Structural principles to steer the selectivity of the electrocatalytic reduction of aliphatic ketones on platinum


Due to a general feedstock shift, the chemical industry is charged with the task of finding ways to transform renewable ketones into value-added products. A viable route to do so is the electrochemical hydrogenation of the carbonyl functional group. Here we report a study on acetone reduction at platinum single-crystal electrodes using online electrochemical mass spectroscopy, in situ Fourier transform infrared spectroscopy and density functional theory calculations. Acetone reduction at platinum displays a remarkable structural sensitivity: not only the activity, but also the product distribution depends on the surface crystallographic orientation. At Pt(111) neither adsorption nor hydrogenation occur. A decomposition reaction that deactivates the electrode happens at Pt(100). Acetone reduction proceeds at the (110) steps: Pt[(n – 1)(111) × (110)] electrodes produce 2-propanol and Pt[(n + 1)(100) × (110)] electrodes produce propane. Using density functional theory calculations, we built a selectivity map to explain the intricacies of the acetone reduction on platinum. Finally, we extend our conclusions to the reduction of higher aliphatic ketones.

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Fig. 1: Influence of the step density of Pt[(n – 1)(111) × (110)] electrodes on acetone reduction.
Fig. 2: Cyclic voltammetry of acetone reduction at Pt[(n + 1)(100) × (110)] electrodes.
Fig. 3: Structure sensitivity of propane formation during acetone reduction.
Fig. 4
Fig. 5: The most favourable reaction pathways computed for acetone reduction to 2-propanol and propane at Pt electrodes.
Fig. 6: Coordination–activity plots for acetone reduction.
Fig. 7: Structure-sensitive selectivity map for acetone reduction to 2-propanol and propane.

Data availability

All the data are available from the authors upon reasonable request.


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This research received funding from the Netherlands Organization for Scientific Research (NWO) in the framework of the fund New Chemical Innovations (project 731.015.204 ELECTROGAS) with financial support from Akzo Nobel Chemicals, Shell Global Solutions, Magneto Special Anodes (Evoqua Water Technologies) and Elson Technologies. F.C.-V. thanks the Spanish MEC for a Ramón y Cajal research contract (RYC-2015-18996) and acknowledges financial support from the Units of Excellence María de Maeztu programme through grant MDM-2017–0767. The use of supercomputing facilities at SURFsara was sponsored by NWO Physical Sciences, with financial support by NWO.

Author information




C.J.B. co-conducted the FTIR experiments and conducted the remaining experimental work (that is, CV, OLEMS and surface enhanced Raman spectroscopy studies), co-conceived the concept of the presented work and co-wrote the manuscript. F.C.V. conducted the theoretical modelling, co-conceived the concept of the presented work and co-wrote the manuscript. M.C.F. co-conducted the FTIR experiments. M.T.M.K. co-conceived the concept of the presented work and co-wrote the manuscript.

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Correspondence to Marc T. M. Koper.

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Bondue, C.J., Calle-Vallejo, F., Figueiredo, M.C. et al. Structural principles to steer the selectivity of the electrocatalytic reduction of aliphatic ketones on platinum. Nat Catal 2, 243–250 (2019).

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