Unveiling the metallic size effect on O2 adsorption and activation for enhanced electro-Fenton degradation of aromatic compounds.

Metal-atom-modified nitrogen-doped carbon materials (M-N-C) have emerged as promising candidates for electro-Fenton degradation of pollutants. Nonetheless, a comprehensive exploration of size-dependent M-N-C catalysts in the electro-Fenton process remains limited, posing challenges in designing surface-anchored metal species with precise sizes. Herein, a heterogeneous-homogeneous coupled electro-Fenton (HHC-EF) system was designed and various M-N-C catalysts anchored with Co single atoms (CoSA-N-C), Co clusters (CoAC-N-C), and Co nanoparticles (CoNP-N-C) were successfully synthesized and employed in an HHC-EF system. Intriguingly, CoAC-N-C achieved outstanding removal efficiencies of 99.9% for BPA and RhB within 10 and 15 min, respectively, with the fastest reaction kinetics (0.70 min for BPA and 0.34 min for RhB). Electron spin resonance and trapping experiments revealed that·OH played a crucial role in the HHC-EF process. Moreover, experiments and theoretical calculations revealed that the unique metallic size effect facilitate the in-situ electro-generation of HO. Specifically, the atomic interaction between neighboring Co atoms in clusters enhanced O adsorption and activation by strengthening the Co-N bond and transforming O adsorption configuration to the Yeager-type. This study provides valuable insights that could inspire the size-oriented metal-based catalyst design from the perspective of the potential atomic distance effect.