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The effect of elastic strain on catalytic activity of platinum (Pt) towardsoxygen reduction reaction (ORR) is investigated through de-alloyed Pt-Cu thinfilms; stress evolution in the de-alloyed layer and the mass of the Cu removedare measured in real-time during electrochemical de-alloying of (111)-texturedthin-film PtCu (1:1, atom %) electrodes. In situ stress measurements are madeusing the cantilever-deflection method and nano-gravimetric measurements aremade using an electrochemical quartz crystal nanobalance. Upon de-alloying viasuccessive voltammetric sweeps between -0.05 and 1.15 V vs. standard hydrogenelectrode, compressive stress develops in the de-alloyed Pt layer at thesurface of thin-film PtCu electrodes. The de-alloyed films also exhibitenhanced catalytic activity towards ORR compared to polycrystalline Pt. In situnanogravimetric measurements reveal that the mass of de-alloyed Cu isapproximately 210 +/- 46 ng/cm2, which corresponds to a de-alloyed layerthickness of 1.2 +/- 0.3 monolayers or 0.16 +/- 0.04 nm. The average biaxialstress in the de-alloyed layer is estimated to be 4.95 +/- 1.3 GPa, whichcorresponds to an elastic strain of 1.47 +/- 0.4%. In addition, densityfunctional theory calculations have been carried out on biaxially strained Pt(111) surface to characterize the effect of strain on its ORR activity; thepredicted shift in the limiting potentials due to elastic strain is found to bein good agreement with the experimental shift in the cyclic voltammograms forthe dealloyed PtCu thin film electrodes.

On the Role of Elastic Strain on Electrocatalysis of Oxygen Reduction Reaction on Pt