The disproportionation of H₂O₂ to H₂O and molecular O₂ catalyzed by platinum nanocatalysts is technologically very important in several energy conversion technologies, such as steam propellant thrust applications and hydrogen fuel cells. However, the mechanism of H₂O₂ decomposition on platinum has been unresolved for more than 100 years and the kinetics of this reaction were poorly understood. Our goal was to quantify the effect of reaction conditions and catalyst properties on the decomposition of H₂O₂ by platinum nanocatalysts and determine the mechanism and rate-limiting step of the reaction. To this end, we have characterized two commercial platinum nanocatalysts, known as platinum black and platinum nanopowder, and studied the effect of different reaction conditions on their rates of H₂O₂ decomposition. These samples have different particle size and surface chemisorbed oxygen abundance, which were varied further by pretreating both samples at variable conditions. The rate of H₂O₂ decomposition was studied systematically as a function of H₂O₂ concentration, pH, temperature, particle size and surface chemisorbed oxygen abundance.

The mechanism of H₂O₂ decomposition on platinum proceeds via two cyclic oxidation-reduction steps. Step 1 is the rate limiting step of the reaction. Step 1: Pt + H₂O₂ → H₂O + Pt(O). Step 2: Pt(O) + H₂O₂ → Pt + O₂ + H₂O. Overall: 2 H₂O₂ → O₂ + 2 H₂O. The decomposition of H₂O₂ on platinum follows 1st order kinetics in terms of H₂O₂ concentration. The effect of pH is small, yet statistically significant. The rate constant of step 2 is 13 times higher than that of step 1. Incorporation of chemisorbed oxygen at the nanocatalyst surface resulted in higher initial rate of H₂O₂ decomposition because more sites initiate their cyclic process in the faster step of the reaction. Particle size does not affect the kinetics of the reaction. This new molecular-scale understanding of the decomposition of H₂O₂ by platinum is expected to help advance many energy technologies that depend on the rate of H₂O₂ decomposition on nanocatalysts of platinum and other metals.