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 <b>In</b>_<b>2.77</b><b>S</b>_<b>4</b> 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 <b>In</b>_<b>2.77</b><b>S</b>_<b>4</b> 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 <i>via</i> 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.