Linker Installation: Engineering Pore Environment with Precisely Placed Functionalities in Zirconium MOFs

Yuan, Shuai; Chen, Ying-Pin; Qin, Jun-Sheng; Lu, Weigang; Zou, Lanfang; Zhang, Qiang; Wang, Xuan; Sun, Xing; Zhou, Hong-Cai

doi:10.1021/jacs.6b04501

Linker Installation: Engineering Pore Environment with Precisely Placed Functionalities in Zirconium MOFs

Journal Article · Sat Jun 25 04:00:00 EDT 2016 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.6b04501· OSTI ID:1388673

Yuan, Shuai ^[1]; Chen, Ying-Pin ^[1]; Qin, Jun-Sheng ^[1]; Lu, Weigang ^[2]; Zou, Lanfang ^[1]; Zhang, Qiang ^[1]; Wang, Xuan ^[1]; Sun, Xing ^[1]; Zhou, Hong-Cai ^[1]

Texas A & M Univ., College Station, TX (United States)
Blinn College, Bryan, TX (United States)

Precise placement of multiple functional groups in a highly ordered metal–organic framework (MOF) platform allows the tailoring of the pore environment, which is required for advanced applications. To realize this, we present a comprehensive study on the linker installation method, in which a stable MOF with coordinatively unsaturated Zr₆ clusters was employed and linkers bearing different functional groups were postsynthetically installed. Specifically, a Zr-MOF with inherent missing linker sites, namely, PCN-700, was initially constructed under kinetic control. Twelve linkers with different substituents were then designed to study their effect on MOF formation kinetics and therefore resulting MOF structures. Guided by the geometrical analysis, linkers with different lengths were installed into a parent PCN-700, giving rise to 11 new MOFs and each bearing up to three different functional groups in predefined positions. Systematic variation of the pore volume and decoration of pore environment were realized by linker installation, which resulted in synergistic effects including an enhancement of H2 adsorption capacities of up to 57%. In addition, a size-selective catalytic system for aerobic alcohol oxidation reaction is built in PCN-700 through linker installation, which shows high activity and tunable size selectivity. Altogether, these results exemplify the capability of the linker installation method in the pore environment engineering of stable MOFs with multiple functional groups, giving an unparalleled level of control.

View Accepted Manuscript (DOE)

Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Center for Gas Separations Relevant to Clean Energy Technologies (CGS)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0001015; EE0007049

