Dopant and Exfoliation Induced Simultaneous Modification of Charge Density and C─C Coupling Sites for Efficient CO ₂ Photoreduction to Ethylene

Abstract The photochemical conversion of CO 2 into C2+ products has emerged as an attractive method for synthesizing valuable chemicals and fuels using abundant solar energy. However, the challenge lies in enhancing the efficiency and selectivity of C2+ product formation. In this study, we employed a heteroatom doping strategy to optimize the photocatalytic parameters and achieve excellent efficiency and selectivity in the photocatalytic CO 2 reduction to C2+ product formation. Our experimental analysis revealed that the local electronic structure of the catalyst, modified by In‐doping, enables enhanced efficiency. Additionally, the incorporation of Cu facilitates the coupling of C1 intermediates, resulting in excellent selectivity towards C2+ products. The CO 2 reduction performance is further enhanced through exfoliation, which increases the exposure of active sites and extends the charge carrier lifetime by reducing the charge diffusion length. We report that the rate of formation of C 2 H 4 reached 54.3 µmol·h −1 ·g −1 with an outstanding selectivity of 91% over the exfoliated CuIn‐doped AgBiP 2 S 6 catalyst. By elucidating the role of heteroatom doping and exfoliation in enhancing both the efficiency and selectivity of C2+ product formation, our study contributes to advancing the development of sustainable and efficient photocatalytic CO 2 conversion technologies.