Theoretical Investigation of the Topology of Spiroborate‐Linked Ionic Covalent Organic Frameworks (ICOFs)

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