Ni2P Aerogels with Pt Single-Atom Doping Tune Competitive Adsorption for Boosted Methanol Electrooxidation

Methanol oxidation reaction (MOR) provides an effective method to attain high-value-added chemicals. Nevertheless, the competitive adsorption between CH3OH and OH– causes poor activity and selectivity. In this work, Ni2P aerogels decorated with single-atom Pt are designed to tune the adsorption behavior of CH3OH and OH–, achieving an unprecedented current density of 2848.3 A gcat–1 and a Faradaic efficiency of 93.3% for formic acid. A series of electrochemical tests, operando spectroscopic characterizations, and theoretical calculations verify that Pt single-atom doping not only accelerates the adsorption of CH3OH and realizes high coverage of CH3OH on Ni active sites to impede the OER, but it also decreases the barrier of the rate-determining step, achieving a high-efficiency MOR. Specifically, an underlying competitive adsorption mechanism between CH3OH and OH– to enhance MOR is proposed. This work is highly instructive for developing promising and efficient electrocatalysts at the atomic scale and contributing to a deeper understanding of the MOR mechanism.