Mastering the surface strain of platinum catalysts for efficient electrocatalysis

Platinum (Pt) has found wide use as an electrocatalyst for sustainable energy conversion systems1–3. The activity of Pt is controlled by its electronic structure (typically, the d-band centre), which depends sensitively on lattice strain4,5. This dependence can be exploited for catalyst design4,6–8, and the use of core–shell structures and elastic substrates has resulted in strain-engineered Pt catalysts with drastically improved electrocatalytic performances7,9–13. However, it is challenging to map in detail the strain–activity correlations in Pt-catalysed conversions, which can involve a number of distinct processes, and to identify the optimal strain modification for specific reactions. Here we show that when ultrathin Pt shells are deposited on palladium-based nanocubes, expansion and shrinkage of the nanocubes through phosphorization and dephosphorization induces strain in the Pt(100) lattice that can be adjusted from −5.1 per cent to 5.9 per cent. We use this strain control to tune the electrocatalytic activity of the Pt shells over a wide range, finding that the strain–activity correlation for the methanol oxidation reaction and hydrogen evolution reaction follows an M-shaped curve and a volcano-shaped curve, respectively. We anticipate that our approach can be used to screen out lattice strain that will optimize the performance of Pt catalysts—and potentially other metal catalysts—for a wide range of reactions. By depositing platinum shells on palladium-based nanocubes, the strain can be controlled by through phosphorization and dephosphorization, making it possible to tune the electrocatalytic activity of the platinum shells.