Work

Sulfone site enables H2O2 practical fabrication over metal-free photocatalyst

Year: 2025

Type: article

Abstract: The photocatalytic synthesis of hydrogen peroxide (H 2 O 2 ) from water and oxygen offers a sustainable route to replace the energy-intensive anthraquinone process. However, the practical application of this technology is hindered by the prevalent issues of ambiguous active sites, elusive reaction mechanisms, and insufficient efficiency in conventional photocatalysts. Herein, we address these challenges by designing a metal-free porous organic polymer, PA-BTDO, featuring well-defined sulfone-based dual‑oxygen sites (O=S=O). This catalyst achieves an exceptional H 2 O 2 production rate of 2090 μmol g −1 h −1 under visible light, ranking among the highest for metal-free systems. Notably, we demonstrate the scalable production of a 1.0 wt% H 2 O 2 solution—directly applicable for medical use—from a laboratory-scale system using merely 1.0 g of catalyst over 24 h. Mechanistic investigations reveal that the dual‑oxygen sites undergo a concerted photochemical transformation into two adjacent S-O-H groups, which synergistically adsorb O 2 via a Yeager-type mode and stabilize a novel seven-membered ring transition state. This unique configuration drastically lowers the reaction barrier, enabling highly efficient H 2 O 2 generation. This work not only establishes a pioneering strategy for active-site design via transition-state engineering but also opens a practical pathway for solar-driven H 2 O 2 production.

Source: Chemical Engineering Journal

DOI: 10.1016/j.cej.2025.172164