Reaction pathways for HCN on transition metal surfaces
Reaction pathways for HCN on transition metal surfaces
复制标题
HCN在过渡金属表面的反应路径
DOI：
10.1039/c8cp07548d
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发表时间：
2019
影响因子：
3.3
通讯作者：
Trenary, Michael
中科院分区：
文献类型：
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作者：
Abdel-Rahman, Mohammed;Feng, Xu;Muir, Mark;Ghale, Kushal;Xu, Ye;Trenary, Michael
用反射吸收红外光谱和密度泛函理论计算研究了HCN在Pd（111）和Ru（001）表面的吸附和分解。结果进行了比较，HCN吸附在Pt（111）和Cu（100）表面上的早期研究。在所有情况下，低温下的初始吸附都会在3300 cm−1处产生ν（C-H）伸缩峰，这非常接近气相值，表明吸附分子保留了CN三键。当Pd（111）表面被加热到室温时，HCN被转化为氨基碳炔物种CNH 2，这也在Pt（111）表面上观察到。DFT计算证实了CNH 2在Pd（111）上的高稳定性，并提出了其形成的双分子机制。当Cu（100）上的HCN被加热时，它不反应地脱附。相反，当表面被加热时，在Ru（001）上没有检测到稳定的中间体，表明HCN完全分解成原子物种。
The adsorption and decomposition of HCN on the Pd(111) and Ru(001) surfaces have been studied with reflection absorption infrared spectroscopy and density functional theory calculations. The results are compared to earlier studies of HCN adsorption on the Pt(111) and Cu(100) surfaces. In all cases the initial adsorption at low temperatures gives rise to a ν(C–H) stretch peak at ∼3300 cm−1, which is very close to the gas phase value indicating that the triple CN bond is retained for the adsorbed molecule. When the Pd(111) surface is heated to room temperature, the HCN is converted to the aminocarbyne species, CNH2, which was also observed on the Pt(111) surface. DFT calculations confirm the high stability of CNH2 on Pd(111), and suggest a bi-molecular mechanism for its formation. When HCN on Cu(100) is heated, it desorbs without reaction. In contrast, no stable intermediates are detected on Ru(001) as the surface is heated, indicating that HCN decomposes completely to atomic species.