Strain effect on adsorption and reactions of AHx (A = C, N, O, x ≤ 3) on In2O3(110), TiO2(110), and ZrO2(101) surfaces

Abstract

More and more attention has been paid to strain-based regulation of catalytic activity. To guide regulation of catalytic performance via strain engineering, adsorption and reactions of AHx (A = C, N, O, x ≤ 3) were investigated on uniformly strained In2O3 (110), rutile TiO2 (110), and tetragonal ZrO2 (101) from −2% to 4%. The results show that adsorption energies vary linearly with strain; expansive strain enhances the adsorption of most adsorbates. Unlike the adsorbate scaling relations that are central atom dependent, the adsorbate scaling relations on strained surfaces are central atom independent. C–H/O–H bonds are elongated/shortened with expansive strain, and adsorption energies of CHx generally change more than those of OHx and NHx, which can be rationalized with effective medium theory and pertinent bond energies. Thermodynamically, In2O3(110)/ZrO2(101) is the most active/inactive. The estimated variation of rate constants at 300 K from 0% to 2% strain based on the Brønsted–Evans–Polanyi relationship demonstrates great strain regulation potential of catalytic performance on these oxide surfaces. Finally, it is demonstrated that strain tends to facilitate the reactions whose sum of the stoichiometric number is positive, which can be used as a rule to guide strain engineering for heterogeneous catalysis.