How Surface Potential Determines the Kinetics of the First Hole Transfer of Photocatalytic Water Oxidation
详细信息 查看全文
- 作者：Matthias M. Waegele ; Xihan Chen ; David M. Herlihy ; Tanja Cuk
- 刊名：Journal of the American Chemical Society
- 出版年：2014
- 出版时间：July 30, 2014
- 年：2014
- 卷：136
- 期：30
- 页码：10632-10639
- 全文大小：492K
- ISSN：1520-5126
文摘
Interfacial hole transfer between n-SrTiO3 and OH鈥?/sup> was investigated by surface sensitive transient optical spectroscopy of an in situ photoelectrochemical cell during water oxidation. The kinetics reveal a single rate constant with an exponential dependence on the surface hole potential, spanning time scales from 3 ns to 8 ps over a 鈮? V increase. A voltage- and laser illumination-induced process moves the valence band edge at the n-type semiconductor/water interface to continuously change the surface hole potential. This single step of the water oxidation reaction is assigned to the first hole transfer h+ + OH鈥?/sup> 鈫?OH鈥?/sup>. The kinetics quantify how much a change in the free energy difference driving this first hole transfer reduces the activation barrier. They are also used to extrapolate the kinetic rate due to the activation barrier when that free energy difference is zero, or the Nernstian potential. This is the first time transient spectroscopy has enabled the separation of the first hole transfer from the full four hole transfer cycle and a direct determination of these two quantities. The Nernstian potential for OH鈥?/sup>/OH鈥?/sup> is also suggested, in rough agreement with gas-phase studies. The observation of a distinct, much longer time scale upon picosecond hole transfer to OH鈥?/sup> suggests that a dominant, more stable intermediate of the water oxidation reaction, possibly a surface bound oxo, may result.