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

Abstract 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.