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Title: Composition-Dependent Functionality of Copper Vanadate Photoanodes

Abstract

To understand functional roles of constituent elements in ternary metal oxide photoanodes, essential photoelectrochemical (PEC) properties are systematically analyzed on a series of copper vanadate compounds with different Cu:V elemental ratios. Here, homogeneous and highly continuous thin films of β-Cu2V2O7, γ-Cu3V2O8, Cu11V6O26, and Cu5V2O10 are grown via reactive co-sputtering and their performance characteristics for the light-driven oxygen evolution reaction are evaluated. All four compounds have similar bandgaps in the range of 1.83-2.03 eV, though Cu-rich phases exhibit stronger optical absorption and higher charge separation efficiencies. Transient photocurrent analysis reveals a reduction of surface catalytic activity with increasing Cu:V elemental ratio due to competitive charge recombination at Cu-related surface states. This comprehensive analysis of PEC functionalities - including photon absorption, carrier separation, and heterogeneous charge transfer - informs strategies for improving PEC activity in the copper vanadate materials system and reveals insights that may aid discovery, design, and engineering of new photoelectrode materials.

Authors:
ORCiD logo [1];  [1];  [1];  [1];  [1];  [1];  [1]; ORCiD logo [2]
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  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  2. Technische Univ. Munchen, Garching (Germany)
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). Chemical Sciences, Geosciences & Biosciences Division
OSTI Identifier:
1506303
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
ACS Applied Materials and Interfaces
Additional Journal Information:
Journal Volume: 10; Journal Issue: 13; Journal ID: ISSN 1944-8244
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; copper vanadate; photoanode; photoelectrochemistry; surface states; transient photocurrent analysis; water oxidation

Citation Formats

Jiang, Chang-Ming, Segev, Gideon, Hess, Lucas H., Liu, Guiji, Zaborski, Gregory, Toma, Francesca M., Cooper, Jason K., and Sharp, Ian D. Composition-Dependent Functionality of Copper Vanadate Photoanodes. United States: N. p., 2018. Web. doi:10.1021/acsami.8b02977.
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Jiang, Chang-Ming, Segev, Gideon, Hess, Lucas H., Liu, Guiji, Zaborski, Gregory, Toma, Francesca M., Cooper, Jason K., & Sharp, Ian D. Composition-Dependent Functionality of Copper Vanadate Photoanodes. United States. doi:10.1021/acsami.8b02977.
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Jiang, Chang-Ming, Segev, Gideon, Hess, Lucas H., Liu, Guiji, Zaborski, Gregory, Toma, Francesca M., Cooper, Jason K., and Sharp, Ian D. Wed . "Composition-Dependent Functionality of Copper Vanadate Photoanodes". United States. doi:10.1021/acsami.8b02977. https://www.osti.gov/servlets/purl/1506303.
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@article{osti_1506303,
title = {Composition-Dependent Functionality of Copper Vanadate Photoanodes},
author = {Jiang, Chang-Ming and Segev, Gideon and Hess, Lucas H. and Liu, Guiji and Zaborski, Gregory and Toma, Francesca M. and Cooper, Jason K. and Sharp, Ian D.},
abstractNote = {To understand functional roles of constituent elements in ternary metal oxide photoanodes, essential photoelectrochemical (PEC) properties are systematically analyzed on a series of copper vanadate compounds with different Cu:V elemental ratios. Here, homogeneous and highly continuous thin films of β-Cu2V2O7, γ-Cu3V2O8, Cu11V6O26, and Cu5V2O10 are grown via reactive co-sputtering and their performance characteristics for the light-driven oxygen evolution reaction are evaluated. All four compounds have similar bandgaps in the range of 1.83-2.03 eV, though Cu-rich phases exhibit stronger optical absorption and higher charge separation efficiencies. Transient photocurrent analysis reveals a reduction of surface catalytic activity with increasing Cu:V elemental ratio due to competitive charge recombination at Cu-related surface states. This comprehensive analysis of PEC functionalities - including photon absorption, carrier separation, and heterogeneous charge transfer - informs strategies for improving PEC activity in the copper vanadate materials system and reveals insights that may aid discovery, design, and engineering of new photoelectrode materials.},
doi = {10.1021/acsami.8b02977},
journal = {ACS Applied Materials and Interfaces},
number = 13,
volume = 10,
place = {United States},
year = {2018},
month = {2}
}
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Journal Article:
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DOI:  10.1021/acsami.8b02977
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