Goodacre Dana, Blum Monika, Buechner Christin, Hoek Harmen, Gericke Sabrina M, Jovic Vedran, Franklin Joseph B, Kittiwatanakul Salinporn, Söhnel Tilo, Bluhm Hendrik, Smith Kevin E
School of Chemical Sciences, University of Auckland, Auckland 1142, New Zealand.
Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, California 94720, USA.
J Chem Phys. 2020 Jan 31;152(4):044715. doi: 10.1063/1.5138959.
In this work, ambient pressure x-ray photoelectron spectroscopy (APXPS) is used to study the initial stages of water adsorption on vanadium oxide surfaces. V 2p, O 1s, C 1s, and valence band XPS spectra were collected as a function of relative humidity in a series of isotherm and isobar experiments. Experiments were carried out on two VO thin films on TiO (100) substrates, prepared with different surface cleaning procedures. Hydroxyl and molecular water surface species were identified, with up to 0.5 ML hydroxide present at the minimum relative humidity, and a consistent molecular water adsorption onset occurring around 0.01% relative humidity. The work function was found to increase with increasing relative humidity, suggesting that surface water and hydroxyl species are oriented with the hydrogen atoms directed away from the surface. Changes in the valence band were also observed as a function of relative humidity. The results were similar to those observed in APXPS experiments on other transition metal oxide surfaces, suggesting that HO-OH and HO-HO surface complex formation plays an important role in the oxide wetting process and water dissociation. Compared to polycrystalline vanadium metal, these vanadium oxide films generate less hydroxide and appear to be more favorable for molecular water adsorption.
在这项工作中,利用常压X射线光电子能谱(APXPS)研究了水在氧化钒表面吸附的初始阶段。在一系列等温线和等压线实验中,收集了V 2p、O 1s、C 1s和价带XPS光谱随相对湿度的变化情况。实验在TiO(100)衬底上的两种VO薄膜上进行,这两种薄膜采用了不同的表面清洁程序制备。识别出了羟基和分子水表面物种,在最低相对湿度下存在高达0.5 ML的氢氧化物,且在相对湿度约为0.01%时出现一致的分子水吸附起始点。发现功函数随相对湿度增加而增大,这表明表面水和羟基物种的取向是氢原子远离表面。还观察到价带随相对湿度的变化。结果与在其他过渡金属氧化物表面的APXPS实验中观察到的结果相似,表明HO-OH和HO-HO表面络合物的形成在氧化物润湿过程和水离解中起重要作用。与多晶钒金属相比,这些氧化钒薄膜产生的氢氧化物较少,似乎更有利于分子水的吸附。