Atomically dispersed Ir catalysts exhibit support-dependent water oxidation kinetics during photocatalysis.

Heterogeneous water oxidation catalysis is central to the development of renewable energy technologies. Recent research has suggested that the reaction mechanisms are sensitive to the hole density at the active sites. However, these previous results were obtained on catalysts of different materials featuring distinct active sites, making it difficult to discriminate between competing explanations. Here, a comparison study based on heterogenized dinuclear Ir catalysts (Ir-DHC), which feature the same type of active site on different supports, is reported. The prototypical reaction was water oxidation triggered by pulsed irradiation of suspensions containing a light sensitizer, Ru(bpy) 3 2+ , and a sacrificial electron scavenger, S 2 O 8 2- . It was found that at relatively low temperatures (288-298 K), the water oxidation activities of Ir-DHC on indium tin oxide (ITO) and CeO 2 supports were comparable within the studied range of fluences (62-151 mW cm -2 ). By contrast, at higher temperatures (310-323 K), Ir-DHC on ITO exhibited a ca. 100% higher water oxidation activity than on CeO 2 . The divergent activities were attributed to the distinct abilities of the supporting substrates in redistributing holes. The differences were only apparent at relatively high temperatures when hole redistribution to the active site became a limiting factor. These findings highlight the critical role of the supporting substrate in determining the turnover at active sites of heterogeneous catalysts.