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Title: Overall Photocatalytic Water Splitting with NiOx-SrTiO3 – A Revised Mechanism

Abstract

NiOx (0 < x < 1) modified SrTiO3 (STO) is one of the best studied photocatalyst for overall water splitting under UV light. The established mechanism for this and many other NiOx containing catalysts assumes water oxidation to occur at the early transition metal oxide and water reduction at NiOx. Here we show that NiOx-STO is more likely a three component Ni-STO-NiO catalyst, in which STO absorbs the light, Ni reduces protons, and NiO oxidizes water. This interpretation is based on systematic H2/O2 evolution tests of appropriately varied catalyst compositions using oxidized, chemically and photochemically added nickel and NiO nanoparticle cocatalysts. Surface photovoltage (SPV) measurements reveal that Ni(0) serves as an electron trap (site for water reduction) and that NiO serves as a hole trap (site for water oxidation). Electrochemical measurements show that the overpotential for water oxidation correlates with NiO content, whereas the water reduction overpotential depends on Ni content. Photodeposition experiments with NiCl2 and H2PtCl6 on NiO-STO show that electrons are available on the STO surface, not on the NiO particles. Based on photoelectrochemistry, both NiO and Ni particles suppress the Fermi level in STO, but the effect of this shift on catalytic activity is not clear. Overall,more » the results suggest a revised role for NiO in NiOx-STO and in many other nickel-containing water splitting systems, including NiOx-La:KTaO3, and many layered perovskites.« less

Authors:
; ;
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1056159
Report Number(s):
PNNL-SA-88342
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Journal Name:
Energy & Environmental Science, 5(11):9543-9550
Additional Journal Information:
Journal Name: Energy & Environmental Science, 5(11):9543-9550
Country of Publication:
United States
Language:
English

Citation Formats

Townsend, Troy K., Browning, Nigel D., and Osterloh, Frank. Overall Photocatalytic Water Splitting with NiOx-SrTiO3 – A Revised Mechanism. United States: N. p., 2012. Web. doi:10.1039/c2ee22665k.
Townsend, Troy K., Browning, Nigel D., & Osterloh, Frank. Overall Photocatalytic Water Splitting with NiOx-SrTiO3 – A Revised Mechanism. United States. doi:10.1039/c2ee22665k.
Townsend, Troy K., Browning, Nigel D., and Osterloh, Frank. Thu . "Overall Photocatalytic Water Splitting with NiOx-SrTiO3 – A Revised Mechanism". United States. doi:10.1039/c2ee22665k.
@article{osti_1056159,
title = {Overall Photocatalytic Water Splitting with NiOx-SrTiO3 – A Revised Mechanism},
author = {Townsend, Troy K. and Browning, Nigel D. and Osterloh, Frank},
abstractNote = {NiOx (0 < x < 1) modified SrTiO3 (STO) is one of the best studied photocatalyst for overall water splitting under UV light. The established mechanism for this and many other NiOx containing catalysts assumes water oxidation to occur at the early transition metal oxide and water reduction at NiOx. Here we show that NiOx-STO is more likely a three component Ni-STO-NiO catalyst, in which STO absorbs the light, Ni reduces protons, and NiO oxidizes water. This interpretation is based on systematic H2/O2 evolution tests of appropriately varied catalyst compositions using oxidized, chemically and photochemically added nickel and NiO nanoparticle cocatalysts. Surface photovoltage (SPV) measurements reveal that Ni(0) serves as an electron trap (site for water reduction) and that NiO serves as a hole trap (site for water oxidation). Electrochemical measurements show that the overpotential for water oxidation correlates with NiO content, whereas the water reduction overpotential depends on Ni content. Photodeposition experiments with NiCl2 and H2PtCl6 on NiO-STO show that electrons are available on the STO surface, not on the NiO particles. Based on photoelectrochemistry, both NiO and Ni particles suppress the Fermi level in STO, but the effect of this shift on catalytic activity is not clear. Overall, the results suggest a revised role for NiO in NiOx-STO and in many other nickel-containing water splitting systems, including NiOx-La:KTaO3, and many layered perovskites.},
doi = {10.1039/c2ee22665k},
journal = {Energy & Environmental Science, 5(11):9543-9550},
number = ,
volume = ,
place = {United States},
year = {2012},
month = {11}
}