Single-atom catalysts (SACs) provide well-defined active sites with 100% atom utilization, and can be prepared using a wide range of support materials. Therefore, they are attracting global attention, especially in the fields of energy conversion and storage. To date, research has focused on transition-metal and precious-metal-based SACs. More recently, rare-earth (RE)-based SACs have emerged as a new frontier in photo/electrocatalysis owing to their unique electronic structure arising from the spin-orbit coupling of the 4f and valence orbitals, unsaturated coordination environment, and unique behavior as charge-transport bridges. However, a systematic review on the role of the RE active sites, catalytic mechanisms, and synthetic methods for RE SACs is lacking. Therefore, in this review, the latest developments in RE SACs having applications in photo/electrocatalysis are summarized and discussed. First, the theoretical advantages of RE SACs for photo/electrocatalysis are briefly introduced, focusing on the roles of the 4f orbitals and coupled energy levels. In addition, the most recent research progress on RE SACs is summarized for several important photo/electrocatalytic reactions and the corresponding catalytic mechanisms are discussed. Further, the synthetic strategies for the production of RE SACs are reported. Finally, challenges for the development of RE SACs are highlighted, along with future research directions and perspectives.
Keywords: electrocatalyses; electronic modulations; photocatalyses; rare earth elements; single-atom catalysts.
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