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Title: Supramolecular metal-organic frameworks that display high homogeneous and heterogeneous photocatalytic activity for H2 production

Abstract

Self-assembly has a unique presence when it comes to creating complicated, ordered supramolecular architectures from simple components under mild conditions. Here, we describe a self-assembly strategy for the generation of the first homogeneous supramolecular metal-organic framework (SMOF-1) in water at room temperature from a hexaarmed [Ru(bpy) 3 ] 2+ -based precursor and cucurbit[8] uril (CB[8]). The solution-phase periodicity of this cubic transition metal-cored supramolecular organic framework (MSOF) is confirmed by small-angle X-ray scattering and diffraction experiments, which, as supported by TEM imaging, is commensurate with the periodicity in the solid state. We further demonstrate that SMOF-1 adsorbs anionic Wells-'Dawson-type polyoxometalates (WD-POMs) in a one-cage-one-guest manner to give WD-POM@SMOF-1 hybrid assemblies. Upon visible-light (500 nm) irradiation, such hybrids enable fast multi-electron injection from photosensitive [Ru(bpy) 3 ] 2+ units to redox-active WD-POM units, leading to efficient hydrogen production in aqueous media and in organic media. The demonstrated strategy opens the door for the development of new classes of liquid-phase and solid-phase ordered porous materials.

Authors:
 [1];  [1];  [1];  [1];  [1];  [1];  [1];  [1];  [2];  [1]
  1. Fudan Univ., Shanghai (China). Dept. of Chemistry
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Molecular Foundry
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1379333
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 7; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE; metal-organic frameworks; photocatalysis

Citation Formats

Tian, Jia, Xu, Zi-Yue, Zhang, Dan-Wei, Wang, Hui, Xie, Song-Hai, Xu, Da-Wen, Ren, Yuan-Hang, Wang, Hao, Liu, Yi, and Li, Zhan-Ting. Supramolecular metal-organic frameworks that display high homogeneous and heterogeneous photocatalytic activity for H2 production. United States: N. p., 2016. Web. doi:10.1038/ncomms11580.
Tian, Jia, Xu, Zi-Yue, Zhang, Dan-Wei, Wang, Hui, Xie, Song-Hai, Xu, Da-Wen, Ren, Yuan-Hang, Wang, Hao, Liu, Yi, & Li, Zhan-Ting. Supramolecular metal-organic frameworks that display high homogeneous and heterogeneous photocatalytic activity for H2 production. United States. doi:10.1038/ncomms11580.
Tian, Jia, Xu, Zi-Yue, Zhang, Dan-Wei, Wang, Hui, Xie, Song-Hai, Xu, Da-Wen, Ren, Yuan-Hang, Wang, Hao, Liu, Yi, and Li, Zhan-Ting. Tue . "Supramolecular metal-organic frameworks that display high homogeneous and heterogeneous photocatalytic activity for H2 production". United States. doi:10.1038/ncomms11580. https://www.osti.gov/servlets/purl/1379333.
@article{osti_1379333,
title = {Supramolecular metal-organic frameworks that display high homogeneous and heterogeneous photocatalytic activity for H2 production},
author = {Tian, Jia and Xu, Zi-Yue and Zhang, Dan-Wei and Wang, Hui and Xie, Song-Hai and Xu, Da-Wen and Ren, Yuan-Hang and Wang, Hao and Liu, Yi and Li, Zhan-Ting},
abstractNote = {Self-assembly has a unique presence when it comes to creating complicated, ordered supramolecular architectures from simple components under mild conditions. Here, we describe a self-assembly strategy for the generation of the first homogeneous supramolecular metal-organic framework (SMOF-1) in water at room temperature from a hexaarmed [Ru(bpy) 3 ] 2+ -based precursor and cucurbit[8] uril (CB[8]). The solution-phase periodicity of this cubic transition metal-cored supramolecular organic framework (MSOF) is confirmed by small-angle X-ray scattering and diffraction experiments, which, as supported by TEM imaging, is commensurate with the periodicity in the solid state. We further demonstrate that SMOF-1 adsorbs anionic Wells-'Dawson-type polyoxometalates (WD-POMs) in a one-cage-one-guest manner to give WD-POM@SMOF-1 hybrid assemblies. Upon visible-light (500 nm) irradiation, such hybrids enable fast multi-electron injection from photosensitive [Ru(bpy) 3 ] 2+ units to redox-active WD-POM units, leading to efficient hydrogen production in aqueous media and in organic media. The demonstrated strategy opens the door for the development of new classes of liquid-phase and solid-phase ordered porous materials.},
doi = {10.1038/ncomms11580},
journal = {Nature Communications},
number = ,
volume = 7,
place = {United States},
year = {2016},
month = {5}
}

