Geometry‐Induced Asymmetry Drives Charge Localization for Accelerated Light‐Driven CO ₂ Reduction

ABSTRACT The efficient utilization of solar energy to convert carbon dioxide into renewable fuels is a compelling strategy for mitigating carbon emissions and realizing sustainable chemical cycles. Herein, we report a Ni–modified oxygen–deficient TiO 2 (Ni/TiO 2‐x ) catalyst that achieves exceptionally high photothermal CO 2 reduction performance under simulated solar irradiation without external heating, reaching a remarkable total production yield of 278.3 mmol·g −1 ·h −1 . Structural and spectroscopic analyses reveal that the asymmetric Ni–V O –Ti interfacial configuration serves as a unique charge polarization center that redistributes charge density and stabilizes reaction intermediates under light–induced thermal excitation. This asymmetric coordination disrupts the electronic degeneracy of the Ti─O framework, thereby lowering the free energy barrier for the rate–determining step. Density functional theory (DFT) calculations further demonstrate that the asymmetric site acts as a dual–function photothermal antenna, where light absorption and heat localization cooperate to accelerate H 2 activation and C─O bond cleavage. This work unveils a paradigm in which geometric asymmetry governs both charge transfer and localized heat management, providing a molecular–level blueprint for next–generation photothermal catalysts for solar–driven CO 2 conversion.