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The mechanisms of formic acid (HCOOH) oxidation on Pt(111) under electrochemical conditions have been studied using density functional theory and then compared with the analogous gas-phase reaction. Results show that HCOOH oxidation under a water-covered surface behaves substantially differently than in the gas phase or using a solvation model involving only a few water molecules. Using these models, we evaluated the detailed reaction process, including energies and geometric structures of intermediates and transition states under the influence of different solvation models and electrode potentials. Our calculations indicate that this potential-dependent electrochemical oxidation proceeds via a multipath mechanism (involving both the adsorbed HCOOH and HCOO intermediates), a result succinctly rationalizing conflicting experimental observations. Moreover, this study highlights how subtle changes in electrochemical reaction environments can influence (electro)catalysis.
Gao et al. (Tue,) studied this question.