Isolated Square‐Planar Copper Center in Boron Imidazolate Nanocages for Photocatalytic Reduction of CO2 to CO

Abstract Photocatalytic reduction of CO 2 to value‐added fuel has been considered to be a promising strategy to reduce global warming and shortage of energy. Rational design and synthesis of catalysts to maximumly expose the active sites is the key to activate CO 2 molecules and determine the reaction selectivity. Herein, we synthesize a well‐defined copper‐based boron imidazolate cage (BIF‐29) with six exposed mononuclear copper centers for the photocatalytic reduction of CO 2 . Theoretical calculations show a single Cu site including weak coordinated water delivers a new state in the conduction band near the Fermi level and stabilizes the *COOH intermediate. Steady‐state and time‐resolved fluorescence spectra show these Cu sites promote the separation of electron–hole pairs and electron transfer. As a result, the cage achieves solar‐driven reduction of CO 2 to CO with an evolution rate of 3334 μmol g −1 h −1 and a high selectivity of 82.6 %.