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-1 for BPA and 0.34 min-1 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 H2O2. Specifically, the atomic interaction between neighboring Co atoms in clusters enhanced O2 adsorption and activation by strengthening the Co-N bond and transforming O2 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.