Revisiting Activity Tuning Using Lattice Strain: CO Decomposition in Terrace Ru(0001) and Stepped Ru(1015) Surfaces

To understand the influence of incongruent strain on heterogeneous catalysis, the effect of isotropic and anisotropic strains in the catalytic activity of terrace Ru(0001) and stepped Ru(1015) surfaces have been studied for the initial step of the Fischer–Tropsch (FT) reaction. Adsorption–strain relations have been investigated using the d-band model and the novel eigenstress model. The adsorption relation in the reactant state follows both models. The eigenstress model can predict similar qualitative changes in the adsorption energies without the need to calculate the d-band center of the slab. Activation energies also scale according to Brønsted–Evans–Polyani (BEP) relation. Some exemptions included new minimum energy pathways, which do not break the scaling relations but reinforce the mechanochemical effect of producing new chemical pathways with the strain. In addition, in the case of a compressed Ru(1015) surface, reactant adsorption energy does not scale with dissociation activation energy. This is explained by the heightened difference in the reactant interaction energy. These results offer a potential novel route to break the BEP relation in catalysis.