Ultrathin Cu-Based Porphyrin Metal–Organic Framework Modified with ZnTe Promotes Highly Selective Photocatalytic CO₂ Reduction to CO

The photocatalytic reduction of carbon dioxide (CO₂) into value-added chemical fuels is an effective strategy to address the fossil fuel crisis and global warming. Herein, a novel p-n junction composed of ZnTe nanoparticles and Cu-TCPP nanosheets was successfully constructed for efficient CO₂-to-CO conversion. Structural and spectroscopic characterization confirmed the establishment of the p-n junction, which enhances charge separation and transfer. The ZnTe/Cu-TCPP composite exhibits enhanced photocatalytic CO₂ reduction with CO as the primary product (120.53 μmol g^-1), achieving 4.8- and 5.9-fold yield improvements over pristine ZnTe and Cu-TCPP, respectively. DFT calculations revealed a significantly enhanced CO₂ adsorption energy (-0.549 eV) on the ZnTe/Cu-TCPP heterojunction, promoting the reaction. In situ DRIFTS analysis confirmed the presence of key intermediates (*COOH, *CH₃, and *CO), validating their roles in the selective CO₂-to-CO conversion pathways. A mechanistic study further elucidated the contribution of each component in the reaction process. Additionally, the ZnTe/Cu-TCPP photocatalyst exhibited excellent stability, demonstrating its potential for sustainable CO₂ reduction.