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Imidazolium-functionalized Mo3P nanoparticles with an ionomer coating for electrocatalytic reduction of CO2 to propane

Abstract

Propane is a tri-carbon (C3) alkane widely used as a fuel. Despite recent advances in CO2 electrocatalysis, the production of C3+ molecules directly from CO2 is challenging due to high reaction barriers and competing reactions to C1, C2 and H2 products. Here we report a catalytic system composed of 1-ethyl-3-methylimidazolium-functionalized Mo3P nanoparticles coated with an anion-exchange ionomer that produces propane from CO2 with a current density of −395 mA cm2 and a Faradaic efficiency of 91% at −0.8 V versus reversible hydrogen electrode over 100 h in an electrolyser. Our characterization and density functional theory calculations suggest that imidazolium functionalization improves the electrocatalytic properties of Mo atoms at the surface and favours the pathway towards propane by increasing the adsorption energies of carbon-based intermediates on the Mo sites. Our results indicate that the ionomer coating layer plays a crucial role in stabilizing the imidazolium-functionalized surface of Mo3P nanoparticles during long-term testing.

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Fig. 1: Characterizations of the catalyst microenvironment of the developed ImF-Mo3P electrocatalytic system studied in a flow electrolyser.
Fig. 2: Electrocatalytic performance of ImF-Mo3P and Mo3P catalysts for the eCO2RR in a flow electrolyser using 1 M KOH electrolyte.
Fig. 3: Electronic structure analyses of the ImF-Mo3P and Mo3P catalysts.
Fig. 4: DFT results.

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The authors declare that the data supporting the findings of this study are available within the paper and its Supplementary Information. Source data are provided with this paper.

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Acknowledgements

M.A. acknowledges financial support from the National Science Foundation (NSF) Catalysis (CBET-2135173), Advanced Research Projects Agency-Energy OPEN2021 (DE-AR0001581) and SHV Energy. We acknowledge support from the Wanger Institute for Sustainable Energy Research (WISER) and Illinois Institute of Technology’s Armour College of Engineering. We also acknowledge the EPIC facility (NUANCE Center, Northwestern University), which has received support from the MRSEC programme (NSF DMR-1121262) at the Materials Research Center; the Nanoscale Science and Engineering Center (NSF EEC − 0647560) at the International Institute for Nanotechnology; and the State of Illinois, through the International Institute for Nanotechnology. Z.J. and A.M.R. acknowledge support from the Department of Energy, Office of Science, Office of Basic Energy Sciences, under grant number DE-SC0019281. R.S.-Y. acknowledges the financial support from the National Science Foundation award number DMR-1809439. Part of the microscopy experiments and M.T.S. efforts were supported from NSF award number DMR-2311104. This work utilized characterization facilities at the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-152205) at Northwestern University and the Electron Microscopy Service at Research Resources Center at the University of Illinois at Chicago.

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M.A. and M.E. conceived the idea of the work. M.E. synthesized the nanostructured materials. M.E., A.M.H. and A.K. performed electrochemical experiments and data analyses. M.E. did XRD and XPS characterizations. M.A. supervised the efforts of M.E., A.M.H. and A.K. M.T.S. and R.S.-Y. performed the TEM and ELNES characterizations. Z.J. performed the DFT calculations and theoretical analyses and designed numerical experiments. A.M.R. supervised Z.J. All authors discussed the results and assisted with paper preparation.

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Correspondence to Mohammad Asadi.

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M.A., M.E. and A.K. filed a provisional patent application. The other authors declare no competing interests.

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Esmaeilirad, M., Jiang, Z., Harzandi, A.M. et al. Imidazolium-functionalized Mo3P nanoparticles with an ionomer coating for electrocatalytic reduction of CO2 to propane. Nat Energy 8, 891–900 (2023). https://doi.org/10.1038/s41560-023-01314-8

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