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Works referenced in this record:

MOF-based electronic and opto-electronic devices
journal, January 2014

  • Stavila, V.; Talin, A. A.; Allendorf, M. D.
  • Chem. Soc. Rev., Vol. 43, Issue 16
  • DOI: 10.1039/C4CS00096J

Controllable Synthesis of Metal-Organic Frameworks: From MOF Nanorods to Oriented MOF Membranes
journal, June 2010


Metal–organic framework materials as catalysts
journal, January 2009

  • Lee, JeongYong; Farha, Omar K.; Roberts, John
  • Chemical Society Reviews, Vol. 38, Issue 5, p. 1450-1459
  • DOI: 10.1039/b807080f

Functional Supramolecular Polymers
journal, February 2012


Supramolecular assemblies built with host-stabilized charge-transfer interactions
journal, January 2007

  • Ko, Young Ho; Kim, Eunju; Hwang, Ilha
  • Chem. Commun., Issue 13
  • DOI: 10.1039/B615103E

The Cucurbit[ n ]uril Family:  Prime Components for Self-Sorting Systems
journal, November 2005

  • Liu, Simin; Ruspic, Christian; Mukhopadhyay, Pritam
  • Journal of the American Chemical Society, Vol. 127, Issue 45
  • DOI: 10.1021/ja055013x

Rational Design, Synthesis, Purification, and Activation of Metal−Organic Framework Materials
journal, August 2010

  • Farha, Omar K.; Hupp, Joseph T.
  • Accounts of Chemical Research, Vol. 43, Issue 8, p. 1166-1175
  • DOI: 10.1021/ar1000617

Dynamers: dynamic molecular and supramolecular polymers
journal, August 2005


Supramolecular gel chemistry: developments over the last decade
journal, January 2011


Introduction to Metal–Organic Frameworks
journal, September 2011

  • Zhou, Hong-Cai; Long, Jeffrey R.; Yaghi, Omar M.
  • Chemical Reviews, Vol. 112, Issue 2, p. 673-674
  • DOI: 10.1021/cr300014x

The construction of a two-dimensional supramolecular organic framework with parallelogram pores and stepwise fluorescence enhancement
journal, January 2015

  • Xu, Shun-Qi; Zhang, Xiang; Nie, Cheng-Bin
  • Chemical Communications, Vol. 51, Issue 91
  • DOI: 10.1039/C5CC05875A

Nanoscale Metal–Organic Frameworks for Biomedical Imaging and Drug Delivery
journal, October 2011

  • Della Rocca, Joseph; Liu, Demin; Lin, Wenbin
  • Accounts of Chemical Research, Vol. 44, Issue 10, p. 957-968
  • DOI: 10.1021/ar200028a

Supramolecular Polymers: Historical Development, Preparation, Characterization, and Functions
journal, March 2015

  • Yang, Liulin; Tan, Xinxin; Wang, Zhiqiang
  • Chemical Reviews, Vol. 115, Issue 15
  • DOI: 10.1021/cr500633b

Selective gas adsorption and separation in metal–organic frameworks
journal, January 2009

  • Li, Jian-Rong; Kuppler, Ryan J.; Zhou, Hong-Cai
  • Chemical Society Reviews, Vol. 38, Issue 5, p. 1477-1504
  • DOI: 10.1039/b802426j

Exceptional Thermal Stability in a Supramolecular Organic Framework: Porosity and Gas Storage
journal, October 2010

  • Yang, Wenbin; Greenaway, Alex; Lin, Xiang
  • Journal of the American Chemical Society, Vol. 132, Issue 41
  • DOI: 10.1021/ja1042935

Enantioselective catalysis with homochiral metal–organic frameworks
journal, January 2009

  • Ma, Liqing; Abney, Carter; Lin, Wenbin
  • Chemical Society Reviews, Vol. 38, Issue 5, p. 1248-1256
  • DOI: 10.1039/b807083k

Self-Assembly at All Scales
journal, March 2002

  • Whitesides, George M.; Grzybowski, Bartosz
  • Science, Vol. 295, Issue 5564, p. 2418-2421
  • DOI: 10.1126/science.1070821

