Strain engineering of metal-based nanomaterials for energy electrocatalysis.

The strain effect, along with the ligand effect and synergistic effect, contributes primarily to the optimization of electrocatalytic activity and stability. The strain effect leads to a shift in the d-band center and alters binding energies toward adsorbates. Under electrocatalytic circumstances, the strain effect and ligand effect by and large function in combination; however, the decay and vanishing of the ligand effect precede the strain effect as the thickness of the shell in the core/shell structure or metallic overlayers on substrates increases. The strain effect on electrocatalytic activity can be well engineered by tuning the thickness of shells or atomic composition. Microstrain, or localized lattice strain, is another type of strain associated with structural defects such as grain boundaries and multi-twinning. In this review, we discuss the origin of the strain effect and how it affects electrocatalytic activity based on the d-band model. We present the structural characterization and quantitative determination of strain. Metal-based nanocrystals are basically grouped into two types of structures to which the strain engineering applies, i.e. lattice strain-associated structures (which include the general core/shell structure and solid solution alloy) and multiple defects-induced structures. Then analysis is performed on the correlation of strain and ligand effects and on the tuning strategies of the strain effect for electrocatalysis. After that, we use representative examples to demonstrate how strain engineering assists in typical electrocatalytic reactions on anodes and cathodes. Finally, we summarize and propose potential research areas in terms of enhancing electrocatalytic activities by strain engineering in the future.