Unleashing the power of directed electron transfer: unraveling the potential of {PV₄}₂ in heterogeneous photocatalysis

In heterogeneous photocatalytic systems, ensuring the directed transfer of photo-generated electrons is a key approach to enhance the utilization rate of photogenerated electrons. To accelerate the directed electron transfer, a vanadium oxygen cluster ([Na-2(H2O)(2)P2V8IV(cit)(4)(bpy)(4)O-16(H2O)(4)](4-), {PV4}(2)) was successfully synthesized to achieve efficient photocatalytic reduction of CO2. The introduction of reductive V atoms increased the light-harvesting range and the directed electron transfer capacity of {PV4}(2), which could accept the photogenerated electrons from [Ru(bpy)(3)](2+) and effectively transfer the photogenerated electrons to CO2. Simultaneously, the citrate ligand had a favorable influence on the stability of the POV structures. The photocatalytic system was highly active with a CO yield of 9113.3 mu mol g(-1) h(-1). The electron consumption rate of the whole heterogeneous system reached 19990.2 mu mol g(-1) h(-1). This work provided novel insights into the design of vanadium oxygen cluster catalysts for heterogeneous CO2 reduction.