Electrochemically Induced Strain Evolution in Pt-Ni Alloy Nanoparticles Observed by Bragg Coherent Diffraction Imaging.

Abstract

Strain is known to enhance the activity of the oxygen reduction reaction in catalytic platinum alloy nanoparticles, whose inactivity is the primary impediment to efficient fuel cells and metal-air batteries. Bragg coherent diffraction imaging (BCDI) was employed to reveal the strain evolution during the voltammetric cycling in Pt-Ni alloy nanoparticles composed of Pt₂Ni₃, Pt₁Ni₁, and Pt₃Ni₂. Analysis of the 3D strain images using a core-shell model shows that the strain as large as 5% is induced on Pt-rich shells due to Ni dissolution. The composition dependency of the strain on the shells is in excellent agreement with that of the catalytic activity. The present study demonstrates that BCDI enables quantitative determination of the strain on alloy nanoparticles during electrochemical reactions, which provides a means to exploit surface strain to design a wide range of electrocatalysts.