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标题：Probing equilibrium of molecular and deprotonated water on TiO2(110)
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作者：Zhi-Tao Wang ; Yang-Gang Wang ; Rentao Mu 等
期刊名称：Proceedings of the National Academy of Sciences
印刷版ISSN：0027-8424
电子版ISSN：1091-6490
出版年度：2017
卷号：114
期号：8
页码：1801-1805
DOI：10.1073/pnas.1613756114
语种：English
出版社：The National Academy of Sciences of the United States of America
摘要：Understanding adsorbed water and its dissociation to surface hydroxyls on oxide surfaces is key to unraveling many physical and chemical processes, yet the barrier for its deprotonation has never been measured. In this study, we present direct evidence for water dissociation equilibrium on rutile-TiO₂(110) by combining supersonic molecular beam, scanning tunneling microscopy (STM), and ab initio molecular dynamics. We measure the deprotonation/protonation barriers of 0.36 eV and find that molecularly bound water is preferred over the surface-bound hydroxyls by only 0.035 eV. We demonstrate that long-range electrostatic fields emanating from the oxide lead to steering and reorientation of the molecules approaching the surface, activating the O–H bonds and inducing deprotonation. The developed methodology for studying metastable reaction intermediates prepared with a high-energy molecular beam in the STM can be readily extended to other systems to clarify a wide range of important bond activation processes.
关键词：adsorbate dynamics ; water ; dissociative adsorption ; titanium dioxide ; kinetic barriers