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Title: Molybdenum Sulfide within a Metal–Organic Framework for Photocatalytic Hydrogen Evolution from Water

Abstract

A representative metal–organic framework, NU-1000, was functionalized with MoSx. The previously determined crystal structure of the material, named MoSx-SIM, consists of monometallic Mo(IV) ions with two sulfhydryl ligands. The metal ions are anchored to the framework by displacing protons presented by the –OH/–OH2 groups on the Zr6 node. As shown previously, the MOF-supported complexes are electrocatalytic for hydrogen evolution from acidified water. The earlier electrocatalysis results, together with the nearly ideal formal potential of the Mo(IV/II) couple (i.e., nearly coincident with that of the hydrogen couple), and the physical proximity of UV-absorbing MOF linkers to the complexes, suggested to us that the linkers might behave photosensitizers for catalyst reduction, and subsequently, for H2 evolution from water. To our surprise, MoSx-SIM, when UV-illuminated in an aqueous buffer at near-neutral pH, displays a biphasic photocatalytic response: an initially slow rate of reaction, i.e. 0.56 mmol g-1 h-1, followed by an increase to 4 mmol g-1 h-1. Ex-situ catalyst examination revealed that nanoparticulate MoSx suspended within the reaction mixture is the actual catalyst. Thus, photo-assisted restructuring and detachment of the catalyst or pre-catalyst from the MOF node appears to be necessary for the catalyst to reduce water at neutral pH.

Authors:
ORCiD logo; ; ; ; ; ORCiD logo
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Center for Light Energy Activated Redox Processes (LEAP); Northwestern Univ., Evanston, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1491951
Alternate Identifier(s):
OSTI ID: 1566728
Grant/Contract Number:  
SC0001059
Resource Type:
Published Article
Journal Name:
Journal of the Electrochemical Society
Additional Journal Information:
Journal Name: Journal of the Electrochemical Society Journal Volume: 166 Journal Issue: 5; Journal ID: ISSN 0013-4651
Publisher:
The Electrochemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Energy Conversion; Hydrogen Evolution; Molybdenum Sulfide; Photocatalysis

Citation Formats

Noh, Hyunho, Yang, Ying, Ahn, Sol, Peters, Aaron W., Farha, Omar K., and Hupp, Joseph T. Molybdenum Sulfide within a Metal–Organic Framework for Photocatalytic Hydrogen Evolution from Water. United States: N. p., 2019. Web. doi:10.1149/2.0261905jes.
Noh, Hyunho, Yang, Ying, Ahn, Sol, Peters, Aaron W., Farha, Omar K., & Hupp, Joseph T. Molybdenum Sulfide within a Metal–Organic Framework for Photocatalytic Hydrogen Evolution from Water. United States. doi:10.1149/2.0261905jes.
Noh, Hyunho, Yang, Ying, Ahn, Sol, Peters, Aaron W., Farha, Omar K., and Hupp, Joseph T. Thu . "Molybdenum Sulfide within a Metal–Organic Framework for Photocatalytic Hydrogen Evolution from Water". United States. doi:10.1149/2.0261905jes.
@article{osti_1491951,
title = {Molybdenum Sulfide within a Metal–Organic Framework for Photocatalytic Hydrogen Evolution from Water},
author = {Noh, Hyunho and Yang, Ying and Ahn, Sol and Peters, Aaron W. and Farha, Omar K. and Hupp, Joseph T.},
abstractNote = {A representative metal–organic framework, NU-1000, was functionalized with MoSx. The previously determined crystal structure of the material, named MoSx-SIM, consists of monometallic Mo(IV) ions with two sulfhydryl ligands. The metal ions are anchored to the framework by displacing protons presented by the –OH/–OH2 groups on the Zr6 node. As shown previously, the MOF-supported complexes are electrocatalytic for hydrogen evolution from acidified water. The earlier electrocatalysis results, together with the nearly ideal formal potential of the Mo(IV/II) couple (i.e., nearly coincident with that of the hydrogen couple), and the physical proximity of UV-absorbing MOF linkers to the complexes, suggested to us that the linkers might behave photosensitizers for catalyst reduction, and subsequently, for H2 evolution from water. To our surprise, MoSx-SIM, when UV-illuminated in an aqueous buffer at near-neutral pH, displays a biphasic photocatalytic response: an initially slow rate of reaction, i.e. 0.56 mmol g-1 h-1, followed by an increase to 4 mmol g-1 h-1. Ex-situ catalyst examination revealed that nanoparticulate MoSx suspended within the reaction mixture is the actual catalyst. Thus, photo-assisted restructuring and detachment of the catalyst or pre-catalyst from the MOF node appears to be necessary for the catalyst to reduce water at neutral pH.},
doi = {10.1149/2.0261905jes},
journal = {Journal of the Electrochemical Society},
number = 5,
volume = 166,
place = {United States},
year = {2019},
month = {1}
}

Journal Article:
Free Publicly Available Full Text
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DOI: 10.1149/2.0261905jes

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Cited by: 5 works
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