Docking in Metal-Organic Frameworks
journal, August 2009

  • Li, Qiaowei; Zhang, Wenyu; Miljanic, Ognjen S.
  • Science, Vol. 325, Issue 5942, p. 855-859
  • DOI: 10.1126/science.1175441

Three-dimensional periodic supramolecular organic framework ion sponge in water and microcrystals
journal, December 2014

  • Tian, Jia; Zhou, Tian-You; Zhang, Shao-Chen
  • Nature Communications, Vol. 5, Issue 1
  • DOI: 10.1038/ncomms6574

Supramolecular Organic Frameworks (SOFs): Water-Phase Periodic Porous Self-Assembled Architectures
journal, January 2015

  • Wang, Hui; Zhang, Danwei; Zhao, Xin
  • Acta Chimica Sinica, Vol. 73, Issue 6
  • DOI: 10.6023/A14120880

Photosensitizing Metal–Organic Framework Enabling Visible-Light-Driven Proton Reduction by a Wells–Dawson-Type Polyoxometalate
journal, February 2015

  • Zhang, Zhi-Ming; Zhang, Teng; Wang, Cheng
  • Journal of the American Chemical Society, Vol. 137, Issue 9
  • DOI: 10.1021/jacs.5b00075

Encapsulation Enhanced Dimerization of a Series of 4-Aryl- N -Methylpyridinium Derivatives in Water: New Building Blocks for Self-Assembly in Aqueous Media
journal, April 2014

  • Zhang, Ying; Zhou, Tian-You; Zhang, Kang-Da
  • Chemistry - An Asian Journal, Vol. 9, Issue 6
  • DOI: 10.1002/asia.201400006

Metal–Organic Frameworks in Biomedicine
journal, September 2011

  • Horcajada, Patricia; Gref, Ruxandra; Baati, Tarek
  • Chemical Reviews, Vol. 112, Issue 2, p. 1232-1268
  • DOI: 10.1021/cr200256v

Carbon Dioxide Capture in Metal–Organic Frameworks
journal, September 2011

  • Sumida, Kenji; Rogow, David L.; Mason, Jarad A.
  • Chemical Reviews, Vol. 112, Issue 2, p. 724-781
  • DOI: 10.1021/cr2003272

Postsynthetic modification of metal–organic frameworks
journal, January 2009

  • Wang, Zhenqiang; Cohen, Seth M.
  • Chemical Society Reviews, Vol. 38, Issue 5
  • DOI: 10.1039/b802258p

Self-Assembling Capsules
journal, August 1997

  • Conn, M. Morgan; Rebek, Julius
  • Chemical Reviews, Vol. 97, Issue 5
  • DOI: 10.1021/cr9603800

Characterization of supramolecular gels
journal, January 2013

  • Yu, Guocan; Yan, Xuzhou; Han, Chengyou
  • Chemical Society Reviews, Vol. 42, Issue 16
  • DOI: 10.1039/c3cs60080g

Toward Self-Organization and Complex Matter
journal, March 2002


Molecular engineering for synthesizing novel structures of metal–organic frameworks with multifunctional properties
journal, December 2009


Supramolecular polymeric hydrogels
journal, January 2012

  • Appel, Eric A.; del Barrio, Jesús; Loh, Xian Jun
  • Chemical Society Reviews, Vol. 41, Issue 18
  • DOI: 10.1039/c2cs35264h

Metal-organic frameworks as potential drug delivery systems
journal, November 2012


A Microporous Hydrogen-Bonded Organic Framework for Highly Selective C 2 H 2 /C 2 H 4 Separation at Ambient Temperature
journal, September 2011

  • He, Yabing; Xiang, Shengchang; Chen, Banglin
  • Journal of the American Chemical Society, Vol. 133, Issue 37
  • DOI: 10.1021/ja2066016

Charge photo-accumulation and photocatalytic hydrogen evolution under visible light at an iridium(iii)-photosensitized polyoxotungstate
journal, January 2013

  • Matt, Benjamin; Fize, Jennifer; Moussa, Jamal
  • Energy & Environmental Science, Vol. 6, Issue 5
  • DOI: 10.1039/c3ee40352a

Porous Metal–Organic Frameworks for Gas Storage and Separation: What, How, and Why?
journal, September 2014

  • Li, Bin; Wen, Hui-Min; Zhou, Wei
  • The Journal of Physical Chemistry Letters, Vol. 5, Issue 20
  • DOI: 10.1021/jz501586e

Supramolecular Polymer Chemistry:  Self-Assembling Dendrimers Using the DDA·AAD (GC-like) Hydrogen Bonding Motif
journal, November 2002

