Abstract In order to elucidate the role of chlorine vacancy on CuCl2 catalyst in species adsorption and the mechanism of SiCl4 dissociation into SiHCl3, density functional theory (DFT) calculations were performed over the CuCl2(0 0 1) surfaces with single and double Cl-vacancy, comparing with those over the perfect CuCl2(0 0 1). The calculation results show that Cl vacancies on the CuCl2(0 0 1) surface cause low-coordination site Cu atoms and the exposed Cu atoms work as the actually catalytic active sites, which can promote species adsorption and dissociation. The CuCl2 catalyst enriched with exposed Cu active sites exhibits higher catalytic activity and higher selectivity of SiHCl3. Bader charge analysis indicates that the smaller positive charge leads to the higher species adsorption energies and better catalytic selectivity and activity of SiCl4 dissociation into SiHCl3. The closer the d-band center is to the Fermi level, the higher the species adsorption energy and the better catalytic selectivity and activity of SiCl4 dissociation into SiHCl3. It suggests that the double Cl-vacancy CuCl2(0 0 1) catalyst has better activity and selectivity to produce SiHCl3 via SiCl4 decomposition, and the favorable pathway is SiCl4 → SiCl3 + Cl+(H) → SiHCl3, which can provide useful guidance on the development of efficient catalysts for SiCl4 dissociation into SiHCl3.

中文翻译：

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CuCl2(001)催化剂中氯空位对SiCl4解离为SiHCl3机理的影响：DFT研究

摘要 为了阐明氯空位对 CuCl2 催化剂的吸附作用以及 SiCl4 解离为 SiHCl3 的机理，对具有单和双氯空位的 CuCl2(0 0 1) 表面进行了密度泛函理论 (DFT) 计算。 , 与完美的 CuCl2(0 0 1) 相比。计算结果表明，CuCl2(0 0 1)表面的Cl空位导致Cu原子配位低，暴露的Cu原子作为实际催化活性位点，可以促进物种吸附和解离。富含暴露的 Cu 活性位点的 CuCl2 催化剂表现出更高的催化活性和更高的 SiHCl3 选择性。Bader 电荷分析表明，较小的正电荷导致更高的物质吸附能和更好的催化选择性和更好的 SiCl4 解离为 SiHCl3 的活性。d 带中心越接近费米能级，物质吸附能越高，SiCl4 解离为 SiHCl3 的催化选择性和活性越好。这表明双Cl-空位CuCl2(0 0 1)催化剂通过SiCl4分解生成SiHCl3具有更好的活性和选择性，有利的途径是SiCl4→SiCl3+Cl+(H)→SiHCl3，这可以提供有益的指导。开发用于 SiCl4 离解为 SiHCl3 的高效催化剂。物质吸附能越高，SiCl4 解离为 SiHCl3 的催化选择性和活性越好。这表明双Cl-空位CuCl2(0 0 1)催化剂通过SiCl4分解生成SiHCl3具有更好的活性和选择性，有利的途径是SiCl4→SiCl3+Cl+(H)→SiHCl3，这可以提供有益的指导。开发用于 SiCl4 离解为 SiHCl3 的高效催化剂。物质吸附能越高，SiCl4 解离为 SiHCl3 的催化选择性和活性越好。这表明双Cl-空位CuCl2(0 0 1)催化剂通过SiCl4分解生成SiHCl3具有更好的活性和选择性，有利的途径是SiCl4→SiCl3+Cl+(H)→SiHCl3，这可以提供有益的指导。开发用于 SiCl4 离解为 SiHCl3 的高效催化剂。