Post-synthetic atomically precise single-CuII sites in a thiacalix[4]arene-supported octahedral Na@Co24 cluster: the Cu-Co synergistic effect for selective photocatalytic conversion of CO2 to CO

A thiacalix[4]arene-supported octahedral Na@Co-24 cluster has been fabricated by the modular assembly of six Co-4-(TC4A) polynuclear secondary building units (PSBUs) and eight 2,4,6-PTC linkers. The post-modification of Na@Co-24 by ion exchange of Na+ with Cu2+ on the surface of the octahedron afforded a structurally well-defined Cu@Co-24 cluster. The obtained Cu@Co-24 cluster achieved improved visible-light absorption and selective photoreduction of CO2 to CO due to the Cu-Co synergistic effect.

Automated summary

A thiacalix[4]arene-supported octahedral Na@Co-24 cluster was formed by assembling six Co-4-(TC4A) polynuclear secondary building units (PSBUs) and eight 2,4,6-PTC linkers. The Na+ in the octahedron was replaced by Cu2+ through ion exchange, leading to a well-defined Cu@Co-24 cluster. The Cu@Co-24 cluster exhibited enhanced visible-light absorption and selective photoreduction of CO2 to CO due to the synergistic effect between Cu and Co.