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Ru-based catalysts have shown great potential for the environmentally friendly industrialization of acetylene hydrochlorination. However, the high cost and reduction of active sites in Ru catalysts have limited their practical applications. In this study, we propose a strategy to optimize the electronic structure of Ru single-atom catalysts by leveraging the strong coordination ability of ligands with the metal and apply this strategy to acetylene hydrochlorination. The experimental results verify that the performance of the catalyst increases with the increase of the ligand. Characterization results indicate that ligands not only optimize the electronic properties of Ru single atoms by forming a RuCl 2 -N structure, but also enhance the adsorption of reactants on the catalysts. DFT calculations reveal that the ligand-modified Ru species can efficiently adsorb and activate acetylene molecules, while the adjacent excessive ligand can adsorb and dissociate HCl molecules. This ultimately leads to an addition reaction between acetylene and HCl through a hydrogen overflow mechanism. [Display omitted] ● The single-atom catalyst with RuCl 2 -N structure are successfully synthesized. ● Enhances catalyst stability by optimising the electronic structure of Ru single atoms. ● Pre-dissociative activation of HCl facilitates the acetylene hydrochlorination reaction. ● This research provides an insight for the design of non-mercury catalysts for vinyl chloride. [ABSTRACT FROM AUTHOR]

There is great potential for carbon-supported gold catalysts to replace toxic mercuric chloride-based catalysts in the acetylene hydrochlorination, which is a key process for producing PVC. However, the catalyst design is essentially hindered by the difficulties in enhancing the catalytic activity of cationic gold and suppressing the deactivation of active species. We report a strategy for self-oxidation of Au3+ by the Au-SILP system with the [Bmim][Cl 3 ] ILs. This strategy can stabilize all gold species in the state of highly oxidized Au3+ instead of coexisting in the Au3+/Au+ site, which makes the catalyst exhibit excellent catalytic activity. High coordination numbers Au-Cl entities reduce the electron transfer between Au3+ and C 2 H 2 and weaken the adsorption of C 2 H 2 on the Au active sites. Furthermore, [Bmim][Cl 3 ] ILs can self-oxidize gold nanoparticles on the support surface into Au3+. This study provides a new method for improving the stability and activity of gold-based acetylene hydrochlorination catalysts. [Display omitted] • The self-oxidation of Au3+ catalyst are successfully synthesized. • Self-oxidation of high-valence gold via sacrificial [Bmim][Cl 3 ] high activity and long lifetime catalyst design of Au-SILP catalysts. • High coordination numbers Au-Cl entities reduce the electron transfer between Au3+ and C 2 H 2 and weaken the adsorption of C 2 H 2 on the Au active sites. [ABSTRACT FROM AUTHOR]