Solar Fuel and Solar Hydrogen

Ab initio modeling of water–semiconductor interfaces for photocatalytic water splitting: role of surface oxygen and hydroxyl

[+] Author Affiliations
Brandon C. Wood, Tadashi Ogitsu, Eric Schwegler

Lawrence Livermore National Laboratory, Quantum Simulations Group, 7000 East Avenue, Livermore, California 94550

J. Photon. Energy. 1(1), 016002 (August 29, 2011). doi:10.1117/1.3625563
History: Received February 08, 2011; Revised May 19, 2011; Accepted July 26, 2011; Published August 29, 2011; Online August 29, 2011
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We perform extensive density-functional theory total-energy calculations and ab initio molecular-dynamics simulations to evaluate the structure, stability, and reactivity of oxygen- and hydroxyl-decorated InP(001) surfaces for photoelectrochemical water cleavage. Surface oxygen is adsorbed in one of two primary local bond topologies: In–O–P and In–O–In. We show that the chemical activity of the oxygen-decorated surface toward water dissociation can be connected to the local oxygen bond topology, with In–O–In bridges promoting spontaneous water dissociation. Surface hydroxyl groups tend to form either In–OH–In bridges, though the second of the two In–OH bonds is easily broken. Dynamics simulations of the full water–semiconductor interface show surface proton transfer when the surface is hydroxylated, facilitated by strong hydrogen bonding between atop OH groups and with interfacial water molecules. Implications for understanding the reaction dynamics at InP(001)–water interfaces are discussed.

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© 2011 Society of Photo-Optical Instrumentation Engineers (SPIE)

Citation

Brandon C. Wood ; Tadashi Ogitsu and Eric Schwegler
"Ab initio modeling of water–semiconductor interfaces for photocatalytic water splitting: role of surface oxygen and hydroxyl", J. Photon. Energy. 1(1), 016002 (August 29, 2011). ; http://dx.doi.org/10.1117/1.3625563


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