  • Ma, Yuguo; Kolotuchin, Sergei V.; Zimmerman, Steven C.
  • Journal of the American Chemical Society, Vol. 124, Issue 46
  • DOI: 10.1021/ja0202006

Homochiral Metal–Organic Frameworks for Asymmetric Heterogeneous Catalysis
journal, September 2011

  • Yoon, Minyoung; Srirambalaji, Renganathan; Kim, Kimoon
  • Chemical Reviews, Vol. 112, Issue 2, p. 1196-1231
  • DOI: 10.1021/cr2003147

Metal-directed self-assembly of two- and three-dimensional synthetic receptors
journal, January 1998

  • Fujita, Makoto
  • Chemical Society Reviews, Vol. 27, Issue 6
  • DOI: 10.1039/a827417z

Supramolecular Polymers
journal, December 2001

  • Brunsveld, L.; Folmer, B. J. B.; Meijer, E. W.
  • Chemical Reviews, Vol. 101, Issue 12
  • DOI: 10.1021/cr990125q

Optimised room temperature, water-based synthesis of CPO-27-M metal–organic frameworks with high space-time yields
journal, January 2015

  • Garzón-Tovar, L.; Carné-Sánchez, A.; Carbonell, C.
  • Journal of Materials Chemistry A, Vol. 3, Issue 41
  • DOI: 10.1039/C5TA04923G

Mesoporous metal–organic framework materials
journal, January 2012

  • Xuan, Weimin; Zhu, Chengfeng; Liu, Yan
  • Chem. Soc. Rev., Vol. 41, Issue 5
  • DOI: 10.1039/C1CS15196G

New approaches for medicinal applications of bioinorganic chemistry
journal, April 2007


Metal–organic frameworks as semiconductors
journal, January 2010

  • Silva, Cláudia Gomes; Corma, Avelino; García, Hermenegildo
  • Journal of Materials Chemistry, Vol. 20, Issue 16
  • DOI: 10.1039/b924937k

The Chemistry and Applications of Metal-Organic Frameworks
journal, August 2013

  • Furukawa, H.; Cordova, K. E.; O'Keeffe, M.
  • Science, Vol. 341, Issue 6149, p. 1230444-1230444
  • DOI: 10.1126/science.1230444

Metal–organic frameworks: a new class of porous materials
journal, August 2004


Metal–Organic Frameworks as A Tunable Platform for Designing Functional Molecular Materials
journal, August 2013

  • Wang, Cheng; Liu, Demin; Lin, Wenbin
  • Journal of the American Chemical Society, Vol. 135, Issue 36
  • DOI: 10.1021/ja308229p

Strategies for Hydrogen Storage in Metal-Organic Frameworks
journal, July 2005

  • Rowsell, Jesse L. C.; Yaghi, Omar M.
  • Angewandte Chemie International Edition, Vol. 44, Issue 30, p. 4670-4679
  • DOI: 10.1002/anie.200462786

Interlocked and Intertwined Structures and Superstructures
journal, December 1995

  • Amabilino, David B.; Stoddart, J. Fraser.
  • Chemical Reviews, Vol. 95, Issue 8
  • DOI: 10.1021/cr00040a005

Free-Standing Monolayer Two-Dimensional Supramolecular Organic Framework with Good Internal Order
journal, November 2015

  • Pfeffermann, Martin; Dong, Renhao; Graf, Robert
  • Journal of the American Chemical Society, Vol. 137, Issue 45
  • DOI: 10.1021/jacs.5b09638

Soft porous crystals
journal, November 2009

  • Horike, Satoshi; Shimomura, Satoru; Kitagawa, Susumu
  • Nature Chemistry, Vol. 1, Issue 9, p. 695-704
  • DOI: 10.1038/nchem.444

Toward a Single-Layer Two-Dimensional Honeycomb Supramolecular Organic Framework in Water
journal, October 2013

  • Zhang, Kang-Da; Tian, Jia; Hanifi, David
  • Journal of the American Chemical Society, Vol. 135, Issue 47
  • DOI: 10.1021/ja4086935

    Works referencing / citing this record:

    From double-shelled grids to supramolecular frameworks
    journal, January 2018

    • Wu, Jianfeng; Guo, Mei; Li, Xiao-Lei
    • Chemical Communications, Vol. 54, Issue 85
    • DOI: 10.1039/c8cc06411c

