skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Supramolecular metal-organic frameworks that display high homogeneous and heterogeneous photocatalytic activity for H 2 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)
OSTI Identifier:
1379333
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Journal Article: 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. https://doi.org/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. https://doi.org/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},
url = {https://www.osti.gov/biblio/1379333}, journal = {Nature Communications},
issn = {2041-1723},
number = ,
volume = 7,
place = {United States},
year = {2016},
month = {5}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 49 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

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


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


Functional Supramolecular Polymers
journal, February 2012


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


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


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


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


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


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


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


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


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


Self-Assembly at All Scales
journal, March 2002


Docking in Metal-Organic Frameworks
journal, August 2009


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


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


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


Metal–Organic Frameworks in Biomedicine
journal, September 2011


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


Postsynthetic modification of metal–organic frameworks
journal, January 2009


Self-Assembling Capsules
journal, August 1997


Characterization of supramolecular gels
journal, January 2013


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


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


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


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


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


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


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


Supramolecular Polymers
journal, December 2001


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


Mesoporous metal–organic framework materials
journal, January 2012


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


Metal–organic frameworks as semiconductors
journal, January 2010


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


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


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


Interlocked and Intertwined Structures and Superstructures
journal, December 1995


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


Soft porous crystals
journal, November 2009


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


Dynamers: Dynamic Molecular and Supramolecular Polymers
journal, January 2010


Supramolecular Assemblies Built with Host-Stabilized Charge-Transfer Interactions
journal, July 2007


Metal–Organic Frameworks as A Tunable Platform for Designing Functional Molecular Materials
text, January 2013


    Works referencing / citing this record:

    Light-Harvesting Fluorescent Supramolecular Block Copolymers Based on Cyanostilbene Derivatives and Cucurbit[8]urils in Aqueous Solution
    journal, December 2017


    Water‐Soluble Conjugated Molecule for Solar‐Driven Hydrogen Evolution from Salt Water
    journal, February 2019


    Modular Assembly of Host–Guest Metal–Phenolic Networks Using Macrocyclic Building Blocks
    journal, November 2019


    Shape-Controllable and Fluorescent Supramolecular Organic Frameworks Through Aqueous Host-Guest Complexation
    journal, December 2017


    Modular Assembly of Host–Guest Metal–Phenolic Networks Using Macrocyclic Building Blocks
    journal, November 2019


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


    Cucurbit[7]uril‐Based Metal–Organic Rotaxane Framework for Dual‐Capture of Molecular Iodine and Cationic Potassium Ion
    journal, January 2020


    Metal-Organic-Framework-Derived Co 3 S 4 Hollow Nanoboxes for the Selective Reduction of Nitroarenes
    journal, August 2018


    Supramolecular Chemistry in Solid State Materials such as Metal-Organic Frameworks
    journal, October 2018


    Supramolecular Polymerization from Controllable Fabrication to Living Polymerization
    journal, July 2017


    Metal Organic Frameworks: A New Generation Coordination Polymers for Visible Light Photocatalysis
    journal, July 2017


    Photolysis Behaviors of Anthryl Derivative Aggregation Mediated by Sulfato‐β‐Cyclodextrin
    journal, December 2019


    Maximizing the photocatalytic hydrogen evolution of Z-scheme UiO-66-NH2@Au@CdS by aminated-functionalized linkers
    journal, February 2019


    Controllable macrocyclic supramolecular assemblies in aqueous solution
    journal, July 2018


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


    Surveying macrocyclic chemistry: from flexible crown ethers to rigid cyclophanes
    journal, January 2017


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


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


    Shining a light on the photo-sensitisation of organic–inorganic hybrid polyoxometalates
    journal, January 2018


    Visible-light initiated aerobic oxidations: a critical review
    journal, January 2018


    Fabrication of nor-seco -cucurbit[10]uril based supramolecular polymers via self-sorting
    journal, January 2019


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


    Encapsulation of the [Ru(bpy) 3 ] 2+ luminophore in a unique hydrogen-bonded host framework
    journal, January 2020


    A study of binding interactions between terpyridine derivatives and cucurbit[10]uril
    journal, April 2018


    Supramolecular organic frameworks (SOFs): homogeneous regular 2D and 3D pores in water
    journal, March 2017


    A mutually stabilized host-guest pair
    journal, November 2019


    Supramolecular concepts and approaches in corrosion and biofouling prevention
    journal, June 2019


    Supramolecular Chemistry and Self-Organization: A Veritable Playground for Catalysis
    journal, February 2019


    Shape‐Controllable and Fluorescent Supramolecular Organic Frameworks Through Aqueous Host–Guest Complexation
    journal, December 2017