The electroreduction of CO2, driven by renewable electricity, can be used to sustainably generate synthetic fuels. So far, only copper-based materials have been used to catalyse the formation of multicarbon products, albeit limited to C2 or C3 molecules. Herein, we disclose that inorganic nickel oxygenate-derived electrocatalysts can generate linear and branched C3 to C6 hydrocarbons with sustained Faradaic efficiencies of up to 6.5%, contrasting with metallic nickel, which is practically inactive. Operando X-ray absorption spectroscopy, electrochemical CO stripping and density functional theory pinpoint the presence of stable, polarized Niδ+ active sites associated with Ni–O bonds, which bind CO moderately. The reduction of selected C1 molecules and density functional theory simulations suggest that the Niδ+ sites promote a mechanism reminiscent of the Fischer–Tropsch synthesis: COOH + CHx coupling followed by successive CHx insertions. Our results disclose atom polarization to be the key that prevents the CO poisoning of nickel and enables CO2 reduction to a wider pool of valuable products.

Long-chain hydrocarbons by CO2 electroreduction using polarized nickel catalysts / Zhou, Yansong; José Martín, Antonio; Dattila, Federico; Xi, Shibo; López, Núria; Pérez-Ramírez, Javier; Siang Yeo, Boon. - In: NATURE CATALYSIS. - ISSN 2520-1158. - 5:6(2022), pp. 545-554. [10.1038/s41929-022-00803-5]

Long-chain hydrocarbons by CO2 electroreduction using polarized nickel catalysts

Federico Dattila;
2022

Abstract

The electroreduction of CO2, driven by renewable electricity, can be used to sustainably generate synthetic fuels. So far, only copper-based materials have been used to catalyse the formation of multicarbon products, albeit limited to C2 or C3 molecules. Herein, we disclose that inorganic nickel oxygenate-derived electrocatalysts can generate linear and branched C3 to C6 hydrocarbons with sustained Faradaic efficiencies of up to 6.5%, contrasting with metallic nickel, which is practically inactive. Operando X-ray absorption spectroscopy, electrochemical CO stripping and density functional theory pinpoint the presence of stable, polarized Niδ+ active sites associated with Ni–O bonds, which bind CO moderately. The reduction of selected C1 molecules and density functional theory simulations suggest that the Niδ+ sites promote a mechanism reminiscent of the Fischer–Tropsch synthesis: COOH + CHx coupling followed by successive CHx insertions. Our results disclose atom polarization to be the key that prevents the CO poisoning of nickel and enables CO2 reduction to a wider pool of valuable products.
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11583/2981912