Electrodeposition-fabricated PtCu-alloy cathode catalysts for high-temperature proton exchange membrane fuel cells

Abstract

Pt electrocatalysts in high-temperature proton exchange membrane fuel cells (HT-PEMFCs) containing phosphoric acid (PA)-doped polymer membranes are prone to poisoning by leaked PA. We performed a preliminary density functional theory (DFT) study to investigate the relationship between the electronic structure of Pt surfaces and their adsorption of PA. Excess charge on Pt was found to weaken its bonding with the oxygen in PA, thus presenting a strategy for the fabrication of PA-resistant catalyst materials. Consequently, PtCu-alloy catalysts with various compositions were prepared by electrodeposition. The morphologies and crystalline structures of the alloys were strongly dependent on alloy composition. Moreover, the Pt atoms in the PtCu-alloy catalysts were found to be in an electron-rich state, similar to that of the excessively charged Pt simulated in the DFT study. As a result, the oxygen reduction reaction activities of the PtCu-alloy catalysts were superior to that of a Pt-only catalyst, regardless of the presence of PA. In the absence of PA, the higher activity of the PtCu-alloy catalysts was ascribable to conventional alloying effects, while the increased activity in the presence of PA was largely due to the enhanced resistance to PA poisoning. Therefore, PtCu-alloy catalysts easily prepared by electrodeposition were found to be strong candidate materials for HT-PEMFC electrodes.