Semimetal-triggered covalent interaction in Pt-based intermetallics for fuel-cell electrocatalysis

Platinum-based intermetallic compounds (IMCs) play a vital role as electrocatalysts in a range of energy and environmental technologies, such as proton exchange membrane fuel cells. However, the synthesis of IMCs necessitates recombination of ordered Pt-M metallic bonds with high temperature driving, which is generally accompanied by side effects for catalysts' structure and performance. In this work, we highlight that semimetal atoms can trigger covalent interactions to break the synthesis-temperature limitation of platinum-based intermetallic compounds and benefit fuel-cell electrocatalysis. Attributed to partial fillings of p-block in semimetal elements, the strong covalent interaction of d-p π backbonding can benefit the recombination of ordered Pt-M metallic bonds (PtGe, PtSb and PtTe) in the synthesis process. Moreover, this covalent interaction in metallic states can further promote both electron transport and orbital fillings of active sites in fuel cells. The semimetal-Pt IMCs were obtained with a temperature 300 K lower than that needed for the synthesis of metal-Pt intermetallic compounds and reached the highest CO-tolerant oxygen reduction activity (0.794 A mg^-1 at 0.9 V and 5.1% decay under CO poisoning) among reported electrocatalysts. We anticipate that semimetal-Pt IMCs will offer new insights for the rational design of advanced electrocatalysts for fuel cells.