Trimetallic Alloys as an Electrocatalyst for Fuel Cells: The Case of Methyl Formate on Pt3Pd3Sn2

Radhey Shyam Yadav, Diwakar Kashyap, Itay Pitussi, Medhanie Gebremedhin Gebru, Hanan Teller, Alex Schechter, Haya Kornweitz

Research output: Contribution to journalArticlepeer-review

Abstract

The shift toward renewable energy sources plays a central role in the quest for a circular economy. In this context, methyl formate (MF) has garnered attention as a compelling hydrogen carrier and alternative fuel, because of its remarkable characteristics (energy density, ease of storage and transport, and low boiling point). In this study, DFT calculations supported by online electrochemical mass spectroscopy (OE-MS) were performed to investigate the MF electro-oxidation (MFEO) on Pt3Pd3Sn2 (111). The DFT calculations provide insight into the role of Pt, Pd, and Sn atoms in MFEO. Pt and Pd together provide a preferred active site for initiating MFEO through the O-H bond scission, and Sn plays an essential role in the mitigation of CO through oxygenation or water activation. By comparing the reaction energies and activation barriers for all possible reactions in MFEO, the suggested path necessitates a minimum energy of 0.14 eV to initiate the MFEO. This value was supported by the experimental results, showing that the oxidation wave of MF starts at 0.15 V (70 °C). Density functional theory (DFT) results, supported by OE-MS, indicate that the hydrolysis of MF prior to MFEO is not preferred on Pt3Pd3Sn2 (111) surfaces, although the formation of methanol is plausible via a CH3O intermediate. Among the three small organic molecules (SOMs) studied─MF, methanol, and formic acid─MF has the lowest activation energy for the initial bond breaking that starts the whole oxidation process (0.13 eV), compared to formic acid (0.45 eV) and methanol (0.61 eV); thus, MF is the preferred fuel on Pt3Pd3Sn2 (111).

Original languageEnglish
Pages (from-to)58573-58586
Number of pages14
JournalACS Applied Materials and Interfaces
Volume16
Issue number43
Early online date16 Oct 2024
DOIs
StatePublished - 30 Oct 2024
Externally publishedYes

Bibliographical note

Publisher Copyright:
© 2024 The Authors. Published by American Chemical Society.

Keywords

  • Density functional theory
  • Electro-oxidation
  • Fuel cells
  • Methyl formate
  • d-band center

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