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Solvation effects on the band edge positions of photocatalysts from first principles

Ping, Yuan and Sundararaman, Ravishankar and Goddard, William A., III (2015) Solvation effects on the band edge positions of photocatalysts from first principles. Physical Chemistry Chemical Physics, 17 (45). pp. 30499-30509. ISSN 1463-9076. doi:10.1039/c5cp05740j.

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The band edge positions of photocatalysts relative to the redox potentials of water play an important role in determining the efficiency of photoelectrochemical cells. These band positions depend on the structure of the solid–liquid interface, but direct ab initio molecular dynamics calculations of these interfaces, while expected to be accurate, are too computationally demanding for high-throughput materials screening. Thus rapid theoretical screening of new photocatalyst materials requires simplified continuum solvation models that are suitable for treating solid–liquid interfaces. In this paper, we evaluate the accuracy of the recently developed CANDLE and SaLSA continuum solvation models for predicting solvation effects on the band positions of several well-studied surfaces [Si(111), TiO_2(110), IrO_2(110) and WO_3(001)] in water. We find that the solvation effects vary considerably, ranging from <0.5 eV for hydrophobic surfaces, 0.5–1 eV for many hydrophilic oxide surfaces, to ∼2 eV for oxygen-deficient surfaces. The solvation model predictions are in excellent agreement (within ∼0.1 eV) with ab initio molecular dynamics results where available, and in good agreement (within ∼0.2–0.3 eV) with experimental measurements. We also predict the energetics for surface oxygen vacancies and their effect on the band positions of the hydrated WO_3(001) surface, leading to an explanation for why the solvation shift observed experimentally is substantially larger than predicted for the ideal surface. Based on the correlation between solvation shift and the type of surface and solvent, we suggest approaches to engineer the band positions of surfaces in aqueous and non-aqueous solutions.

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Sundararaman, Ravishankar0000-0002-0625-4592
Goddard, William A., III0000-0003-0097-5716
Additional Information:© 2015 the Owner Societies. This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. Received 24th September 2015, Accepted 26th October 2015, First published online 26 Oct 2015. We thank Giulia Galli and Tuan Anh Pham for many useful discussions. This publication is based upon work performed by the Joint Center for Artificial Photosynthesis, a DOE Energy Innovation Hub, supported through the Office of Science of the U.S. Department of Energy under Award Number DESC0004993.
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Department of Energy (DOE)DE-SC0004993
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Issue or Number:45
Record Number:CaltechAUTHORS:20151103-075722264
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Official Citation:Solvation effects on the band edge positions of photocatalysts from first principles Yuan Ping, Ravishankar Sundararamana and William A. Goddard III Phys. Chem. Chem. Phys., 2015, 17, 30499-30509 DOI: 10.1039/C5CP05740J
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:61780
Deposited By: Tony Diaz
Deposited On:03 Nov 2015 16:36
Last Modified:10 Nov 2021 22:53

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