LAUSR

Nearly theoretical 100% atomic utilization (supposing each atom could serve as independent sites to play a role in catalyz) of single‐atom catalysts (SACs) makes it highly promising for various applications. However, for most SACs, single‐atom sites are trapped in a solid carbon matrix, which makes the inner parts hardly available for reaction. Herein, a hollow N‐doped carbon confined single‐atom Rh (Rh‐SACs/HNCR) is developed via a coordination‐template method. Both aberration‐corrected scanning transmission electron microscopy and energy dispersive X‐ray spectroscopy mapping confirm the uniform distribution of Rh single atoms. Owning to the unique hollow structure and effective carbon confinement, excessive conversion from pyridinic/pyrrolic N to graphic N is hindered. As a proof of concept, Rh‐SACs/HNCR exhibits superior activity, stability, selectivity, and anti‐poisoning capability in formic acid oxidation reaction compared with the counterpart Rh/C, Pd/C, and Pt/C catalysts. This work provides a powerful strategy for synthesizing hollow carbon confined single‐atom catalysts apply in various energy‐related systems.