Orbital Occupancy and Spin Polarization: From Mechanistic Study to Rational Design of Transition Metal-Based Electrocatalysts toward Energy Applications

Over the past few decades, development of electrocatalysts for energy applications has extensively transitioned from trial-and-error methodologies to more rational and directed designs at the atomic levels via either nanogeometric optimization or modulating electronic properties of active sites. Regarding the modulation of electronic properties, nonprecious transition metal-based materials have been attracting large interest due to the capability of versatile tuning d-electron configurations expressed through the flexible orbital occupancy and various possible degrees of spin polarization. Herein, recent advances in tailoring electronic properties of the transition-metal atoms for intrinsically enhanced electrocatalytic performances are reviewed. We start with discussions on how orbital occupancy and spin polarization can govern the essential atomic level processes, including the transport of electron charge and spin in bulk, reactive species adsorption on the catalytic surface, and the electron transfer between catalytic centers and adsorbed species as well as reaction mechanisms. Subsequently, different techniques currently adopted in tuning electronic structures are discussed with particular emphasis on theoretical rationale and recent practical achievements. We also highlight the promises of the recently established computational design approaches in developing electrocatalysts for energy applications. Lastly, the discussion is concluded with perspectives on current challenges and future opportunities. We hope this review will present the beauty of the structure–activity relationships in catalysis sciences and contribute to advance the rational development of electrocatalysts for energy conversion applications.