PdGa nanoalloys loaded on single atom Co dispersed nitrogen doped carbon for ethanol electrooxidation: improved C1 pathway selectivity and durability

Abstract

Direct ethanol fuel cells (DEFCs) are among the most efficient and environmentally friendly energy conversion devices, and the development of ethanol oxidation reaction (EOR) catalysts with high C1 pathway selectivity and electrochemical durability is essential for the commercialization of DEFCs. In this study, we demonstrate that engineering a single-atom Co dispersed support is an effective strategy for modulating the electronic structure of supported PdGa alloy nanoparticle catalysts, thereby significantly enhancing the EOR performance. In an alkaline system, PdGa/CoSA-NC exhibits a C1 path selectivity of 34.3% at 0.8 VRHE, being 2.3 and 7.0 times those of PdGa/NC and commercial Pd/C, respectively. Also, in the accelerated durability testing PdGa/CoSA-NC well retains 74.2% and 35.0% of the initial activity after 1000 and 2500 cycles, respectively. Our theoretical calculations show that PdGa alloy nanoparticles exhibit significantly enhanced electron transfer to the CoSA-NC support compared to their PdGa/NC counterpart, leading to a substantial increase in charge density at the interfacial region of PdGa/CoSA-NC. The well modified electron structures optimize the adsorption energies of key intermediate species on Pd sites, simultaneously promoting both C-C bond cleavage and *CO oxidation, thus enhancing the C1 pathway selectivity and EOR durability on PdGa/CoSA-NC.