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Dependence on the structure and surface polarity of ZnS photocatalytic activities of water splitting: first-principles calculations

Meng, Xiangying and Xiao, Hai and Wen, Xiaohong and Goddard, William A., III and Li, Song and Qin, Gaowu (2013) Dependence on the structure and surface polarity of ZnS photocatalytic activities of water splitting: first-principles calculations. Physical Chemistry Chemical Physics, 15 (24). pp. 9531-9539. ISSN 1463-9076. doi:10.1039/c3cp50330e. https://resolver.caltech.edu/CaltechAUTHORS:20130708-093932692

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Abstract

It has been reported that phase structure and surface polarity largely affect the photocatalytic efficiency of semiconductor nanostructures. To understand the chemical activity of ZnS at the electronic level, we investigate electron structures and carrier transportation ability for bulk intrinsic zinc blende (ZB) and wurtzite (WZ) ZnS, as well as the reaction pathway of hydrogen generation from water splitting on Zn- and S-terminated polar surfaces. The electron structure calculations prove that the WZ phase possesses a higher reducing ability than the ZB phase. The conductivity of the bulk ZB phase surpasses that of the WZ phase at or above room temperature. As the temperature increases, the asymptotic conductivity ratio of WZ/ZB is close to the Golden Ratio, 0.62. Reaction kinetics studies indicate that Zn-terminated polar surfaces are more chemically active than S-terminated polar surfaces in the reaction of hydrogen generation from water splitting. The calculation results suggest that the first H splitting from water on Zn-terminated polar surfaces can occur with ground state electronic structures, while photo-assistance is necessary for the first H splitting on the S-terminated surfaces. Electronic triplet states calculations further show that Zn-terminated surfaces are more photosensitive than S-terminated surfaces.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1039/c3cp50330e DOIArticle
http://pubs.rsc.org/en/Content/ArticleLanding/2013/CP/c3cp50330ePublisherArticle
ORCID:
AuthorORCID
Xiao, Hai0000-0001-9399-1584
Goddard, William A., III0000-0003-0097-5716
Additional Information:© 2013 the Owner Societies. Received 23 Jan 2013, Accepted 16 Apr 2013. First published online 22 Apr 2013. The authors gratefully acknowledge financial support by the National Natural Science Foundation of China (no. 51001025 and 51002026), the Fundamental Research Funds for the Central Universities (no. 110405003, 110810001 and 100702001) and National 863 project (2012AA030314).
Funders:
Funding AgencyGrant Number
National Natural Science Foundation of China51001025
National Natural Science Foundation of China51002026
Fundamental Research Funds for the Central Universities110405003
Fundamental Research Funds for the Central Universities110810001
Fundamental Research Funds for the Central Universities100702001
National 863 Project2012AA030314
Issue or Number:24
DOI:10.1039/c3cp50330e
Record Number:CaltechAUTHORS:20130708-093932692
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20130708-093932692
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:39243
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:12 Aug 2013 22:12
Last Modified:09 Nov 2021 23:43

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