Shift of the Optimum Binding Energy at Higher Rates of Catalysis.

The binding energy between the catalyst and the reactant is considered to be the primary descriptor of catalytic activity. Therefore, identifying the optimum binding energy that would yield maximum activity is fundamentally important for the development of efficient catalysts. Here, we show analytically how the binding energy that maximizes the activity at large reaction rates, i.e., the operating conditions of catalysis, may deviate from the traditional understanding obtained near equilibrium. This shift can be on the order of 0.5 eV, which is easily sufficient for the optimum material to change. This binding energy shift is consistent with experimental observations in the literature, suggesting that a reinvestigation of materials previously considered to be inactive may be necessary.