Ternary engineered linear polymers with a controllable cascade electron transfer pathway for efficient H2O2 photosynthesis coupled with biomass conversion

Abstract

Linear polymer-based photocatalysts have attracted significant research attention in photocatalytic hydrogen peroxide (H₂O₂) production due to their designable molecular structures and highly tunable electronic properties. However, their photocatalytic performance is severely hindered by the insufficient separation of photogenerated charge carriers. Herein, we designed and synthesized a linear polymer, PS-TAA-AQ-Ru, integrating three functional moieties of N,N-diphenylaniline (TAA), anthraquinone (AQ), and a [Ru(bpy)₃]²⁺ complex via a one-pot reversible addition–fragmentation chain transfer (RAFT) polymerization strategy. Compared to polymers (such as PS-TAA-Ru, PS-AQ-Ru, or PS-Ru) with a single-step electron transfer channel, the ternary functionalized PS-TAA-AQ-Ru photocatalyst achieves spatially separated charge carriers and efficient charge migration through its stepwise electron transfer channel of TAA → AQ → Ru. Remarkably, the H₂O₂ production rate of PS-TAA-AQ-Ru dramatically reaches 1550 ± 50 μmol g⁻¹ h⁻¹ upon introducing furfuryl alcohol (FFA) biomass into an air/water photocatalytic system, while FFA is concurrently converted to furfural (FF) at a rate of 300 ± 20 μmol g⁻¹ h⁻¹ with 100% selectivity under visible-light irradiation.