Semi‐Covalent Interaction‐Induced Electron Transfer in Single‐Atom Alloy Catalysts Enhance Singlet Oxygen Generation for Efficient Pollutant Removal

Abstract Selectively producing singlet oxygen ( 1 O 2 ) through peroxymonosulfate (PMS) activation holds significant promise for sustainable water pollution control. Single‐atom alloy catalysts (SAACs) possess unique active sites and electronic structures, demonstrating strong potential to enhance 1 O 2 generation. However, the effect of single atom metal insertion on the electronic structures of SAACs and their catalytic performance of activated PMS remains unclear. Herein, a series of SAACs (M‐Co 3 O 4 /C), in which metal atoms M (M = Mn, Fe, Cu, or Ni) are atomically dispersed on carbon‐supported hollow dodecahedral Co 3 O 4 are synthesized. These catalysts exhibit exceptional catalytic activity in mediating PMS self‐decomposition to selectively generate 1 O 2 for the degradation of bisphenol A (BPA), with the k obs of the Cu‐Co 3 O 4 /C/PMS (2.90 min −1 ) being 4.32 times higher than that of Co 3 O 4 /C. Experimental and computational studies reveal that the remarkable catalytic activity of M‐Co 3 O 4 /C/PMS systems originates from the semi‐covalent coupling between M and Co, which induces electron transfer from Co to the M site. This electron redistribution enhances PMS adsorption at the electron‐rich M site and lowers the reaction energy barrier for efficient pollutant degradation. This study offers atomic‐scale insights into PMS activation mechanisms, providing guidance for designing advanced SAACs to enhance pollutant degradation efficiency.