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8-fold, while that of HCOO- increases by 35%. The AQY of V12B18-Co and V12B18-Ni is 1.1% and 0.93%, respectively. These values are higher than most of the reported POM materials under similar conditions. The density functional theory (DFT) calculations illuminate the active site of CO2RR and the reduction mechanism. This work provides new insights into the design of stable, high-performance, and low-cost photocatalysts for CO2 reduction.The synthesis of novel tunable electroactive species remains a key challenge for a wide range of chemi