Pb induced dislocation defects of PtCo systems: Strain-triggered oxygen reduction reaction for PEMFC

Design and development of advanced electrocatalysts with high performance and low Pt consumption are crucial for reducing the kinetic energy barrier of the cathode oxygen reduction reaction(ORR)and improving the efficiency of proton exchange membrane fuel cells(PEMFC).In this study,we demonstrate a Pb-modulated PtCo system for efficient ORR,in which the inclusion of Pb in ternary alloys induces dislocation defects due to the significant difference in atomic radius.Dislocation-PtCoPb was confirmed to exhibit significantly higher ORR activity and stability in acidic ORR.In practical PEMFC applications,it outperforms the corresponding commercial Pt/C with a mass activity of 0.58 A·mgPt^(-1),making it a promising alternative to state-of-the-art Pt-based catalysts.The combination of experimental results and density functional theory(DFT)calculations offers valuable atomic-level insights into the dislocation structures.Pb with a larger atomic radius is located in the lattice stretching region below the dislocation slip plane,forming a structure similar to a Cottrell atmosphere,which reduces the dislocation energy and puts the system in a lower energy state.The Cottrell atmosphere pins the dislocation structure and stabilizes the ternary alloy.By adjusting the amount of added Pb,a moderate level of dislocation density induces a tuned strain effect,thereby enhancing the electrocatalytic mechanism by optimizing the electronic structure of the alloy surface and the adsorption and desorption of oxygen species.This work provides valuable insights into the design and development of lattice dislocation defect structures to trigger strain effects for improving ORR performance.

Small amount but big impact:Trace oxygen interstitially inserted PtCu alloys by microalloying for efficient oxygen reduction catalysis

The introduction of small size non-metal elements(e.g.,oxygen)into solid solution alloys may be a promising strategy for fabricating efficient Pt-based catalysts with high activity and stability toward oxygen reduction reaction(ORR).Herein,oxygen interstitially inserted PtCu(O-PtCu)alloys are firstly designed by an oxygen-microalloying strategy,through ultraviolet(UV)irradiation-assisted galvanic replacement in an aqueous solution containing H_(2)PtCl_(6) and Cu_(2)O nanowires as sacrificial templates.The obtained O-PtCu alloys feature a typical face-centered cubic(FCC)structure with majority Pt,Cu atoms as building bricks and trace interstitial oxygen(1.65 wt.%)existed in the octahedral sites surrounding Cu atoms,leading to a short-range disordered structure.The alloy reaches a recorded half-wave potential of 0.96 V(vs.reversible hydrogen electrode(RHE))and mass activity of 0.48 A·mgPt^(−1),much higher than those of commercial Pt/C.During the accelerated degradation test(ADT),the mass activity lost only 4.2%after 10k cycles,while the commercial Pt/C lost 66.7%under the same conditions.Compared with pure Pt and undoped PtCu alloy,the remarkably improved performance can be attributed to the lattice distortion and energy band reconstruction caused by the interstitial oxygen atoms in form of Cu–O bonds.Moreover,the stable Cu–O bonds delay the possible place exchange between surface Pt atoms and surface-adsorbed oxygen species,thereby hindering Pt dissolution,providing a new paradigm to address Pt degradation issue.Therefore,the introduction of interstitial oxygen into Pt-based alloys may be a facile and smart strategy for the development of advanced Pt-based alloys electrocatalysts.