Nanocarbon catalysts with co‐active S−P−C sites enhance metal‐free direct oxidation of alcohols

Abstract

In this study, a sulfur–phosphorus co‐doped nanocarbon (SPC) catalyst was synthesized using a straightforward one‐step colloidal carbonization method and demonstrated high performance in the metal‐free direct oxidation of alcohols to aldehydes. This metal‐free SPC catalyst showed exceptional efficiency, achieving a conversion rate of 90% for benzyl alcohol and a selectivity of 94% toward benzaldehyde within only 1 h at 130°C. Moreover, it displays exceptional cycle stability and a high turnover frequency (17.1 × 10−3 mol g−1 h−1). Theoretical analysis suggested that the catalyst's superior performance is attributed to the presence of unsaturated edge defects and S−P− moieties, which increase the density of states at the Fermi level, lower the band gap energy, and promote electron localization. Additionally, the doping introduces cooperative co‐active S−P−C sites, facilitating a synergistic multisite catalytic effect that lowers the energy barriers. These findings represent a significant advancement in the field of metal‐free direct alcohol oxidation.