    Synergistic catalysis for light-driven proton reduction using a polyoxometalate-based Cu–Ni heterometallic–organic framework
    journal, January 2019

    • Sun, Wenlong; He, Cheng; Liu, Tao
    • Chemical Communications, Vol. 55, Issue 26
    • DOI: 10.1039/c8cc09285k

    Outer Surface Interactions of Cucurbit[6]uril That Trigger the Assembly of Supramolecular Three-Dimensional Polycatenanes
    journal, January 2017

    • Cui, Xiaowei; Zhao, Wenxuan; Chen, Kai
    • Chemistry - A European Journal, Vol. 23, Issue 12
    • DOI: 10.1002/chem.201605045

    Anion-adaptive crystalline cationic material for 99TcO4− trapping
    journal, April 2019


    C–C to CC conversion within a supramolecular framework of tetrathiafulvalene: a confinement effect and an oxygen related dehydrogenation
    journal, January 2018

    • Zhang, Ping; Huo, Peng; Zhang, Xuan
    • Chemical Communications, Vol. 54, Issue 53
    • DOI: 10.1039/c8cc03197e

    Stepwise syntheses and supramolecular assemblies of a series of polyoxovanadate hybrids with various architectures
    journal, January 2018

    • Huang, Bo; Wang, Nan; Yang, Kang
    • New Journal of Chemistry, Vol. 42, Issue 8
    • DOI: 10.1039/c7nj04727d

    2:2 Complexes from Diphenylpyridiniums and Cucurbit[8]uril: Encapsulation-Promoted Dimerization of Electrostatically Repulsing Pyridiniums
    journal, April 2018

    • Yang, Bo; Yu, Shang-Bo; Wang, Hui
    • Chemistry - An Asian Journal, Vol. 13, Issue 10
    • DOI: 10.1002/asia.201701816

    Triptycene walled glycoluril trimer: synthesis and recognition properties
    journal, January 2020

    • Ndendjio, Sandra Zebaze; Liu, Wenjin; Yvanez, Nicolas
    • New Journal of Chemistry, Vol. 44, Issue 2
    • DOI: 10.1039/c9nj05336k

    2:2 Complexes from Diphenylpyridiniums and Cucurbit[8]uril: Encapsulation-Promoted Dimerization of Electrostatically Repulsing Pyridiniums
    journal, April 2018

    • Yang, Bo; Yu, Shang-Bo; Wang, Hui
    • Chemistry - An Asian Journal, Vol. 13, Issue 10
    • DOI: 10.1002/asia.201701816

    Outer Surface Interactions of Cucurbit[6]uril That Trigger the Assembly of Supramolecular Three-Dimensional Polycatenanes
    journal, January 2017

    • Cui, Xiaowei; Zhao, Wenxuan; Chen, Kai
    • Chemistry - A European Journal, Vol. 23, Issue 12
    • DOI: 10.1002/chem.201605045

    Anion-adaptive crystalline cationic material for 99TcO4− trapping
    journal, April 2019


    Stepwise syntheses and supramolecular assemblies of a series of polyoxovanadate hybrids with various architectures
    journal, January 2018

    • Huang, Bo; Wang, Nan; Yang, Kang
    • New Journal of Chemistry, Vol. 42, Issue 8
    • DOI: 10.1039/c7nj04727d

    C–C to CC conversion within a supramolecular framework of tetrathiafulvalene: a confinement effect and an oxygen related dehydrogenation
    journal, January 2018

    • Zhang, Ping; Huo, Peng; Zhang, Xuan
    • Chemical Communications, Vol. 54, Issue 53
    • DOI: 10.1039/c8cc03197e

    From double-shelled grids to supramolecular frameworks
    journal, January 2018

    • Wu, Jianfeng; Guo, Mei; Li, Xiao-Lei
    • Chemical Communications, Vol. 54, Issue 85
    • DOI: 10.1039/c8cc06411c

    Synergistic catalysis for light-driven proton reduction using a polyoxometalate-based Cu–Ni heterometallic–organic framework
    journal, January 2019

    • Sun, Wenlong; He, Cheng; Liu, Tao
    • Chemical Communications, Vol. 55, Issue 26
    • DOI: 10.1039/c8cc09285k

    Triptycene walled glycoluril trimer: synthesis and recognition properties
    journal, January 2020

    • Ndendjio, Sandra Zebaze; Liu, Wenjin; Yvanez, Nicolas
    • New Journal of Chemistry, Vol. 44, Issue 2
    • DOI: 10.1039/c9nj05336k