Volcano Plots and Rate Theory Models

A key advance that greatly accelerated progress in computational catalyst screening was the development of computational analogues of the volcano plots that, as mentioned earlier, had been known for some time in the experimental catalysis community. Both computational and experimental volcanos typically plot the rate of a catalytic 

The successful development of volcano plots is intimately tied both to the identification of appropriate descriptors and to the relation of these descriptors to the catalytic properties of interest. Many approaches, of varying levels of complexity, are available to identify suitable descriptors and to incorporate these into volcano plots. Some classes of volcanoes have been developed in an empirical or semiempirical manner, by essentially correlating experimental reaction rates with experimentally or computationally determined values of catalytic parameters. An early example of a purely empirical volcano, in the field of electrocatalysis, was 

FIGURE 7.1 Theoretically derived volcano for the electrocatalytic HER. The maximum of the volcano represents the optimal compromise between the rate of hydrogen discharge onto the surface and that of hydrogen removal. Experimental data points are indicated by solid or filled circles. Reprinted with permission fiom Ref. [40]. American Chemical Society. 

FIGURE 7.2 BEP relationships, and definition of energies, for specific locations on a molecular backbone applied to selective hydrogenation reactions on Ptflll). Reprinted with permission from Ref. [56], John Wiley Sons. 

FIGURE 7.4 Potential energy diagrams of carbon hydrogenation to CH on surface defects of Re, Fe, Ru, Co, and Rh. Reprinted with permission from Ref. [64]. American Chemical Society. 

---