An isolated doughnut-like molybdenum(v) cobalto-phosphate cluster exhibiting excellent photocatalytic performance for carbon dioxide conversion

Abstract

An isolated doughnut-like molybdenum(V) cobalto-phosphate cluster with the formula (C₁₁NH₁₀)₂{[Co(H₂O)₆]@[H₂₉Co₁₆Mo₁₆(H₂O)₁₆(PO₄)₂₄O₃₆]}(H₂PO₄)·25H₂O has been successfully synthesized by a hydrothermal method. Single crystal X ray diffraction analysis shows that four {Co₄O₆₀} tetramers and eight {Mo₂O₁₀} dimers are linked by oxygen atoms and phosphate groups to construct a doughnut-type structure for [Co@{Co₁₆Mo₁₆}], in which one [Co^II(H₂O)₆]²⁺ octahedron is enclosed. More importantly, [Co@{Co₁₆Mo₁₆}] exhibits promising photocatalytic performance for CO₂ reduction with the CO formation rate of 6764.3 μmol g⁻¹ h⁻¹ and the selectivity of 96.89%. In addition, the cycling test indicated that [Co@{Co₁₆Mo₁₆}] can be reused for at least four cycles without significant loss of catalytic activity. The result of this work may provide new insight for the synthesis of highly efficient POM-based photocatalysts for CO₂ reduction.