OSTI ID:: 1388673

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 28 Vol. 138; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Construction of hierarchically porous metal–organic frameworks through linker labilization Yuan, Shuai; Zou, Lanfang; Qin, Jun-Sheng Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/ncomms15356	journal	May 2017
Ionic liquid accelerates the crystallization of Zr-based metal–organic frameworks Sang, Xinxin; Zhang, Jianling; Xiang, Junfeng Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/s41467-017-00226-y	journal	August 2017
Retrosynthesis of multi-component metal−organic frameworks Yuan, Shuai; Qin, Jun-Sheng; Li, Jialuo Nature Communications, Vol. 9, Issue 1 https://doi.org/10.1038/s41467-018-03102-5	journal	February 2018
Diverse structures of metal–organic frameworks via a side chain adjustment: interpenetration and gas adsorption Shen, Kang; Qin, Ling; Zheng, He-Gen Dalton Transactions, Vol. 45, Issue 41 https://doi.org/10.1039/c6dt03086f	journal	January 2016
Selective adsorption of chlorinated volatile organic compound vapours by microcrystalline 1D coordination polymers Cametti, Massimo; Martí-Rujas, Javier Dalton Transactions, Vol. 45, Issue 47 https://doi.org/10.1039/c6dt03803d	journal	January 2016
Mixed-linker strategy for the construction of multifunctional metal–organic frameworks Qin, Jun-Sheng; Yuan, Shuai; Wang, Qi Journal of Materials Chemistry A, Vol. 5, Issue 9 https://doi.org/10.1039/c6ta10281f	journal	January 2017
A terbium( iii ) lanthanide–organic framework as a platform for a recyclable multi-responsive luminescent sensor Chen, Min; Xu, Wen-Ming; Tian, Jia-Yue Journal of Materials Chemistry C, Vol. 5, Issue 8 https://doi.org/10.1039/c6tc05615f	journal	January 2017
Stepwise engineering of pore environments and enhancement of CO ₂ /R22 adsorption capacity through dynamic spacer installation and functionality modification Chen, Cheng-Xia; Qiu, Qian-Feng; Cao, Chen-Chen Chem. Commun., Vol. 53, Issue 83 https://doi.org/10.1039/c7cc06352k	journal	January 2017
Stable metal–organic frameworks as a host platform for catalysis and biomimetics Qin, Jun-Sheng; Yuan, Shuai; Lollar, Christina Chemical Communications, Vol. 54, Issue 34 https://doi.org/10.1039/c7cc09173g	journal	January 2018
Linker functionalisation triggers an alternative 3D-topology for Zn-isophthalate-4,4′-bipyridine frameworks Schneemann, Andreas; Rudolf, Robin; Henke, Sebastian Dalton Transactions, Vol. 46, Issue 25 https://doi.org/10.1039/c7dt01195d	journal	January 2017
Four new metal–organic frameworks based on diverse secondary building units: sensing and magnetic properties Yan, Yang-Tian; Zhang, Wen-Yan; Zhang, Fang Dalton Transactions, Vol. 47, Issue 5 https://doi.org/10.1039/c7dt04696k	journal	January 2018
Improving analyte selectivity by post-assembly modification of metal–organic framework based photonic crystal sensors von Mankowski, A.; Szendrei-Temesi, K.; Koschnick, C. Nanoscale Horizons, Vol. 3, Issue 4 https://doi.org/10.1039/c7nh00209b	journal	January 2018
A flexible thioether-based MOF as a crystalline sponge for structural characterization of liquid organic molecules Yang, Xin-Yu; Yuan, Shuai; Qin, Jun-Sheng Materials Chemistry Frontiers, Vol. 1, Issue 9 https://doi.org/10.1039/c7qm00152e	journal	January 2017
Electrochemical and diffuse reflectance study on tetrahedral ε-Keggin-based metal–organic frameworks Nie, Zhong-Bin; Zhang, Min; Su, Tan RSC Advances, Vol. 7, Issue 50 https://doi.org/10.1039/c7ra04771a	journal	January 2017
A robust two-dimensional zirconium-based luminescent coordination polymer built on a V-shaped dicarboxylate ligand for vapor phase sensing of volatile organic compounds Du, Pei-Yao; Lustig, William P.; Teat, Simon J. Chemical Communications, Vol. 54, Issue 58 https://doi.org/10.1039/c8cc03496f	journal	January 2018
Remoulding a MOF’s pores by auxiliary ligand introduction for stability improvement and highly selective CO ₂ -capture Zhang, Qing-Qing; Liu, Xiao-Fei; Ma, Lin Chemical Communications, Vol. 54, Issue 85 https://doi.org/10.1039/c8cc06593d	journal	January 2018
Investigating the crystal engineering of the pillared paddlewheel metal–organic framework Zn ₂ (NH ₂ BDC) ₂ DABCO McGrath, D. T.; Downing, V. A.; Katz, M. J. CrystEngComm, Vol. 20, Issue 39 https://doi.org/10.1039/c8ce00848e	journal	January 2018
From fundamentals to applications: a toolbox for robust and multifunctional MOF materials Kirchon, Angelo; Feng, Liang; Drake, Hannah F. Chemical Society Reviews, Vol. 47, Issue 23 https://doi.org/10.1039/c8cs00688a	journal	January 2018
