From Charge to Spin: An In‐Depth Exploration of Electron Transfer in Energy Electrocatalysis

Abstract

Catalytic materials play crucial roles in various energy‐related processes, ranging from large‐scale chemical production to advancements in renewable energy technologies. Despite a century of dedicated research, major enduring challenges associated with enhancing catalyst efficiency and durability, particularly in green energy‐related electrochemical reactions, remain. Focusing only on either the crystal structure or electronic structure of a catalyst is deemed insufficient to break the linear scaling relationship (LSR), which is the golden rule for the design of advanced catalysts. The discourse in this review intricately outlines the essence of heterogenous catalysis reactions by highlighting the vital roles played by electron properties. The physical and electrochemical properties of electron charge and spin that govern catalysis efficiencies are analyzed. Emphasis is placed on the pronounced influence of external fields in perturbing the LSR, underscoring the vital role that electron spin plays in advancing high‐performance catalyst design. The review culminates by proffering insights into the potential applications of spin catalysis, concluding with a discussion of extant challenges and inherent limitations. This article is protected by copyright. All rights reserved

Manipulating Superexchange Interaction of Ru–O–Fe Sites for Enhanced Electrocatalytic Nitrate-to-Ammonia Selectivity

“…21−24 It must be emphasized that the electron-transfer kinetics and selectivity in the reduction process largely depend on the electronic filling of the metal e g orbital. 25 In general, low e g filling corresponds to low electron occupancy in the antibonding orbitals of small molecules, leading to overstrong bonding. Conversely, higher filling leads to weaker interactions.…”

“…To address the above challenges, various catalysts have been developed, such as Cu-based materials, − Fe-based materials, − and noble metals (e.g., Ru, Pd). − Among these candidate catalysts, Fe-based materials show great promise in ammonia synthesis due to their active d-orbital electrons. Although various atomic/electronic structure modulation strategies have been explored, the catalytic activity and NH 3 selectivity of Fe-based materials have not reached the optimal level. − It must be emphasized that the electron-transfer kinetics and selectivity in the reduction process largely depend on the electronic filling of the metal e g orbital . In general, low e g filling corresponds to low electron occupancy in the antibonding orbitals of small molecules, leading to overstrong bonding.…”