Modulating the Moderate d-Band Center of Indium in InVO₄ Nanobelts by Synergizing MnO_x and Oxygen Vacancies for...

Modulating the electronic properties of transition metal sites in photocatalysts at the atomic level is essential for achieving high-activity carbon dioxide photoreduction (CO₂PR). An electronic strategy is herein proposed to engineer In-d-band center of InVO₄ by incorporating MnO_x nanoparticles and oxygen vacancies (V_O) into holey InVO₄ nanobelts (MnO_x/V_O-InVO₄), which synergistically modulates the In-d-band center to a moderate level and consequently leads to high-efficiency CO₂PR. The MnO_x/V_O-InVO₄ 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 InVO₄-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 CO₂PR-to-CO reaction. This work not only demonstrates the effective engineering of the d orbital of the low-coordination In atoms to promote CO₂PR, but also paves the way for the application of tuning d-band center to develop high-efficiency catalysts.