Highly exposed PtPdTe alloy planting with oxyphilic Cu single sites boosting durable multiple alcohol oxidation electrocatalysis

Abstract

Platinum group alloys have an excellent electronic structure for oxidation of alcohols, but the active sites are more susceptible to deactivation by CO adsorbates (CO_ads). The precise integration of single-atom and alloy structures is highly attractive for energy conversion but still a challenge. Here, we report an ion-exchange coupled in situ reduction strategy to fabricate hollow PtPdTe alloy nanoreactors loaded with atomically dispersed Cu sites (Cu_SA/h-PtPdTe NRs). The planted oxyphilic Cu single sites and resulted compressive strains are conductive to modulating the electronic structure of the active sites, which changes the rate-determining step of the reaction while inhibiting the formation of CO_ads and modulating the adsorption of intermediates, resulting in the improved activity and stability. Specifically, the obtained Cu_SA/h-PtPdTe NRs exhibit an excellent oxidation performance of multiple alcohols, especially for methanol and ethanol, with 8.0 and 10.3 times of the mass activity higher than Pt/C, and the activity could be recovered by refreshing the electrolyte and could be sustained for 72,000 and 36,000 s, respectively. Meanwhile, Cu_SA/h-PtPdTe NRs show superior oxidation performance and durability to ethylene glycol and glycerol. This work pioneers the realization of precise modulation of catalytic sites using single atoms and provides an encouraging pathway for the design of efficient and stable electrocatalysts for the oxidation of multiple alcohols, which could broaden the range of options and sources of fuel cells.