Evans–Showell-type polyoxometalate-based metal–organic complexes with novel 3D structures constructed from flexible bis-pyrazine–bis-amide ligands and copper metals: syntheses, structures, and fluorescence and catalytic properties Li, Feng-Cai; Li, Xi-Li; Tan, Li-Kun Dalton Transactions, Vol. 48, Issue 6 https://doi.org/10.1039/c8dt04698k	journal	January 2019
A 2D porous pentiptycene-based MOF for efficient detection of Ba ²⁺ and selective adsorption of dyes from water Zhang, Minghui; Qi, Ziqiang; Feng, Yang Inorganic Chemistry Frontiers, Vol. 5, Issue 6 https://doi.org/10.1039/c8qi00098k	journal	January 2018
One-pot synthesis of mercapto functionalized Zr-MOFs for the enhanced removal of Hg ²⁺ ions from water Lin, Daiwu; Liu, Xiao; Huang, Renliang Chemical Communications, Vol. 55, Issue 47 https://doi.org/10.1039/c9cc03481a	journal	January 2019
Made-to-order porous electrodes for supercapacitors: MOFs embedded with redox-active centers as a case study Mallick, Arijit; Liang, Hanfeng; Shekhah, Osama Chemical Communications, Vol. 56, Issue 12 https://doi.org/10.1039/c9cc08860a	journal	January 2020
A Zn( ii ) metal–organic framework constructed by a mixed-ligand strategy for CO ₂ capture and gas separation Zou, Lifei; Yuan, Jiaqi; Yuan, Yang CrystEngComm, Vol. 21, Issue 21 https://doi.org/10.1039/c9ce00343f	journal	January 2019
The chemistry of multi-component and hierarchical framework compounds Feng, Liang; Wang, Kun-Yu; Day, Gregory S. Chemical Society Reviews, Vol. 48, Issue 18 https://doi.org/10.1039/c9cs00250b	journal	January 2019
Molecular design of chiral zirconium metal–organic frameworks for asymmetric transfer hydrogenation of imines Li, Xu; Jiang, Jianwen Catalysis Science & Technology, Vol. 9, Issue 18 https://doi.org/10.1039/c9cy00770a	journal	January 2019
A fast and highly selective Congo red adsorption material based on a cadmium-phosphonate network Ai, Jing; Tian, Hong-Rui; Min, Xue Dalton Transactions https://doi.org/10.1039/c9dt01545k	journal	January 2020
New linker installation in metal–organic frameworks Pang, Qingqing; Tu, Binbin; Li, Qiaowei Dalton Transactions, Vol. 48, Issue 32 https://doi.org/10.1039/c9dt02335f	journal	January 2019
Rational modifications of PCN-700 to induce electrical conductivity: a computational study Chong, Sanggyu; Kim, Jihan Dalton Transactions, Vol. 49, Issue 1 https://doi.org/10.1039/c9dt03865e	journal	January 2020
Computational screening, synthesis and testing of metal–organic frameworks with a bithiazole linker for carbon dioxide capture and its green conversion into cyclic carbonates Müller, Philipp; Bucior, Benjamin; Tuci, Giulia Molecular Systems Design & Engineering, Vol. 4, Issue 5 https://doi.org/10.1039/c9me00062c	journal	January 2019
Uniform and simultaneous orthogonal functionalization of a metal–organic framework material Samarakoon, Kanchana P.; Yazdanparast, Mohammad S.; Day, Victor W. Molecular Systems Design & Engineering, Vol. 5, Issue 4 https://doi.org/10.1039/c9me00182d	journal	January 2020
The synthesis and applications of chiral pyrrolidine functionalized metal–organic frameworks and covalent-organic frameworks Zhou, Mi; El-Sayed, El-Sayed M.; Ju, Zhanfeng Inorganic Chemistry Frontiers, Vol. 7, Issue 6 https://doi.org/10.1039/c9qi01103j	journal	January 2020
Alterations to secondary building units of metal–organic frameworks for the development of new functions Ha, Junsu; Lee, Jae Hwa; Moon, Hoi Ri Inorganic Chemistry Frontiers, Vol. 7, Issue 1 https://doi.org/10.1039/c9qi01119f	journal	January 2020
Insights into the water adsorption mechanism in the chemically stable zirconium-based MOF DUT-67 – a prospective material for adsorption-driven heat transformations Bon, Volodymyr; Senkovska, Irena; Evans, Jack D. Journal of Materials Chemistry A, Vol. 7, Issue 20 https://doi.org/10.1039/c9ta00825j	journal	January 2019
In-MOF-derived ultrathin heteroatom-doped carbon nanosheets for improving oxygen reduction Huang, Qi; Guo, Yuanyuan; Wang, Xian Nanoscale, Vol. 12, Issue 18 https://doi.org/10.1039/d0nr02007a	journal	January 2020
Technology for the Remediation of Water Pollution: A Review on the Fabrication of Metal Organic Frameworks Bian, Yongning; Xiong, Nana; Zhu, Guocheng Processes, Vol. 6, Issue 8 https://doi.org/10.3390/pr6080122	journal	August 2018

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CCDC 1496833: Experimental Crystal Structure Determination Yuan, Shuai; Chen, Ying-Pin; Qin, Jun-Sheng https://doi.org/10.5517/ccdc.csd.cc1m7kyc The current record is supplemented by this dataset	dataset	January 2016
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Linker Installation: Engineering Pore Environment with Precisely Placed Functionalities in Zirconium MOFs

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