Propane Activation on Pt Electrodes at Room Temperature: Quantification of Adsorbate Identity and Coverage

Bhadouria, Ashutosh; Heil, Joseph N.; Parab, Durvesh E.; Greeley, Jeffrey P.; Tackett, Brian M.

doi:10.1002/ange.202421613

Title: Propane Activation on Pt Electrodes at Room Temperature: Quantification of Adsorbate Identity and Coverage

Journal Article · 07 January 2025 · Angewandte Chemie

DOI: https://doi.org/10.1002/ange.202421613 · OSTI ID:2497858

^[1]; Heil, Joseph N. ^[1]; Parab, Durvesh E. ^[1]; Greeley, Jeffrey P. ^[1];

^[1]

Davidson School of Chemical Engineering Purdue University Forney Hall of Chemical Engineering, 480 Stadium Mall Drive West Lafayette IN 47907-2100 USA

Abstract C−H bond activation is the first step in manufacturing chemical products from readily available light alkane feedstock and typically proceeds via carbon‐intensive thermal processes. The ongoing emphasis on decarbonization via electrification motivates low‐temperature electrochemical alternatives that could lead to sustainable chemicals production. Platinum (Pt) electrocatalysts have shown activity towards reacting alkanes; however, little is known about propane electrocatalytic activation and conditions suitable for enabling selective oxidation to valuable products. Herein, we utilize a combination of electrochemical mass spectrometry (ECMS) and density functional theory (DFT) calculations to elucidate the potential dependence of propane activation on Pt electrocatalysts. Results show a strong dependence of adsorption on the applied potential in room‐temperature aqueous acidic electrolyte, with a maximum coverage of propane‐derived adsorbates at 0.30 V vs RHE. Using charge deconvolution and deuterated experiments, the mechanism of adsorption was elucidated, and C ₃ H ₂ ^* was determined as the average dehydrogenated propane‐derived adsorbate species. DFT calculations further corroborate these results, showing that the formation of deeply dehydrogenated species is energetically accessible at room temperature. The combined theoretical and experimental findings yield insights for selective activation of paraffinic C−H bonds at room temperature, aqueous conditions—a critical step towards decarbonized chemical manufacturing.

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Sponsoring Organization:: USDOE

Grant/Contract Number:: SC0023257

OSTI ID:: 2497858

Journal Information:: Angewandte Chemie, Journal Name: Angewandte Chemie Journal Issue: 11 Vol. 137; ISSN 0044-8249

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

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