Post-synthetic Metalation on the Ionic TiO2 Surface to Enhance Metal-CO2 Interaction During Photochemical CO2 Reduction.

During the photochemical CO2 reduction reaction, CO2 adsorption on the catalyst's surface is a crucial step where the binding mode of the [metal-CO2] adduct directs the product selectivity and efficiency. Herein, an ionic TiO2 nanostructure stabilized by polyoxometalates (POM), ([POM]x@TiO2), is prepared and the sodium counter ions present on the surface to balance the POMs' charge are replaced with copper(II) ions, (Cux[POM]@TiO2). The microscopic and spectroscopic studies affirm the copper exchange without altering the TiO2 core and weak coordination of copper (II) ions to the POMs' surface. Band structure analysis suggests the photo-harvesting efficiency of the TiO2 core with the conduction band edge higher than the reduction potential of CuII/I and multi-electron CO2 reduction potentials. Photochemical CO2 reduction with Cux[POM]@TiO2 results in 30 µmol gcat.-1 CO (79%) and 8 µmol gcat-1 of CH4 (21%). Quasi-in-situ Raman study provides evidence in support of CO2 adsorption on the Cux[POM]@TiO2 surface. 13C and D2O labeling studies validates the {Cu-[CO2]-} adduct formation. Despite the photo-harvesting ability of Nax[POM]@TiO2 itself, the poor CO2 adsorption ability of sodium ions highlights the crucial role of copper ion CO2 photo-reduction. Characterization of the {M-[η2-CO2]-} species via surface tuning validates the CO2 activation and photochemical reduction pathway proposed earlier.