Hydroxyl Formation on Pt(553)

Hydroxyl Formation on Pt(553)
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Pt(553) 上的羟基形成

DOI:
10.1021/acs.jpcc.3c02010
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发表时间:
2023
期刊:
The Journal of Physical Chemistry C
影响因子:
--
通讯作者:
Watanabe Kazuya
Watanabe Kazuya
中科院分区:
--
文献类型:
--
作者:
Nagatsuka Naoki;Kamibashira Shota;Shibata Noboru;Koitaya Takanori;Watanabe Kazuya

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本文在145K超高真空条件下,用外差探测的振动和频产生谱研究了氧原子和水分子(D2O)在铂(553)表面的共吸附,成功地获得了氧修饰台阶位上亚单层水覆盖的氢键O-D伸缩区表面非线性极化率的虚部(Imχ(2))。水分子发生解离,导致在台阶上形成羟基。在2 6 0 0-2 70 0 cm-1处发现了羟基物种的O-D伸缩带,在Imχ(2)光谱中显示出正信号。根据Imχ(2)的符号和强度,估算出羟基的OD键与表面法线的平均夹角为∼60°。此外,在2460 cm~(-1)处观察到一个负峰,该负峰归因于D2O在台阶上与羟基共吸附。提出了水和羟基络合物氢键网络结构的可能结构。阶梯上的氧气装饰对阶地上水网络的质子构型也有很大影响。
In this paper, the coadsorption of oxygen atoms and water molecules (D2O) on Pt(553) is studied by using heterodyne-detected vibrational sum-frequency generation spectroscopy under ultrahigh vacuum conditions at 145 K. The imaginary parts of the surface nonlinear susceptibility (Imχ(2)) of the hydrogen-bonded O–D stretching region are successfully obtained for submonolayer water coverage on oxygen-decorated step sites. Dissociation of the water molecules occurs that leads to hydroxyl formation at the steps. The O–D stretching bands of the hydroxyl species are identified at 2600–2700 cm–1, which show positive signals in the Imχ(2)spectra. From the sign and the intensity of Imχ(2), the average angle of the OD bond of the hydroxyl is estimated to be ∼60° from the surface normal. In addition, a negative peak at 2460 cm–1is observed that is ascribed to D2O coadsorbed with the hydroxyl at the steps. Possible structures of the hydrogen bond network of the water and hydroxyl complex are proposed. It is also shown that the oxygen decoration at the step strongly affects the proton configuration of the water network at the terrace.
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