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Single-atom catalyst (SAC) attracts extensive interest in heterogeneous catalysis. Although single metal atoms (M1) can serve as the dominant active site, growing evidences reveal that the directly coordinated heteroatoms usually determine the geometric and electronic structure of single-atom center. However, the impact of the peripheral environment, not bonded to M1, is in its infancy while plays a significant role. In this review, we survey the recent progresses of optimizing SAC performance through modulation of the peripheral species, either by influencing the main M1 center or serving as additional active site. Firstly, we introduce the basic principles of single-atom catalysis and the role of the peripheral environment in modifying catalytic behaviors. It is proposed that the single-atom site constitutes an active domain with the microenvironment, and the regulation of peripheral species within this active domain can effectively improve the catalytic performance. Subsequently, the design strategies and characterizations of peripheral environment are summarized. The peripheral effects on thermal, electro-, photo-catalysis and the underlying reaction mechanisms are then elucidated. Finally, the challenges and future prospects regarding the involvement of peripheral species in SAC are put forward. This review underscores the significance of the peripheral environment in SAC, which can provide important implications for the enhancement of catalysis through peripheral dopant engineering.
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COORDINATION CHEMISTRY REVIEWS
ISSN: 0010-8545
Year: 2025
Volume: 536
2 0 . 3 0 0
JCR@2023
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ESI Highly Cited Papers on the List: 0 Unfold All
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30 Days PV: 2
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