Tuning OH binding energy enables selective electrochemical oxidation of ethylene to ethylene glycol

Abstract

There is significant interest in developing efficient electrochemical processes for commodity chemical manufacturing, all directly powered by renewable electricity. A vital chemical is ethylene glycol, with an annual consumption of around 20 million tonnes due to its use as antifreeze and as a polymer precursor. Here we report a one-step electrochemical route at ambient temperature and pressure in aqueous media to the selective partial oxidation of ethylene to ethylene glycol. Tuning of the catalyst OH binding energy was hypothesized to be crucial for facilitating the transfer of OH to *C2H4OH to form ethylene glycol. Computational studies suggested that a gold-doped palladium catalyst could perform this step efficiently, and experimentally we found it to exhibit an approximate 80% Faradaic efficiency to ethylene glycol, retaining its performance for 100 hours of continuous operation. These findings represent a significant advance in the development of selective anodic partial oxidation reactions in aqueous media under mild conditions.

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Fig. 1: An electrochemical route to ethylene glycol.
Fig. 2: Electron microscopy characterization and ethylene oxidation using the Pd DNT and commercial Pd/C catalysts.
Fig. 3: Investigation of the activation process involving the Pd DNT catalyst.
Fig. 4: Cyclic voltammetry experiments.
Fig. 5: Density functional theory calculations for ethylene oxidation to ethylene glycol.
Fig. 6: Characterization and bulk electrolysis testing of PdAu DNT catalyst.

Data availability

The data that support the findings of this study are available from the corresponding author on reasonable request.

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Acknowledgements

This material is based upon work supported by the Ontario Research Fund Research Excellence Program, the Natural Sciences and Engineering Research Council (NSERC) of Canada and the CIFAR Bio-Inspired Solar Energy program. The authors thank Z. Finfrock and D. M. Meira for technical support at the 20BM beamline of the Advanced Photon Source (Lemont, IL). This research used resources of the Advanced Photon Source, an Office of Science User Facility operated for the US Department of Energy (DOE) Office of Science by Argonne National Laboratory and was supported by the US DOE under Contract No. DE-AC02-06CH11357 and the Canadian Light Source and its funding partners. We acknowledge S. Fakra and the use of Beamline 10.3.2 at the Advanced Light Source for the collection of XAS data. The authors thank C. Andrei of the Canadian Centre for Electron Microscopy (CCEM) for TEM analysis. D.S. acknowledges the NSERC for an E. W. R. Steacie Memorial Fellowship. J.L. acknowledges the Banting Postdoctoral Fellowships program. All DFT computations were performed on the IBM BlueGene/Q supercomputer with support from the Southern Ontario Smart Computing Innovation Platform (SOSCIP) and Niagara supercomputer at the SciNet HPC Consortium. SOSCIP is funded by the Federal Economic Development Agency of Southern Ontario, the Province of Ontario, IBM Canada Ltd, Ontario Centres of Excellence, Mitacs and 15 Ontario academic member institutions. SciNet is funded by: the Canada Foundation for Innovation, the Government of Ontario, Ontario Research Fund—Research Excellence and the University of Toronto. We acknowledge the Ontario Centre for the Characterization of Advanced Materials (OCCAM) for characterization facilities.

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Contributions

E.H.S. supervised the project. Y.L. and E.H.S. conceived the idea and designed the experiments. Y.L. and J.E.H. carried out all the experimental work. Y.L. performed the DFT calculations. Z.W. supervised the DFT calculations. Y.L. and W.R.L. performed the TEA. M.L. carried out some of the TEM measurements. B.C. analysed the TEM results. Y.L. and D.H.N. carried out XAS measurements. Y.L. and J.L. analysed the XAS data. J.W. performed the XPS measurements. D.H.N carried out PXRD measurements. Y.C.L. and Y.W. performed SEM measurements. C.-T.D., T.-T.Z., F.L., T.-K.S. and D.S. contributed to data analysis and manuscript editing. Y.L. and E.H.S. co-wrote the manuscript. All authors discussed the results and assisted during the manuscript preparation.

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Correspondence to Edward H. Sargent.

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Supplementary Figures 1–39, Tables 1–5, Notes 1–3 and references.

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Lum, Y., Huang, J.E., Wang, Z. et al. Tuning OH binding energy enables selective electrochemical oxidation of ethylene to ethylene glycol. Nat Catal 3, 14–22 (2020). https://doi.org/10.1038/s41929-019-0386-4

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