Breaking symmetry for better catalysis: insights into single-atom catalyst design

Abstract

Breaking structural symmetry has emerged as a powerful strategy for fine-tuning the electronic structure of catalytic sites, thereby significantly enhancing the electrocatalytic performance of single-atom catalysts (SACs). The inherent symmetric electron density in conventional SACs, such as M–N₄ configurations, often leads to suboptimal adsorption and activation of reaction intermediates, limiting their catalytic efficiency. By disrupting this symmetry of SACs, the electronic distribution around the active center can be modulated, thereby improving both the selectivity and adsorption strength for key intermediates. These changes directly impact the reaction pathways, lowering energy barriers, and enhancing catalytic activity. However, achieving precise modulation through SAC symmetry breaking for better catalysis remains challenging. This review focuses on the atomic-level symmetry-breaking strategies of catalysts, including charge breaking, coordination breaking, and geometric breaking, as well as their electrocatalytic applications in electronic structure tuning and active site modulation. Through modifications to the M–N₄ framework, three primary configurations are achieved: unsaturated coordination M–N_x(x=1,2,3), non-metallic doping MX–N_x(x=1,2,3), and bimetallic doping M₁M₂–N₄. Advanced characterization techniques combined with density functional theory (DFT) elucidate the impact of these strategies on oxidation, reduction, and bifunctional catalytic reactions. This review highlights the significance of symmetry-breaking structures in catalysis and underscores the need for further research to achieve precise control at the atomic-level.