Boosting selective chlorine evolution reaction: Impact of Ag doping in RuO2 electrocatalysts.

The chlor-alkali process is critical to the modern chemical industry because of the wide utilization of chlorine gas (Cl2). More than 95 % of global Cl2 production relies on electrocatalytic chlorine evolution reaction (CER) through chlor-alkali electrolysis. The RuO2 electrocatalyst serves as the main active component widely used in commercial applications. However, oxygen evolution reaction (OER) generally competes with CER electrocatalysts at RuO2 electrocatalyst owing to the intrinsically scaling reaction energy barrier of *OCl and *OOH intermediates, leading to decreased CER selectivity, high energy consumption, and increased cost. Here, the effect of Ag doping on selective CER over RuO2 electrocatalysts prepared by a sol-gel method has been systematically studied. We found that Ag-doping can effectively improve the Faradaic efficiency of RuO2 electrocatalyst for CER. Furthermore, the improved CER selectivity of Ag-doped RuO2 electrocatalysts is highly dependent on the Ag-doping concentration. The optimized Ag0.15Ru0.85O2 electrocatalyst displays an overpotential of 105 mV along with a selectivity of 84.64 ± 1.84 % in 5.0 M NaCl electrolyte (pH = 2.0 ± 0.05), significantly outperforming undoped one (142 mV, 72.75 ± 1.52 %). Our experiments and density functional theory (DFT) calculations show electron transfer from Ag+ to Ru4+ suppresses *OOH intermediates desorption on Ag-doped RuO2, enabling improved CER selectivity. Such designs of Ag-doped RuO2 electrocatalysts are expected to be favorable for practical chlor-alkali applications.