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Synergistic Core-shell Interactions Enable Ultra-low Overpotentials for Enhanced CO2 Electro-reduction Activity

Abstract

Carbon dioxide is major delinquent of climate change, dramatically warming earth with its accu- mulation in atmosphere. Converting CO2 to high end fuels could potentially solve environmental problems and create a sustainable energy cycle. In spite of Cu being the most successful cata- lyst capable of producing hydrocarbons from CO2, its efficiency suffers from high overpotentials, which originates from the highly endothermic CO protonation to CHO. Using density functional theory (DFT), we optimize the composition of bimetallic core TMxNi13−x (TM = 3d transition met- als; x = 3, 6, and 9) encapsulated in a 42 atom Cu icosahedral shell to lower CO2 reduction over- potential. On Sc5(6)Ni8(7)−Cu42, this overpotential reduces to an unprecedented value of ∼ 0.17 V below the standard potential value (SPV). These specific core compositions optimize the position of d-band center of shell, required for better interaction with CHO π orbitals than CO, giving exer- gonic CO reduction. Estimated statistical coverage of CHO exceeds 60% at ambient conditions on Sc6Ni7−Cu42, which will promote CO2 conversion to high end fuel CH4 without CO poisoning of the catalyst. The effect of implicit solvent is found to be marginal on the stability, reaction barriers and overpotentials, ensuring robustness of Sc5(6)Ni8(7)−Cu42 for efficient CO2 electro-reduction.

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Publication details

The article was received on 09 Jul 2018, accepted on 01 Oct 2018 and first published on 02 Oct 2018


Article type: Paper
DOI: 10.1039/C8TA06587J
Citation: J. Mater. Chem. A, 2018, Accepted Manuscript
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    Synergistic Core-shell Interactions Enable Ultra-low Overpotentials for Enhanced CO2 Electro-reduction Activity

    R. Ahmad and A. K. Singh, J. Mater. Chem. A, 2018, Accepted Manuscript , DOI: 10.1039/C8TA06587J

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