Chlorine evolution reaction (CER) is crucial for industrial-scale production of high-purity Cl. Despite the development of classical dimensionally stable anodes to enhance CER efficiency, the competitive oxygen evolution reaction (OER) remains a barrier to achieving high Cl selectivity. Herein, a binder-free electrode, Ru nanoparticles (NPs)-decorated NiMoO nanorod arrays (NRAs) supported on Ti foam (Ru-NiMoO/Ti), was designed for active CER in saturated NaCl solution (pH = 2). The Ru-NiMoO/Ti electrode exhibits a low overpotential of 20 mV at 10 mA cm current density, a high Cl selectivity exceeding 90%, and robust durability for 90h operation. The marked difference in Tafel slopes between CER and OER indicates the high Cl selectivity and superior reaction kinetics of Ru-NiMoO/Ti electrode. Further studies reveal a strong metal-support interaction (SMSI) between Ru and NiMoO, facilitating electron transfer through the Ru-O bridge bond and increasing the Ru 3d-Cl 2p antibonding orbital occupancy, which eventually results in weakened Ru-Cl bonding, promoted Cl desorption, and enhanced Cl evolution. Our findings provide new insights into developing electrodes with enhanced CER performance through antibonding orbital occupancy engineering.
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