Electron-deficient Cu site catalyzed acetylene hydrochlorination

Rational design of catalytic sites to activate the CC bond is of paramount importance to advance acetylene hydrochlorination. Herein, Cu sites with electron-rich and electron-deficient states were constructed by controlling the impregnation solutions. The π electrons flowing from acetylene to Cu site are facilitated over the electron-deficient Cu sites, achieving high activation of CC bond. The contradiction between the increased activation of acetylene required for enhanced catalytic activity and the resistance of Cu site to reduction by acetylene required for maintaining catalytic stability can be balanced by establishing strong interactions of Cu site with pyrrolic-N species. The catalytic activity displays a volcano shape scaling relationship as a function of Cu particle size. Tribasic copper chloride is concomitantly generated with the construction of electron-deficient Cu sites. The H–Cl bond of HCl can be activated over the tribasic copper chloride, accelerating the surface reaction of vinyl chloride production. This strategy of inducing electron deficiency provides new insight into the rational design of catalysts for the synthesis of vinyl chloride with a high catalytic performance. [Display omitted] •Cu sites stabilized by pyrrolic-N are responsible for the formation of electron-deficient states.•High activation of CC bond in acetylene is facilitated over the electron-deficient Cu sites.•The bond of H–Cl can be activated over the tribasic copper chloride, accelerating the surface reaction process of VCM production.