金催化乙炔氢氯化的密度泛函理论研究进展

乙炔氢氯化(AH)是生产氯乙烯的主要途径之一，传统上使用高毒性的汞催化剂，因此开发无汞催化剂迫在眉睫。金(Au)催化剂是最有潜力的替代催化剂之一，然而其活性Au物种、反应物的活化过程或反应过渡态结构等催化机理仍不够清晰。密度泛函理论（DFT）在研究由Au催化AH的反应机理中发挥了极其重要的作用。本文综述了DFT对金催化剂活性位点、反应物在催化剂上的吸附性质及反应机理的研究进展。重点讨论了DFT对阳离子金和金簇催化AH反应过程的模拟计算，包括Au电子状态、其它原子掺杂及金簇尺寸和形状对催化AH反应影响的模拟。结果表明DFT模拟计算在微观分子尺度上研究反应物的吸附、反应中间体及过渡态等方面发挥了关键作用，对理解Au催化AH反应机理做出了重要贡献。

Research Progress of the DFT Study on the Acetylene Hydrochlorination over Gold Catalyst

Acetylene hydrochlorination (AH) is one of the primary ways for producing vinyl chloride. AH traditionally uses highly toxic mercury catalysts, so the development of mercury-free catalysts is urgent. Gold (Au) catalyst is one of the most promising alternative catalysts. However, the catalytic mechanism like the active Au species, the activation process of the reactants or the transition state in the reaction system is not very clear yet. Density functional theory (DFT) has played a highly important role in studying the reaction mechanism of Au catalyzed AH. This work reviews the research progress of the DFT study on the active sites, the adsorption properties of reactants on the Au catalysts, and the reaction mechanism. The DFT simulation of the catalytic AH reaction process over cationic Au and Au clusters is emphatically discussed, including the simulation for the effects of the electron state of Au, the doping by other metals, as well as the size and shape of Au cluster on the catalytic AH reaction. The results indicate that DFT calculations have played a crucial role in studying the adsorption, reaction intermediates, and transition state at the molecular scale, which significantly contributes to understanding the mechanism of Au-catalyzed AH reactions.