A cyclic trinuclear silver complex for photosynthesis of hydrogen peroxide

Abstract

The development of metal complexes for photosynthesis of hydrogen peroxide (H₂O₂) from pure water and oxygen using solar energy, especially in the absence of any additives (e.g., acid, co-catalysts, and sacrificial agents), is a worthwhile pursuit, yet still remains highly challenging. More importantly, the O₂ evolution from the water oxidation reaction has been impeded by the classic bottleneck, the photon-flux-density problem of sunlight that could be attributed to rarefied solar radiation for a long time. Herein, we reported synthesis of boron dipyrromethene (BODIPY)-based cyclic trinuclear silver complexes (Ag-CTC), and they exhibited strong visible-light absorption ability, a suitable energy bandgap, excellent photochemical properties and efficient charge separation ability. The integration of BODIPY motifs as oxygen reduction reaction sites and silver ions as water oxidation reaction sites allows Ag-CTC to photosynthesize H₂O₂ either from pure water or from sea water in the absence of any additives with a high H₂O₂ production rate of 183.7 and 192.3 μM h⁻¹, which is higher than that of other reported metal-based photocatalysts. The photocatalytic mechanism was systematically and ambiguously investigated by various experimental analyses and density functional theory (DFT) calculations. Our work represents an important breakthrough in developing a new Ag photocatalyst for the transformation of O₂ into H₂O₂ and H₂O into H₂O₂.