Engineering atomic Rb-N configurations to tune radical pathways for highly selective photocatalytic H2O2 synthesis coupled with biomass valorization

Photocatalytic oxygen reduction for hydrogen peroxide (H₂O₂) synthesis presents a green and cost-effective production method. However, achieving highly selective H₂O₂ synthesis remains challenging, necessitating precise control over free radical reaction pathways and minimizing undesirable oxidative by-products. Herein, we report for the visible light-driven simultaneous co-photocatalytic reduction of O₂ to H₂O₂ and oxidation of biomass using the atomic rubidium-nitride modified carbon nitride (CNRb). The optimized CNRb catalyst demonstrates a record photoreduction rate of 8.01 mM h⁻¹ for H₂O₂ generation and photooxidation rate of 3.75 mM h⁻¹ for furfuryl alcohol to furoic acid, achieving a remarkable solar-to-chemical conversion (SCC) efficiency of up to 2.27%. Experimental characterizations and DFT calculation disclosed that the introducing atomic Rb–N configurations allows for the high-selective generation of superoxide radicals while suppressing hydroxyl free radical formation. This is because the Rb–N serves as the new alternative site to perceive a stronger connection position for O₂ adsorption and reinforce the capability to extract protons, thereby triggering a high selective redox product formation. This study holds great potential in precisely regulating reactive radical processes at the atomic level, thereby paving the way for efficient synthesis of H₂O₂ coupled with biomass valorization.