The role of the morphological motifs in syngas product selectivity during CO2 photoreduction

Bimetallic-driven high-performance artificial photosynthesis is quite challenging. In this work, it is shown that NiO was introduced to construct N and C doped bimetallic composite catalyst, and the structure of the composite catalyst was adjusted to promote charge separation and transfer. The resulting syngas possesses adjustable component ratios. The results indicate that ZnNC/Ni exhibits broader light absorption range, faster separation and migration efficiency of photo-induced charge carriers, hence displaying enhanced photocatalytic activity and good stability. Density Functional Theory calculations demonstrate that the bimetallic Ni and Zn active sites can lower the adsorption energy of CO2, suggesting a high affinity of ZnNC/Ni towards CO2 molecules. In-situ Fourier Transform Infrared spectroscopy combined with theoretical calculations reveal that ZnNC/Ni facilitates the activation of CO2 molecules, reducing the energy barrier for the formation of key reaction intermediates such as *COOH. This work provides new insights into the photoreduction of CO2 by MOF-derived bimetallic composite catalysts to improve the activity and product selectivity of CO2 photoreduction.