Formic acid oxidation on different coverages of Bismuth-modified Pt (100): A detailed voltammetric and FTIR study

The formic acid oxidation reaction (FAOR) on bismuth-modified Pt(1 0 0) is studied using electrochemical techniques and FITR spectroscopy at different bismuth coverages and formic acid concentrations. The results clearly show that: (1) The measured currents for the Bi-modified Pt(1 0 0) surface contain contributions from both the Pt-Bi ensembles and the Pt sites far from the Bi adatoms. (2) The catalytic effect of bismuth is not linked to the adsorption of formate on Pt sites. (3) The bismuth not only improves the activity of the FAOR through the active intermediate but also inhibits the CO poison by a third-body effect. (4) The experimental results indicate that the catalytic activity is linked to the Pt-Bi ensembles. The active species, formate, adsorbs on the Bi site and the neighboring Pt sites facilitate the cleavage of the C-H bond. (5) From the concentration dependence, the reaction order for formate on bismuthmodified Pt(1 00) is 1 at low potentials. In contrast, a reaction order of 0.5 is obtained at higher potentials. These results are in agreement with the proposed mechanism.& COPY; 2023 The Author(s). Published by Elsevier Inc. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).