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pore engineering for Covalent Organic Framework Membranes

Chemical Research in Chinese Universities 2022年第2期38卷 364-372页

作者： YAO Jin LU Ya SUN Huihui ZHAO Xin Key Laboratory of Synthetic and Self-assembly Chemistry for Organic Functional Molecules Shanghai Institute of Organic ChemistryChinese Academy of SciencesShanghai 200032P.R.China School of Chemistry and Materials Science Hangzhou Institute for Advanced StudyUniversity of Chinese Academy of SciencesHangzhou 310024P.R.China College of Chemistry and Materials Science Shanghai Normal UniversityShanghai 200234P.R.China

Membrane technology is of particular significance for the sustainable development of society owing to its potential capacity to tackle the energy shortage and environmental *** materials are the core part of membrane *** have always been pursuing predictable structures of advanced membrane materials,which provides a possibility to fully unlock the potential of *** organic frameworks(COFs),with the advantage of controllable pore microenvironment,are considered to be promising candidates to achieve this design *** customizable function of COF membranes through pore engineering does well in the enhancement of selective permeability performance,which offers COF membranes with great application potentials in separation and transportation *** this context,COF-based membranes have been developed rapidly in recent ***,we present a brief overview on the strategies developed for pore engineering of COF membranes in recent years,including skeleton engineering,pore surface engineering,host-guest chemistry and membrane ***,the features of transmission or separation of molecules/ions based on COF membranes and corresponding applications are also *** the last part,the challenges and prospects of the development of COF membranes are discussed.

关键词： Membrane technology Covalent organic framework(COF) pore engineering Separation Ion transportation

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Different Routes to the pore engineering of Spherical MCM-41

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Journal of Wuhan University of Technology(Materials Science) 2003年第2期18卷 1-5页

作者：刘世权 E F Vansant University of Antwerp (Belgium)

Different routes,including the replacements of the template,addition of pore expander and hydrothermal post-synthesis treatment have been used for the pore engineering of spherical MCM-41.A comparison among the pore engineering effects of these methods has been *** results show that the hydrothermal post-synthesis treatment affords the synthesized material with a larger pore size and narrow pore size distribution without changing the spherical *** far as the pore-size expansion is concerned,the addition of DMTA is the most effective one,but this might be limited by the spherical *** the replacement of C 16TMABr with the Gemini surfactant GEM 16-8-16 with an addition of DMTA gives rise to the largest pore volume and surface area.

关键词： spherical MCM-41 pore engineering pore expander post-synthesis treatment Gemini surfactant

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A topology approach to overcome the pore size/volume trade-offs for autonomous indoor humidity control

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Science China Chemistry 2024年第9期67卷 2968-2974页

作者： Zhi-Shuo Wang Xue-Wen Zhang Kai Zheng Xiao-Xian Chen Dong-Dong Zhou Jie-Peng Zhang MOE Key Laboratory of Bioinorganic and Synthetic Chemistry GBRCE for Functional Molecular Engineering School of ChemistryIGCME Sun Yat-Sen University Chemistry and Chemical engineering Guangdong Laboratory

Autonomous indoor humidity control is gaining more and more attention but is limited by the trade-offs among pore volume,pore size and water stability of water adsorbents. We solve this problem by using a unique coordination network topology combined with hydrolytically stable M（III） carboxylate clusters. By extending the ligand length from 9.0 to 11.2 and 13.7 ?, the pore volume significantly increases from 0.99 to 1.40 and 1.78 cm3g–1, which proportionally increases the saturated water adsorption capacity. Meanwhile, the pore size slightly increases from 10.4 to 11.0 and 13.5 ?, which restricts the isotherm inflection pressure and hysteresis width to meet the requirement of indoor humidity control. Large single-crystals suitable for Xray diffraction studies were obtained by using Fe（III） salts, while isostructural frameworks with sufficiently high water stabilities were synthesized by using Cr（III） salts, which offer record working capacity of 0.90 and 1.10 g g–1for indoor humidity control.

关键词： metal-organic frameworks water adsorption indoor humidity control water stability pore engineering

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Efficient Splitting of Trans-/Cis-Olefins Using an Anion-Pillared Ultramicroporous Metal-Organic Framework with Guest-Adaptive pore Channels

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engineering 2022年第4期8卷 80-86页

作者： Zhaoqiang Zhang Xili Cui Xiaoming Jiang Qi Ding Jiyu Cui Yuanbin Zhang Youssef Belmabkhout Karim Adil Mohamed Eddaoudi Huabin Xing Key Laboratory of Biomass Chemical engineering of Ministry of Education College of Chemical and Biological EngineeringZhejiang UniversityHangzhou 310027China State Key Laboratory of Structural Chemistry Fujian Institute of Research on the Structure of MatterChinese Academy of SciencesFuzhou 350002China Advanced Membranes and Porous Materials Center King Abdullah University of Science and TechnologyThuwal 23955Saudi Arabia

