Selective transformation of aqueous methanol to value-added formic acid and hydrogen on bifunctional Mo2P monolayers in fuel cells

Abstract Direct methanol fuel cell (DMFC) running on hydrogen is an attractive alternative power source for a wide range of applications. Importantly, the required hydrogen can be in situ released from the stable liquid, which ensures its safe transformation and storage. However, the catalyst in DMFC is usually poisoned by the generated CO species, thus it is challenging to find an efficient and durable catalyst for practical applications. Here, the mechanism of methanol oxidation reaction (MOR) on the Mo2P monolayer is first studied using density functional theory. Compared with the initial C–H and C–O bond scissions, the initial O–H bond scission is found to be the most favorable. The reason is systematically analyzed based on steric effect, activation Gibbs free energy (Gact) decomposition and the Bronsted − Evans − Polanyi (BEP) relationships. The further dehydrogenation of CH2OH via the O–H bond scission has a significantly lower Gact than that of CH3O, thus the methanol decomposition on the Mo2P monolayer may proceed via two competitive pathways, i.e., CH 3 OH → CH 3 O → CH 2 O → CHO → CO and CH 3 OH → CH 2 OH → CH 2 O → CHO → CO . Then, through overcoming a relatively low barrier, the generated CO species can be combined with hydroxyl group from water dissociation on the Mo2P monolayer to produce formic acid, which can be easily desorbed from the catalyst surface to avoid the block of active sites. This study provides a better understanding of the MOR mechanism and paves the way for further advancing the catalyst in DMFCs.