The decomposition of HO to HO and O catalyzed by platinum nanocatalysts controls the energy yield of several energy conversion technologies, such as hydrogen fuel cells. However, the reaction mechanism and rate-limiting step of this reaction have been unsolved for more than 100 years. We determined both the reaction mechanism and rate-limiting step by studying the effect of different reaction conditions, nanoparticle size, and surface composition on the rates of HO decomposition by three platinum nanocatalysts with average particle sizes of 3, 11, and 22 nm. Rate models indicate that the reaction pathway of HO decomposition is similar for all three nanocatalysts. Larger particle size correlates with lower activation energy and enhanced catalytic activity, explained by a smaller work function for larger platinum particles, which favors chemisorption of oxygen onto platinum to form Pt(O). Our experiments also showed that incorporation of oxygen at the nanocatalyst surface results in a faster reaction rate because the rate-limiting step is skipped in the first cycle of reaction. Taken together, these results indicate that the reaction proceeds in two cyclic steps and that step 1 is the rate-limiting step. Step 1: Pt + H O → H O + Pt( O). Step 2: Pt( O) + H O → Pt + O + H O. Overall: 2 H O → O + 2 H O. Establishing relationships between the properties of commercial nanocatalysts and their catalytic activity, as we have done here for platinum in the decomposition of HO, opens the possibility of improving the performance of nanocatalysts used in applications. This study also demonstrates the advantage of combining detailed characterization and systematic reactivity experiments to understand property-behavior relationships.

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