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Title: Electrochemical Water Oxidation by a Catalyst-Modified Metal-Organic Framework Thin Film

Abstract

Water oxidation, a key component in artificial photosynthesis, requires high overpotentials and exhibits slow reaction kinetics that necessitates the use of stable and efficient heterogeneous water-oxidation catalysts (WOCs). Here, we report the synthesis of UiO-67 metal–organic framework (MOF) thin films doped with [Ru(tpy)(dcbpy)OH2]2+ (tpy=2,2':6',2''-terpyridine, dcbpy=5,5'-dicarboxy-2,2'-bipyridine) on conducting surfaces and their propensity for electrochemical water oxidation. The electrocatalyst oxidized water with a turnover frequency (TOF) of (0.2±0.1) s-1 at 1.71 V versus the normal hydrogen electrode (NHE) in buffered solution (pH~7) and exhibited structural and electrochemical stability. The electroactive sites were distributed throughout the MOF thin film on the basis of scan-ratedependent voltammetry studies. This work demonstrates a promising way to immobilize large concentrations of electroactive WOCs into a highly robust MOF scaffold and paves the way for future photoelectrochemical water-splitting systems.

Authors:
 [1];  [2];  [1];  [1];  [1];  [1];  [2];  [1]
  1. Department of Chemistry, Virginia Polytechnic Institute and State University, Blacksburg Virginia 24061 United States
  2. Department of Physics, Purdue University, 525 Northwestern Avenue West Lafayette Indiana 47907 United States
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1356411
Resource Type:
Journal Article
Journal Name:
ChemSusChem
Additional Journal Information:
Journal Volume: 10; Journal Issue: 3; Journal ID: ISSN 1864-5631
Publisher:
ChemPubSoc Europe
Country of Publication:
United States
Language:
ENGLISH
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE

Citation Formats

Lin, Shaoyang, Pineda-Galvan, Yuliana, Maza, William A., Epley, Charity C., Zhu, Jie, Kessinger, Matthew C., Pushkar, Yulia, and Morris, Amanda J. Electrochemical Water Oxidation by a Catalyst-Modified Metal-Organic Framework Thin Film. United States: N. p., 2016. Web. doi:10.1002/cssc.201601181.
Lin, Shaoyang, Pineda-Galvan, Yuliana, Maza, William A., Epley, Charity C., Zhu, Jie, Kessinger, Matthew C., Pushkar, Yulia, & Morris, Amanda J. Electrochemical Water Oxidation by a Catalyst-Modified Metal-Organic Framework Thin Film. United States. doi:10.1002/cssc.201601181.
Lin, Shaoyang, Pineda-Galvan, Yuliana, Maza, William A., Epley, Charity C., Zhu, Jie, Kessinger, Matthew C., Pushkar, Yulia, and Morris, Amanda J. Thu . "Electrochemical Water Oxidation by a Catalyst-Modified Metal-Organic Framework Thin Film". United States. doi:10.1002/cssc.201601181.
@article{osti_1356411,
title = {Electrochemical Water Oxidation by a Catalyst-Modified Metal-Organic Framework Thin Film},
author = {Lin, Shaoyang and Pineda-Galvan, Yuliana and Maza, William A. and Epley, Charity C. and Zhu, Jie and Kessinger, Matthew C. and Pushkar, Yulia and Morris, Amanda J.},
abstractNote = {Water oxidation, a key component in artificial photosynthesis, requires high overpotentials and exhibits slow reaction kinetics that necessitates the use of stable and efficient heterogeneous water-oxidation catalysts (WOCs). Here, we report the synthesis of UiO-67 metal–organic framework (MOF) thin films doped with [Ru(tpy)(dcbpy)OH2]2+ (tpy=2,2':6',2''-terpyridine, dcbpy=5,5'-dicarboxy-2,2'-bipyridine) on conducting surfaces and their propensity for electrochemical water oxidation. The electrocatalyst oxidized water with a turnover frequency (TOF) of (0.2±0.1) s-1 at 1.71 V versus the normal hydrogen electrode (NHE) in buffered solution (pH~7) and exhibited structural and electrochemical stability. The electroactive sites were distributed throughout the MOF thin film on the basis of scan-ratedependent voltammetry studies. This work demonstrates a promising way to immobilize large concentrations of electroactive WOCs into a highly robust MOF scaffold and paves the way for future photoelectrochemical water-splitting systems.},
doi = {10.1002/cssc.201601181},
journal = {ChemSusChem},
issn = {1864-5631},
number = 3,
volume = 10,
place = {United States},
year = {2016},
month = {12}
}

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