How strain can break the scaling relations of catalysis

Abstract

Heterogeneous catalysts control the rates of chemical reactions by changing the energy levels of bound intermediates relative to one another. However, the design flexibility in catalysis is limited by scaling relations: when a catalyst binds one adsorbate more strongly, it tends to bind similar adsorbates more strongly as well. Here we show how strain can break this constraint by employing a mechanics-based eigenstress model to rationalize the effect of strain on adsorbate–catalyst bonding. This model suggests that the sign of the binding-energy response to strain depends on the coupling of the adsorbate-induced eigenstress with the applied strain; thus, tensile strain can make binding either stronger or weaker, depending on the eigenstress characteristics of the adsorbate on the surface. We then suggest how these principles can be used in conjunction with anisotropic strain to engineer opposite responses of adjacent adsorbates to strain; such effects are expected to allow larger changes to reaction rates than predicted by scaling relations.

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Fig. 1: Illustration of adsorbate and transition-state scaling relations.
Fig. 2: Site dependency of the binding-energy response to strain.
Fig. 3: Determination of the sign of eigenstress.
Fig. 4: Strain-induced deviation from the adsorbate scaling relations.
Fig. 5: Uniaxial loading.
Fig. 6: Self-diffusion on a Pt(100) surface.
Fig. 7: Self-diffusion on a Pt(111) surface.
Fig. 8: N2 association over a Pt(100) surface.

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Acknowledgements

The authors are grateful to the Army Research Office (ARO) for funding under Award W911NF-11-1-0353. We benefited from the fruitful discussions with W. A. Curtin at École Polytechnique Fédérale de Lausanne, P. R. Guduru at Brown University, B. Hammer at Aarhus University and H. Ashouri-Choshali at Worcester Polytechnic Institute. High-performance computational work was carried out at Brown’s Center for Computation & Visualization (CCV).

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A.K. and A.A.P. collaboratively designed the research. A.K. and J.V. performed the calculations of self-diffusion on a Pt(100) surface. A.K. performed all other calculations of the paper. A.K. and A.A.P. collaboratively analysed the data, developed the eigenstress model, wrote the paper and prepared revisions. J.H. gave the idea of projecting the d-band along different directions.

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Correspondence to Andrew A. Peterson.

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Supplementary Notes 1–5; Supplementary Figures 1–15; Supplementary Tables 1 and 2; Supplementary References

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Khorshidi, A., Violet, J., Hashemi, J. et al. How strain can break the scaling relations of catalysis. Nat Catal 1, 263–268 (2018). https://doi.org/10.1038/s41929-018-0054-0

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