Trans-/cis-olefin isomers play a vital role in the petrochemical *** paucity of energy-efficient technologies for their splitting is mainly due to the similarities of their physicochemical ***,two new tailor-made anion-pillared ultramicroporous metal–organic frameworks(MOFs),ZU-36-Ni and ZU-36-Fe(GeFSIX-3-Ni and GeFSIX-3-Fe)are reported for the first time for the efficient trans-/cis-2-butene(trans-/cis-C_(4)H_(8))mixture splitting by enhanced molecular ***,ZU-36-Ni unexpectedly exhibited smart guest-adaptive pore channels for trapping trans-C_(4)H_(8)with a remarkable adsorption capacity(2.45 mmol∙g^(−1))while effectively rejecting cis-C_(4)H_(8)with a high purity of 99.99%.The dispersion-corrected density functional theory(DFT-D)calculation suggested that the guest-adaptive behavior of ZU-36-Ni in response to trans-C_(4)H_(8)is derived from the organic linker rotation and the optimal pore dimensions,which not only improve the favorable adsorption/diffusion of trans-C_(4)H_(8)with optimal host–guest interactions,but also enhance the size-exclusion of cis-C_(4)H_(8).This work opens a new avenue for pore engineering in advanced smart or adaptive porous materials for specific applications involving guest molecular recognition.

关键词： Adsorption and separation Trans-/cis-butene Ultramicroporous metal-organic frameworks pore engineering Guest-adaptive

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Ultrathin 2D Covalent Organic Framework Film Fabricated via Langmuir-Blodgett Method with a“Two-in-One”Type Monomer

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Chemical Research in Chinese Universities 2022年第2期38卷 440-445页

作者： MENG Weijia LI Yang ZHAO Ziqiang SONG Xiaoyu LU Fanli CHEN Long Department of Chemistry Tianjin Key Laboratory of Molecular Optoelectronic ScienceTianjin UniversityTianjin 300072P.R.China State Key Laboratory of Supramolecular Structure and Materials College of ChemistryJilin UniversityChangchun 130012P.R.China

In recent years, covalent organic frameworks(COFs) are evolving as a novel kind of porous materials for catalysis and molecular separation, gas adsorption, etc. Various functional building blocks have been explored to tune the pore channels, including the pore size and structures. In this article, a new terphenyl(TP) based COF(TP-COF) was developed via a “two-in-one” strategy by using a symmetric A2B2monomer, i.e., 4,4''-diamino-2',5'-diformyl-1,1':4',1''-terphenyl(DADFTP). The pore size of TP-COF was only 0.99 nm by shortening the arm length of the DADFTP monomer. Freestanding, continuous and ultrathin COF films could be facilely prepared at the air-liquid interface through the modified Langmuir-Blodgett(LB) method. TP-COF films exhibited high rejection of over 90% for dyes removal.

关键词： “Two-in-one”strategy Covalent organic framework film Molecular sieving pore engineering

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pore-Directed Solid-State Selective Photoinduced E–Z Isomerization and Dimerization within Metal–Organic Frameworks

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CCS Chemistry 2023年第5期5卷 1225-1232页

作者： Shu-Li Chen Yan Mi Fei-Long Hu David James Young Jianping Lang Key Laboratory of Chemistry and engineering of Forest Products State Ethnic Affairs CommissionGuangxi Minzu UniversityNanning 530006Guangxi College of Chemistry Chemical Engineering and Materials ScienceSoochow UniversitySuzhou 215123Jiangsu College of engineering IT and EnvironmentCharles Darwin UniversityDarwin 0909Northern Territory

Design and construction of suitable pore microenvironments for selective catalytic reactions of small guest molecules is a major goal for ***,we report control of competitive E–Z photoisomerization and photodimerization within porous metal–organic frameworks(MOFs)by fine-tuning the pore microenvironments using different dicarboxylate *** with small pores((E)-X_(MOF_(1))and(E)-X_(MOF_(1))′)favor the photoinduced E–Z isomerization of one encapsulated diaryl alkene substrate while those with large pores(((E)-X)_(2MOF_(2)))prefer the photodimerization of two encapsulated alkene *** reactions show broad functional group compatibility and proceed stereospecifically in good yields under mild *** local concentration of diaryl alkene ligands and their preorientation within pores facilitate stereoselective *** pore engineering strategy is applicable to control and create pore microenvironemnts for other photoinduced organic reactions within porous MOFs.

关键词： pore engineering E–Z photoisomerization photodimerization metal–organic frameworks solid-state reaction

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