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

Abstract 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.