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

Abstract

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 ([Na₂(H₂O)₂P₂V^IV₈(cit)₄(bpy)₄O₁₆(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 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 CO₂ reduction.