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Intrinsic Charge Polarization in Bi19S27Cl3 Nanorods Promotes Selective C-C Coupling Reaction during Photoreduction of CO2 to Ethanol

Das, K and Das, R and Riyaz, M and Parui, A and Bagchi, D and Singh, AK and Singh, AK and Vinod, CP and Peter, SC (2022) Intrinsic Charge Polarization in Bi19S27Cl3 Nanorods Promotes Selective C-C Coupling Reaction during Photoreduction of CO2 to Ethanol. In: Advanced Materials .

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Official URL: https://doi.org/10.1002/adma.202205994


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, Bi19S27Cl3, 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 Bi19S27Cl3. 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. © 2022 Wiley-VCH GmbH.

Item Type: Journal Article
Publication: Advanced Materials
Publisher: John Wiley and Sons Inc
Additional Information: The copyright for this article belongs to John Wiley and Sons Inc
Keywords: Alkalinity; Carbon dioxide; Charge transfer; Chemical bonds; Chlorine compounds; Cyclic voltammetry; Efficiency; Electric fields; Ethanol; Fourier transform infrared spectroscopy; High resolution transmission electron microscopy; Nanorods; Polarization; Product design; Reaction intermediates; X ray absorption spectroscopy; X ray photoelectron spectroscopy, Bismuth centres; C-C bond formation; C-C coupling; C-C coupling reactions; Carbon products; Charge polarization; CO 2 reduction; Multi-electron; Photo reduction; Product selectivities, Bismuth compounds
Department/Centre: Division of Chemical Sciences > Materials Research Centre
Date Deposited: 31 Jan 2023 06:44
Last Modified: 31 Jan 2023 06:44
URI: https://eprints.iisc.ac.in/id/eprint/79603

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