Welcome to the new version of CaltechAUTHORS. Login is currently restricted to library staff. If you notice any issues, please email coda@library.caltech.edu
Published April 22, 2013 | Published
Journal Article Open

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


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.

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).

Attached Files

Published - c3cp50330e.pdf


Files (4.1 MB)
Name Size Download all
4.1 MB Preview Download

Additional details

August 19, 2023
October 24, 2023