Complete electron economy by pairing electrolysis with hydrogenation

Abstract

Electrosynthesis provides a method of driving organic reaction chemistry under ambient conditions with electricity. Pairing two reactions together enables the synthesis of two valuable chemicals with no waste product. Here we report the paired electrolysis of 4-methoxybenzyl alcohol to 4-methoxybenzaldehyde with the concomitant formation of 1-hexene from 1-hexyne in an electrochemical cell. These reaction chambers are separated by a dense palladium membrane that reduces protons formed at the anode to hydrogen atoms that can permeate through the palladium foil to hydrogenate 1-hexyne. The palladium membrane enables two reactions to be performed in distinct reaction conditions: hydrogenation in organic solvents and electrochemical oxidation in aqueous electrolyte. The starting materials in both chambers react quantitatively over 5 hours of electrolysis, and selectivities ≥95% can be achieved for 4-methoxybenzaldehyde and 1-hexene with control of reaction conditions. Exquisite control of the reaction kinetics and selectivities of each of the individual reactions is demonstrated.

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Fig. 1: Three-compartment cell configuration designed for paired electrolysis.
Fig. 2: Hydrogen evolution on both sides of the palladium membrane.
Fig. 3: Catalyst morphology and product distribution for palladium membrane chemical hydrogenation.
Fig. 4: Product conversion and distribution in paired electrolysis.
Fig. 5: Hydrogenation and oxidation current efficiencies at various applied currents.
Fig. 6: Hydrogenation selectivity with applied current and electrolyte.

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Acknowledgements

The authors are grateful to the Canadian Natural Science and Engineering Council (RGPIN 337345-13), Canadian Foundation for Innovation (229288), Canadian Institute for Advanced Research (BSE-BERL-162173), Canada Research Chairs and Google for financial support. Thank you to Y. Ling in the University of British Columbia Mass Spectrometry Centre for assistance with the gas chromatography–mass spectrometer instrument and to G. Owen in the Centre for High-Throughput Phenogenomics for assistance with scanning electron microscope imaging.

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R.S.S., B.P.M. and C.P.B. devised the concept. R.S.S. and R.S.D. performed preliminary proof-of-concept experiments. R.S.S. performed paired electrolysis experiments. V.A.C. helped with characterization. R.S.S. and C.P.B. wrote the manuscript. C.P.B. supervised the project.

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Correspondence to Curtis P. Berlinguette.

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Sherbo, R.S., Delima, R.S., Chiykowski, V.A. et al. Complete electron economy by pairing electrolysis with hydrogenation. Nat Catal 1, 501–507 (2018). https://doi.org/10.1038/s41929-018-0083-8

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