Abstract
Heterogeneous catalysts are widely used to promote chemical reactions. Although it is known that chemical reactions usually happen on catalyst surfaces, only specific surface sites have high catalytic activity. Thus, identifying active sites and maximizing their presence lies at the heart of catalysis research1,2,3,4, in which the classic model is to categorize active sites in terms of distinct surface motifs, such as terraces and steps1,5,6,7,8,9,10. However, such a simple categorization often leads to orders of magnitude errors in catalyst activity predictions and qualitative uncertainties of active sites7,8,11,12, thus limiting opportunities for catalyst design. Here, using stepped Pt(111) surfaces and the electrochemical oxygen reduction reaction (ORR) as examples, we demonstrate that the root cause of larger errors and uncertainties is a simplified categorization that overlooks atomic site-specific reactivity driven by surface stress release. Specifically, surface stress release at steps introduces inhomogeneous strain fields, with up to 5.5% compression, leading to distinct electronic structures and reactivity for terrace atoms with identical local coordination, and resulting in atomic site-specific enhancement of ORR activity. For the terrace atoms flanking both sides of the step edge, the enhancement is up to 50 times higher than that of the atoms in the middle of the terrace, which permits control of ORR reactivity by either varying terrace widths or controlling external stress. Thus, the discovery of the above synergy provides a new perspective for both fundamental understanding of catalytically active atomic sites and design principles of heterogeneous catalysts.
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Acknowledgements
Work at Purdue was supported through the US Department of Energy, Office of Science, Office of Basic Energy Sciences, Chemical, Biological, and Geosciences Division under DE-SC0010379. Z.Z. acknowledges support from an ECS Toyota Young Investigator Fellowship. J.G. acknowledges the computing resources provided by the National Energy Research Scientific Computing Center (NERSC). G.L., Z.Z. and J.G. acknowledge the computing resources provided by Purdue Rosen Center for Advanced Computing (RCAC). H.D. acknowledges the computing resources provided the National Supercomputing Center in Changsha. I.T.M. acknowledges support from the European Union’s Horizon 2020 Research and Innovation Framework Programme under the Marie Skłodowska-Curie grant agreement no. 707404 and start-up support from Clarkson University. M.L. acknowledges support from the European Union’s Horizon 2020 Research and Innovation Framework Programme under the Marie Skłodowska-Curie Actions Individual Fellowship (no. 897818)
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Z.Z. and G.L. conceived the project and performed the computation. A.J.S., K.O., X.C., M.L. and I.T.M. performed the experiments. H.D., M.T.M.K., J.G. and Z.Z. supervised the project and provided the funding. Z.Z. wrote the manuscript. Z.Z., G.L., A.J.S., M.T.M.K. and J.G. revised the manuscript, and all authors contributed to the discussion and revision of the manuscript.
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Extended data figures and tables
Extended Data Fig. 1 Surface stress σxx and σyy of stepped Pt(111) surfaces with respect to the terrace width.
Surface stress of Pt[n(111)-(110)] (a) and Pt[n(111)-(100)] (b) with respect to the terrace width n, and the inverse of terrace width, i.e. 1/n, which corresponds to the step density. As a comparison surface stress of Pt(111) is also given. nis the number of atomic rows on the (111) terrace. The presence of steps leads surface stress release in the direction perpendicular to the step edges, which is in the y direction (σyy) for Pt[n(111)-(110)] and x direction (σxx) for Pt[n(111)-(100)], respectively. It is worth noting that surface stress release is proportional to the inverse of terrace width, i.e., step density.
Extended Data Fig. 2 Atomic site-resolved surface strain of Pt(221) surface with a terrace width of 0.8 nm (n = 3).
Surface sites correspond to atoms in the top layer of the side view (upper panel). τ is intrinsic tensile surface stress, which is spontaneously released by introducing step to break symmetry, accompanied by the simultaneous generation of compressive surface strain. The terrace width is indicated by double arrow lines.
Extended Data Fig. 3 Atomic site-resolved strain, electronic structure and surface reactivity as a function of the terrace width (n) and the inverse of terrace width (1/n), i.e., the step density.
Shown are strain (a), d-band centre shift dεd (b) and OH adsorption energy shift dEad(OH) (c) values, all evaluated with respect to that of Pt(111) for step edge atoms, atoms in the middle of terrace, and terrace atoms located immediately above (upper) and below (lower) the step edge, as indicated in the side view (upper panel).
Extended Data Fig. 4 Atomic site-resolved electronic structure, surface reactivity and ORR activity of Pt(221) with respect to that of Pt(111) surface.
Shown are d-band centre shift dεd (a), OH adsorption energy shift dEad(OH) (b), and ORR improvement factor (c). Surface sites correspond to atoms in the top layer of the side view (upper panel). The terrace width is indicated by double arrow lines.
Extended Data Fig. 5 The relationship between the predicted ORR activity enhancement and the terrace width n of Pt[n(111)-(110)].
(a) the enhancement factors (with respect to Pt(111)) versus the inverse of the terrace width, i.e. 1/n, which corresponds to the step density, (b) the enhancement factors versus the terrace width n. It is worth noting that the main reason of showing enhancement factors versus step density is to compare with previous experiments9,24,25.
Extended Data Fig. 6 Stress release and average surface strain of Pt[n(111)-(100)].
(a) Stress release and average strain as a function of the terrace width n and the inverse of terrace with, i.e., 1/n, which corresponds to the step density, (b) illustrating the linear relationship between the two parameters.
Extended Data Fig. 7 Atomic site-resolved surface strain of Pt[n(111)-(100)] surfaces.
(a) Pt(322) surface and (b) Pt(544) surface with a terrace width of 1.1 nm (n = 5) and 2.1 nm (n = 9), respectively. The terrace width is indicated by double arrow lines. Surface sites correspond to atoms in the top layer of the side views (upper panels). τ is intrinsic tensile surface stress, which is spontaneously released by introducing step to break symmetry, accompanied by the simultaneous generation of compressive surface strain.
Extended Data Fig. 8 The relationship between the predicted ORR activity enhancement and the terrace width n of Pt[n(111)-(100)].
(a) The enhancement factors (with respect to Pt(111)) versus the inverse of the terrace width, i.e., 1/n, which corresponds to the step density, (b) the enhancement factors versus the terrace width n. It is worth noting that the main reason of showing enhancement factors versus step density is to compare with previous experiments9,24.
Extended Data Fig. 9 Experimentally measured ORR limiting current as a function of predicted ORR limiting current.
Experimental data for ORR on Pt(111) are taken from ref. 53; and for ORR on Pt(111) and Pt(554) from this work. ORR reaction conditions: O2-saturated 0.1 M HClO4 at 23 °C at 0.5 VRHE with a scan rate of 10 mV s−1 and varying rotation rates.
Extended Data Fig. 10 ORR polarization curves for Pt(554) surface with 0 ML to 0.9 ML Au deposited at the step edge.
(a) The full polarization curves in the potential region from 0.05 to 1 VRHE. (b) The polarization curves in the potential region from 0.85 to 0.95 VRHE.
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Liu, G., Shih, A.J., Deng, H. et al. Site-specific reactivity of stepped Pt surfaces driven by stress release. Nature 626, 1005–1010 (2024). https://doi.org/10.1038/s41586-024-07090-z
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DOI: https://doi.org/10.1038/s41586-024-07090-z
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