Modulating the Moderate d-Band Center of Indium in InVO 4 Nanobelts by Synergizing MnO x and Oxygen Vacancies for High-Efficiency CO 2 Photoreduction.

Modulating the electronic properties of transition metal sites in photocatalysts at the atomic level is essential for achieving high-activity carbon dioxide photoreduction (CO 2 PR). An electronic strategy is herein proposed to engineer In-d-band center of InVO 4 by incorporating MnO x nanoparticles and oxygen vacancies (V O ) into holey InVO 4 nanobelts (MnO x /V O -InVO 4 ), which synergistically modulates the In-d-band center to a moderate level and consequently leads to high-efficiency CO 2 PR. The MnO x /V O -InVO 4 catalyst with optimized electronic property exhibits a single carbon evolution rate of up to 145.3 µmol g -1 h -1 and a carbon monoxide (CO) product selectivity of 92.6%, coming out in front of reported InVO 4 -based materials. It is discovered that the modulated electronic property favors the interaction between the In sites and their intermediates, which thereby improves the thermodynamics and kinetics of the CO 2 PR-to-CO reaction. This work not only demonstrates the effective engineering of the d orbital of the low-coordination In atoms to promote CO 2 PR, but also paves the way for the application of tuning d-band center to develop high-efficiency catalysts.