02564nas a2200289   4500008004100000022001400041245013800055210006900193260000800262490000700270520158500277653001701862653002401879653001801903653001201921653001901933100001601952700001501968700001601983700001601999700002202015700002702037700002702064700002802091700002502119856013002144       2023                        eng d  a0935-964800aIntrinsic charge polarization in Bi19S27Cl3 nanorods promotes selective C-C coupling reaction during photoreduction of CO2 to ethanol0 aIntrinsic charge polarization in Bi19S27Cl3 nanorods promotes se  cFEB0 v353 a<p>
	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 C-2 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.</p>
10aC-C coupling10acharge polarization10aCO2 reduction10aEthanol10aPhotocatalysis1 aDas, Kousik1 aDas, Risov1 aRiyaz, Mohd1 aParui, Arko1 aBagchi, Debabrata1 aSingh, Ashutosh, Kumar1 aSingh, Abhishek, Kumar1 aVinod, Chathakudath, P.1 aPeter, Sebastian, C.  uhttps://library.ncl.res.in/content/intrinsic-charge-polarization-bi19s27cl3-nanorods-promotes-selective-c-c-coupling-reaction