Carbon Nanospheres Loaded with Ir Single Atoms: Enhancing the Activity toward Formic Acid Oxidation by Increasing the Porosity

Theoretically, single‐atom catalysts (SACs) offer 100 % atom utilization, making them strong candidates to replace expensive nanoparticles for catalysis. However, the structural supports used to anchor the SACs dramatically reduce the utilization efficiency of atoms (i. e., the percent of atoms actually accessible by reactants) by either encapsulating the SACs completely or creating severe diffusion limitation. Either of which leads to an overall low atom utilization and thus poor electrocatalytic activity similar to that of nanoparticles. In addressing this issue, we systematically investigated how the porous structure of carbon nanospheres affects the activity of Ir‐SACs toward formic acid oxidation (FAO). Specifically, we utilized a kinetically‐controlled growth strategy to produce uniform carbon nanospheres featuring yolk‐shell, mesoporous, and hollow structures with Ir‐SACs loaded throughout the structure. At a high specific surface area of 441 m2 g−1 and exposed metal content of 1.82 wt %, the Ir‐SACs based on mesoporous carbon nanospheres showed a remarkable FAO peak current density of 30.6 mA cm−2, which was 283 and 46 times greater when benchmarked against the catalysts based on solid carbon nanospheres and 20 wt % Ir/C, respectively. Iridium single‐atoms loaded on carbon nanospheres with varying architectures: solid, yolk‐shell, hollow, and mesoporous carbon nanospheres loaded with Ir SACs have been prepared using a simple, one‐pot synthesis. Benefiting from the improved active site exposure and mass diffusion, these catalysts exhibit high activities toward formic acid oxidation.