Orbital Occupancy Modulation to Optimize Intermediate Absorption for Efficient Electrocatalysts in Water Electrolysis and Zinc–Ethanol–Air Battery

Abstract Spin engineering is a promising way to modulate the interaction between the metal d‐orbital and the intermediates and thus enhance the catalytic kinetics. Herein, an innovative strategy is reported to modulate the spin state of Co by regulating its coordinating environment. o‐c‐CoSe₂‐Ni is prepared as pre‐catalyst, then in situ electrochemical impedance spectroscopy (EIS) and in situ Raman spectroscopy are employed to prove phase transition, and CoOOH/Co₃O₄ is formed on the surface as active sites. In hybrid water electrolysis, the voltage has a negative shift, and in zinc–ethanol–air battery, the charging voltage is lowered and the cycling stability is greatly increased. Coordinated atom substitution and crystalline symmetry change are combined to regulate the absorption ability of reaction intermediates with balanced optimal adsorption. Coordinated atom substitution weakens the adsorption while the crystalline symmetry change strengthens the adsorption. Importantly, the tetrahedral sites are introduced by Ni doping which enables the co‐existence of four‐coordinated sites and six‐coordination sites in o‐c‐CoSe₂‐Ni. The dz² + dx²‐y² orbital occupancy decreases after the atomic substitution, while increases after replacing the CoSe₆‐O_h field with CoSe₆‐O_h/CoSe₄‐T_d. This work explores a new direction for the preparation of efficient catalysts for water electrolysis and innovative zinc–ethanol–air battery.