Engineering the charge density on an In_2.77S₄/porous organic polymer hybrid photocatalyst for CO₂-to-ethylene conversion reaction

Abstract

The development of an efficient photocatalyst for C2 product formation from CO₂ is of urgent importance toward the deployment of solar-fuel production. Here, we report a template-free, cost-effective synthetic strategy to develop a carbazole-derived porous organic polymer (POP)-based composite catalyst. The composite catalyst is comprised of In2.77S4 and porous organic polymer (POP) and is held together by induced-polarity-driven electrostatic interaction. Utilizing the synergy of the catalytically active In centers and light-harvesting POPs, the catalyst showed 98.9% selectivity toward the generation of C₂H₄, with a formation rate of 67.65 μmol g^–1 h^–1. Two different oxidation states of the In_2.77S₄ spinel were exploited for the C–C coupling process, and this was investigated by X-ray photoelectron spectroscopy (XPS), X-ray absorption spectroscopy (XAS), and density functional theory (DFT) calculations. The role of POP was elucidated via several photophysical and photoelectrochemical studies. The electron transfer was mapped by several correlated approaches, which assisted in establishing the Z-scheme mechanism. Furthermore, the mechanism of C₂H₄ formation was extensively investigated using density functional theory (DFT) calculations from multiple possible pathways.