Transition-Metal-Modified Vanadoborate Clusters as Stable and Efficient Photocatalysts for CO₂ Reduction

Photocatalytic carbon dioxide reduction (CO₂RR) is considered to be a promising sustainable and clean approach to solve environmental issues. Polyoxometalates (POMs), with advantages in fast, reversible, and stepwise multiple-electron transfer without changing their structures, have been promising catalysts in various redox reactions. However, their performance is often restricted by poor thermal or chemical stability. In this work, two transition-metal-modified vanadoborate clusters, [Co(en)₂]₆[V₁₂B₁₈O₅₄(OH)₆]·17H₂O (V₁₂B₁₈-Co) and [Ni(en)₂]₆[V₁₂B₁₈O₅₄(OH)₆]·17H₂O (V₁₂B₁₈-Ni), are reported for photocatalytic CO₂ reduction. V₁₂B₁₈-Co and V₁₂B₁₈-Ni can preserve their structures to 200 and 250 °C, respectively, and remain stable in polar organic solvents and a wide range of pH solutions. Under visible-light irradiation, CO₂ can be converted into syngas and HCOO^- with V₁₂B₁₈-Co or V₁₂B₁₈-Ni as catalysts. The total amount of gaseous products and liquid products for V₁₂B₁₈-Co is up to 9.5 and 0.168 mmol g^-1 h^-1. Comparing with V₁₂B₁₈-Co, the yield of CO for V₁₂B₁₈-Ni declines by 1.8-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.