A cyclic trinuclear silver complex for photosynthesis of hydrogen peroxide.

The development of metal complexes for photosynthesis of hydrogen peroxide (HO) from pure water and oxygen using solar energy, especially in the absence of any additives (, acid, co-catalysts, and sacrificial agents), is a worthwhile pursuit, yet still remains highly challenging. More importantly, the O 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 HO either from pure water or from sea water in the absence of any additives with a high HO production rate of 183.7 and 192.3 μM h, 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 O into HO and HO into HO.