Unleashing the power of directed electron transfer: unraveling the potential of {PV 4 } 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 (H 2 O) 2 P 2 VIV8(cit) 4 (bpy) 4 O 16 (H 2 O) 4 ] 4− , {PV 4 } 2 ) was successfully synthesized to achieve efficient photocatalytic reduction of CO 2 . The introduction of reductive V atoms increased the light-harvesting range and the directed electron transfer capacity of {PV 4 } 2 , which could accept the photogenerated electrons from [Ru(bpy) 3 ] 2+ and effectively transfer the photogenerated electrons to CO 2 . 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 μmol g −1 h −1 . The electron consumption rate of the whole heterogeneous system reached 19990.2 μmol g −1 h −1 . This work provided novel insights into the design of vanadium oxygen cluster catalysts for heterogeneous CO 2 reduction.