乙炔氢氯化反应铜系催化剂的反应机理

以电石乙炔法制备氯乙烯的非汞催化反应体系为研究对象,用量子化学密度泛函理论(DFT)研究了以Cu基催化剂为代表的非汞催化剂的反应机理.模拟了以石墨烯为载体的乙炔氢氯化反应在Cu基催化剂作用下的两条反应路径及其过渡态.将该反应机理应用到不同金属氯化物催化剂中,通过计算相应的活化自由能和反应速率常数讨论了不同金属氯化物的活性顺序,与实验结果相比较印证了反应机理的合理性.讨论了Cu基催化剂的失活原因以及在载体中掺杂氮原子或磷原子对反应活性的影响.为非贵金属无汞催化剂的研究提供了一定的理论指导.

Reaction mechanism of acetylene hydrochlorination in Cu-based catalyst

The reaction mechanism of acetylene hydrochlorination in Cu-based catalyst was studied using the density function theory (DFT). Two possible paths for acetylene hydrochlorination reaction in Cu-based catalyst were illustrated with corresponding transition states. We applied the reaction mechanism to various metal chlorides and obtained an order of different catalyst by analyzing the activation free energies and reaction rate constants. The result was compared with experimental ones to verify the reaction mechanism. The deactivation reason of Cu-based catalyst and the reaction on the N/P-doped graphene were also discussed. The conclusion from this study will shed light on the experimental design of novel non-mercury catalysts with high performance.