Regulating orbital interaction to construct quasi-covalent bond networks in Pt intermetallic alloys for high-performance fuel cells

The long-standing challenges facing Pt-based alloy catalysts in oxygen reduction reactions (ORRs) are rapid oxidation and loss of transition metal/Pt in proton exchange membrane fuel cells (PEMFCs). In this work, we report a concept of "covalentization" in intermetallic L1₀-PtMM' (M = Fe, Co, Ni and M' = one of the 4^th-period elements (from Ti to Ge)) alloys to enhance their electrochemical stability. Specifically, the formation of a quasi-covalent bond network in L1₀-PtMM' due to the less occupied antibonding states induced by high d-band positions of M' elements (e.g., Ti, V, Cr) enhances atomic bond order and strength, diminishing Co anodic dissolution via strengthened Pt/Co-M' bonds and reducing Co cathodic corrosion by inhibiting Pt oxidation through an electron buffering effect. The developed L1₀-PtCoCr/C catalysts show a high mass activity (MA = 1.27 A mg_Pt^-1) and rated power (16.5 W mg_Pt^-1) in PEMFCs at a low total Pt loading of 0.075 mg_Pt cm^-2. The catalysts also exhibit high electrochemical stability with ~3% and 5% loss of MA and rated power after 30,000 accelerated durability testing cycles and projects a lifetime of about 42,000 hours.