Rationalization of Nonlinear Adsorption Energy-Strain Relations and Brønsted-Evans-Polanyi and Transition State Scaling Relationships under Strain.

Abstract

Scaling relations play a vital role in high-throughput screening of catalytic materials, and more and more attention is being paid to strain-based regulation of catalytic performance. Here we investigated the variation of several energetics, including adsorption energies in the initial state, transition state, and final state, reaction energies, and energy barriers with strain, by studying CO, BH, NH, CH, and NO adsorption and dissociation on M(111) (M = Cu, Ag, Ni, Pd, or Pt) surfaces. We show that energy barriers, reaction energies, and adsorption energies can vary either linearly or nonlinearly (quadratically) with strain. Systems with stronger adsorbate-substrate interaction and weaker atom-atom interaction in substrates are more likely to exhibit nonlinear relations. The well-known Brønsted-Evans-Polanyi relationships and transition state scaling relationships under strain were also examined, and both of them can be nonlinear under strain, in principle. The observed nonlinear relationships were satisfactorily rationalized with the equations derived from Mechanics of Solids.