On the shifting peak of volcano plots for oxygen reduction and evolution

A general but still unknown characteristic of active oxygen evolution electrocatalysts

“…Before continuing, we note that ample discussions on the use of 4.92 eV instead of the DFT-calculated values (which tend to underestimate the experimental value) are provided in other works, where the effects of this choice on free-energy diagrams and Sabatier-type activity plots are also illustrated. 24,25 In addition, Δ G OH , is defined with respect to water and proton–electron pairs as shown in eqn (1) and (5), while Δ G O and Δ G OOH are the free energies of reaction of eqn (9) and (10), respectively.H 2 O + * → *O + 2H + + 2e − 2H 2 O + * → *OOH + 3H + + 3e − …”

Automated versus Chemically Intuitive Deconvolution of Density Functional Theory (DFT)-Based Gas-Phase Errors in Nitrogen Compounds

“…In addition, gas-phase corrections have also been shown to improve the prediction of equilibrium and onset potentials for the electroreduction of CO 2 to CO, and brought DFT-calculated adsorption energies of CO on several metals closer to experimental values . Finally, the importance of gas-phase corrections has also been illustrated for free-energy diagrams and volcano plots for O 2 reduction and evolution , and H 2 O 2 production …”

“…potentials for the electroreduction of CO 2 to CO, 30 and brought DFT-calculated adsorption energies of CO on several metals closer to experimental values. 50 Finally, the importance of gasphase corrections has also been illustrated for free-energy diagrams and volcano plots for O 2 reduction and evolution 39,51 and H 2 O 2 production. 40 Furthermore, if a given compound X participates in a catalytic reaction but no experimental data are available for it, one can decompose it in its bonds and/or groups of atoms and anticipate the errors present in its DFT-calculated free energy of formation.…”

On the mechanistic complexity of oxygen evolution: potential-dependent switching of the mechanism at the volcano apex

“…[68][69][70] For the scaling relation between the *OH and *O adsorbates (cf. eqn (35)), a sensitivity analysis is provided in the ESI † (cf. Fig.…”

“…Volcano plots have been established as a powerful tool in electrocatalysis research to comprehend the trends of catalysts in a homologous series of materials, particularly if they factor overpotential and kinetic effects into the evaluation of binding energies. [32][33][34][35] For the OER, though, the common approach refers to the construction of volcano curves based on the mononuclear mechanism (cf. eqn (2)-( 5)) under equilibrium conditions (Z OER = 0 V), and the volcano analysis based on the descriptor Z TD indicates that either the formation of the *OOH or the *O adsorbate refers to the potential-dependent step (PDS) at the left and right volcano legs, respectively (cf.…”