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Title: Hydrogen production by photoelectrolytic decomposition of H/sub 2/O using solar energy. Final report, July 22, 1977-July 21, 1978

Abstract

The purpose of this program is to develop new semiconducting electrodes for the economical efficient photoelectrochemical decomposition of H/sub 2/O using solar energy. Due to the intimacy of the liquid-solid rectifying junction, this technique is particularly well-suited to inexpensive polycrystalline electrode fabrications. During the past year, work has concentrated on photoanode development, specifically anodically robust semiconducting oxides. It was found that some thin film oxides formed by a simple chemical vapor deposition (CVD) procedure perform quite well, with maximum solar power conversion efficiencies of 0.5 to 1.0% for CVD TiO/sub 2/ despite a band gap of 3.1 eV, which is a poor match for the solar spectrum. CuO, Fe/sub 2/O/sub 3/, WO/sub 3/ and some mixed oxide thin film electrodes were also prepared pyrolytically and showed good photoresponse. The argument is put forth, however, that no stable oxide photoanodes yet discovered have the combined properties of low electron affinity (EA) and optimal band gap required for the efficient photoelectrolysis of H/sub 2/O. Compounds like TiO/sub 2/ and SrTiO/sub 3/ have satisfactory EA's, but their valence bands lie too deep, rendering their band gaps impractically large. It is probable that only d-band oxides would have valence bands high enough in energymore » to give rise to this combination of properties. In order to produce such materials, over 60 new perovskites and rutiles containing d/sup n/ transition metals have been synthesized and evaluated as sintered disc photoelectrodes. Mostly 3d metal oxides were investigated. Sensitization of photocurrents to the visible portion of the spectrum was noted in several cases confirming this materials design philosophy. As a rule, photocurrent quantum yields were lower for the d/sup n/-substituted oxides than for the wide band gap, d/sup 0/-oxides like SrTiO/sub 3/ and TiO/sub 2/. This is ascribed partially to poor mobility of the d electrons.« less

Authors:
; ; ;
Publication Date:
Research Org.:
EIC Corp., Newton, MA (USA)
OSTI Identifier:
5306382
Report Number(s):
COO-5060-4
DOE Contract Number:  
EC-77-C-01-5060
Resource Type:
Technical Report
Country of Publication:
United States
Language:
English
Subject:
08 HYDROGEN; 14 SOLAR ENERGY; 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; HYDROGEN PRODUCTION; PHOTOELECTROLYSIS; PHOTOANODES; DESIGN; FABRICATION; TESTING; COPPER OXIDES; IRON OXIDES; SEMICONDUCTOR MATERIALS; TITANIUM OXIDES; TUNGSTEN OXIDES; WATER; ANODES; CHALCOGENIDES; COPPER COMPOUNDS; ELECTRODES; ELECTROLYSIS; HYDROGEN COMPOUNDS; IRON COMPOUNDS; LYSIS; MATERIALS; OXIDES; OXYGEN COMPOUNDS; TITANIUM COMPOUNDS; TRANSITION ELEMENT COMPOUNDS; TUNGSTEN COMPOUNDS; 080101* - Hydrogen- Production- Electrolysis; 140505 - Solar Energy Conversion- Photochemical, Photobiological, & Thermochemical Conversion- (1980-); 400201 - Chemical & Physicochemical Properties

Citation Formats

Rauh, R.D., Alkaitis, S.A., Buzby, J.M., and Reise, T.F. Hydrogen production by photoelectrolytic decomposition of H/sub 2/O using solar energy. Final report, July 22, 1977-July 21, 1978. United States: N. p., 1979. Web.
Rauh, R.D., Alkaitis, S.A., Buzby, J.M., & Reise, T.F. Hydrogen production by photoelectrolytic decomposition of H/sub 2/O using solar energy. Final report, July 22, 1977-July 21, 1978. United States.
Rauh, R.D., Alkaitis, S.A., Buzby, J.M., and Reise, T.F. Thu . "Hydrogen production by photoelectrolytic decomposition of H/sub 2/O using solar energy. Final report, July 22, 1977-July 21, 1978". United States.
@article{osti_5306382,
title = {Hydrogen production by photoelectrolytic decomposition of H/sub 2/O using solar energy. Final report, July 22, 1977-July 21, 1978},
author = {Rauh, R.D. and Alkaitis, S.A. and Buzby, J.M. and Reise, T.F.},
abstractNote = {The purpose of this program is to develop new semiconducting electrodes for the economical efficient photoelectrochemical decomposition of H/sub 2/O using solar energy. Due to the intimacy of the liquid-solid rectifying junction, this technique is particularly well-suited to inexpensive polycrystalline electrode fabrications. During the past year, work has concentrated on photoanode development, specifically anodically robust semiconducting oxides. It was found that some thin film oxides formed by a simple chemical vapor deposition (CVD) procedure perform quite well, with maximum solar power conversion efficiencies of 0.5 to 1.0% for CVD TiO/sub 2/ despite a band gap of 3.1 eV, which is a poor match for the solar spectrum. CuO, Fe/sub 2/O/sub 3/, WO/sub 3/ and some mixed oxide thin film electrodes were also prepared pyrolytically and showed good photoresponse. The argument is put forth, however, that no stable oxide photoanodes yet discovered have the combined properties of low electron affinity (EA) and optimal band gap required for the efficient photoelectrolysis of H/sub 2/O. Compounds like TiO/sub 2/ and SrTiO/sub 3/ have satisfactory EA's, but their valence bands lie too deep, rendering their band gaps impractically large. It is probable that only d-band oxides would have valence bands high enough in energy to give rise to this combination of properties. In order to produce such materials, over 60 new perovskites and rutiles containing d/sup n/ transition metals have been synthesized and evaluated as sintered disc photoelectrodes. Mostly 3d metal oxides were investigated. Sensitization of photocurrents to the visible portion of the spectrum was noted in several cases confirming this materials design philosophy. As a rule, photocurrent quantum yields were lower for the d/sup n/-substituted oxides than for the wide band gap, d/sup 0/-oxides like SrTiO/sub 3/ and TiO/sub 2/. This is ascribed partially to poor mobility of the d electrons.},
doi = {},
journal = {},
number = ,
volume = ,
place = {United States},
year = {1979},
month = {2}
}

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