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Linear paired electrochemical valorization of glycerol enabled by the electro-Fenton process using a stable NiSe2 cathode

Abstract

Electrochemical valorization of surplus biomass-derived feedstocks, such as glycerol, into high-value chemicals offers a sustainable route for utilization of biomass resources and decarbonization of chemical manufacturing; however, glycerol is typically valorized solely via anodic oxidation, with lower-value products such as hydrogen gas generated at the cathode. Here, we establish the efficient cathodic valorization of glycerol to the desirable C3 oxidation products via the electro-Fenton process at a stable NiSe2 cathode, built upon the theoretical understanding and experimental demonstration of the high selectivity and stability of NiSe2 toward acidic H2O2 electrosynthesis. A proof-of-concept linear paired electrochemical process for concurrent valorization of glycerol into the same oxidation products at both NiSe2 cathode and Pt anode achieves high selectivity for value-added C3 products and high glycerol conversion with little external energy input needed, when the electro-Fenton generation of hydroxyl radicals is carefully controlled. This conceptual strategy of linear pairing is generalizable for enabling atom-efficient electro-refinery of diverse biomass-derived feedstocks.

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Fig. 1: Different pairing strategies for electrochemical valorization of glycerol.
Fig. 2: Computations of ORR energetics and surface stability of c-NiSe2 versus c-CoSe2.
Fig. 3: Electrocatalytic properties and stability for acidic H2O2 electrosynthesis.
Fig. 4: Glycerol valorization enabled by the electro-Fenton process at the NiSe2 cathode.
Fig. 5: Linear paired glycerol valorization at NiSe2 cathode and Pt anode.

Data availability

The data that support the findings of this study are presented in the article and Supplementary Information. Source data are provided with this paper. Any other relevant data are also available from the corresponding authors upon reasonable request.

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Acknowledgements

This research was supported by the National Science Foundation (NSF, grant no. CHE-1955074) for materials synthesis and electrochemical experiments (H.S., R.D.R. and S.J.) and for computational modelling (A.N.J., K.L. and J.R.S.). The calculations performed utilized computational resources from the Extreme Science and Engineering Discovery Environment supported by NSF grant no. TG-CHE120088. The Bruker AVANCE III 600 MHz NMR spectrometer was supported by National Institutes of Health grant no. S10 OK012245. The authors gratefully acknowledge use of the facilities and instrumentation at the UW-Madison Wisconsin Centers for Nanoscale Technology (wcnt.wisc.edu), partially supported by the NSF through the University of Wisconsin Materials Research Science and Engineering Center (no. DMR-1720415). We thank J. Lazarcik for help with gaining access to the ICP–MS spectrometer supported by the Water Science and Engineering Laboratory at UW-Madison. This research used resources of the APS, a US Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under contract no. DE-AC02-06CH11357. We thank Y. Ding for help with XAS experiments performed at APS Beamline 10-BM-B.

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H.S. and S.J. designed the experiments. H.S. carried out materials synthesis, materials characterization (with the help of R.D.R.), electrochemical measurements and product analyses of glycerol valorization (with the help of H.H.). A.N.J. and J.R.S. conceived computational modelling of the catalyst. A.N.J. and K.L. performed computational modelling. H.S. and S.J. wrote the manuscript, and all authors commented on it.

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Correspondence to J. R. Schmidt or Song Jin.

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A provisional patent has been filed based on this work by some of the authors of this manuscript (H.S., A.N.J., R.D.R., K.L., J.R.S. and S.J.). The remaining author (H.H.) declares no competing interests.

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Sheng, H., Janes, A.N., Ross, R.D. et al. Linear paired electrochemical valorization of glycerol enabled by the electro-Fenton process using a stable NiSe2 cathode. Nat Catal 5, 716–725 (2022). https://doi.org/10.1038/s41929-022-00826-y

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