Intrinsic Charge Polarization in Bi₁₉ S₂₇ Cl₃ Nanorods Promotes Selective CC Coupling Reaction during Photoreduction of CO₂ to Ethanol.

Abstract

Obtaining multi-carbon products via CO₂  photoreduction is a major catalytic challenge involving multielectron-mediated CC bond formation. Complex design of multicomponent interfaces that are exploited to achieve this chemical transformation, often leads to untraceable deleterious changes in the interfacial chemical environment affecting CO₂  conversion efficiency and product selectivity. Alternatively, robust metal centers having asymmetric charge distribution can effectuate CC coupling reaction through the stabilization of intermediates, for desired product selectivity. However, generating inherent charge distribution in a single component catalyst is a difficult material design challenge. Here, a novel photocatalyst, Bi₁₉ S₂₇ Cl₃ , is presented which selectively converts CO₂  to a C₂  product, ethanol, in high yield under visible light irradiation. Structural analysis through transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and X-ray absorption spectroscopy reveals the presence of charge polarized bismuth centers in Bi₁₉ S₂₇ Cl₃ . The intrinsic electric field induced by charge polarized bismuth centers renders better separation efficiency of photogenerated electron-hole pair. Furthermore, charge polarized centers yield better adsorption of CO* intermediate and accelerate the rate determining CC coupling step through the formation of OCCOH intermediate. Formation of these intermediates is experimentally mapped by in situ Fourier-transform infrared spectroscopy and further confirmed by theoretical calculation.