Biomass Native Structure Into Functional Carbon-Based Catalysts for Fenton-Like Reactions

Advancing biomass-derived carbon materials requires a systematic understanding of how distinct biomass structures influence their properties and functionality. To address this, eight 2D flaky and 1D acicular plant biomasses is systematically compared to synthesize pristine carbon, N-doped carbon, and cobalt/graphitic carbon for Fenton-like peroxymonosulfate (PMS) activation. Biomass pyrolysis under 5% NH₃ generates surface N-doped amorphous carbon, facilitating a selective electron transfer pathway (ETP), where high N incorporation, specific surface area, and atomic-level control over O groups synergistically enhance its efficiency. While COOH groups contribute positively, excessive defects and C═O groups hinder ETP performance. Notably, compared to 2D biomass, 1D acicular biomass induces tubular carbon with lower C═O content, promoting the ETP regime. 2D flaky biomass facilitates Co nanoparticle incorporation in cobalt/graphitic carbon, where high contents of N, Co, defects, and oxygen groups (C═O/C─O/COOH) enhance sulfate radical (SO₄^•−)-dominated catalysis, whereas excessive sp² C (>75–80 at.%) negatively affects performance. Through structural characterization, mechanistic analysis, and quantitative linear fitting correlations, this study identifies biomass-derived key active site interactions governing electron transfer and SO₄^•−-driven oxidation mechanisms. These insights establish a framework for sustainable, biomass-structure-driven carbon design for environmental catalysis.