Tailoring of Active Sites from Single to Dual Atom Sites for Highly Efficient Electrocatalysis.

Single atom catalysts (SACs) have been attracting extensive attention in electrocatalysis because of their unusual structure and extreme atom utilization, but the low metal loading and unified single site induced scaling relations may limit their activity and practical application. Tailoring of active sites at the atomic level is a sensible approach to break the existing limits in SACs. In this review, SACs were first discussed regarding carbon or non-carbon supports. Then, five tailoring strategies were elaborated toward improving the electrocatalytic activity of SACs, namely strain engineering, spin-state tuning engineering, axial functionalization engineering, ligand engineering, and porosity engineering, so as to optimize the electronic state of active sites, tune d orbitals of transition metals, adjust adsorption strength of intermediates, enhance electron transfer, and elevate mass transport efficiency. Afterward, from the angle of inducing electron redistribution and optimizing the adsorption nature of active centers, the synergistic effect from adjacent atoms and recent advances in tailoring strategies on active sites with binuclear configuration which include simple, homonuclear, and heteronuclear dual atom catalysts (DACs) were summarized. Finally, a summary and some perspectives for achieving efficient and sustainable electrocatalysis were presented based on tailoring strategies, design of active sites, and in situ characterization.