Optimizing Hydrogen Adsorption by d–d Orbital Modulation for Efficient Hydrogen Evolution Catalysis

Abstract Unraveling the essence of hydrogen adsorption and desorption behaviors can fundamentally guide catalyst design and promote catalytic performance. Herein, the regulation of hydrogen adsorption is systematically investigated by d–d orbital interaction of metallic tungsten dioxide (WO 2 ). Theoretical simulations show that the incorporation of post‐transition metal atoms including Fe, Co, Ni, and Cu can gradually reduce the bond order of W—M sites, consequently weakening the hydrogen adsorption and accelerating the hydrogen evolution reaction (HER) process. Under that theoretical guidance, various 3d metal doped WO 2 electrocatalysts are systematically screened for HER catalysis. Among them, the Ni‐WO 2 /nickel foam exhibits an overpotential of 41 mV (−10 mA cm −2 ) and Tafel slope down to 47 mV dec −1 representing the best tungsten‐based HER catalysts so far. This work demonstrates that optimizing hydrogen adsorption via d–d orbital modulation is an effective approach to developing efficient and robust catalysts.