Tungsten‐Doped RuO ₂ Enables Direct Chloride Adsorption and Accelerated Krishtalik Kinetics for Industrial Chlor‐Alkali Electrolysis

ABSTRACT As one of the largest and most energy‐intensive electrochemical sectors, the chlor‐alkali industry heavily relies on the use of iridium‐based dimensionally stable anodes (DSAs) with high cost and limited catalytic performance. Herein, we report a tungsten(W)‐doped ruthenium oxide (RuWO _x ) anodic catalyst, which delivers efficient chlorine evolution reaction (CER) under industrial chlor‐alkali conditions and achieves an ultralow overpotential of 15.9 mV at 10 mA cm ⁻² with 99.6% chlorine selectivity. Experimental and theoretical analysis reveal that W effectively withdraws electrons from Ru sites, changes chloride adsorption from indirect Ru─O─Cl motifs to direct Ru─Cl binding, thereby accelerating the ^* Cl→ ^* Cl ⁺ electron‐transfer (Krishtalik) step. Furthermore, the catalyst can work stably for over 1100 h in a zero‐gap catalyst‐coated membrane (CCM) cell, with a low cell voltage of 2.58 V at 0.5 A cm ⁻² and chlorine selectivity exceeding 94%, demonstrating its industrial application potential.