Metal hybridization in dilute-alloy catalysts promotes sintering resistance by decreasing surface mobility

Nature Materials (2026)Cite this article Dilute-metal-alloy nanoparticles exhibit enhanced catalytic performance compared with monometallic nanoparticles for many reactions. Anecdotal reports indicate that very dilute alloying can also slow the sintering rates of supported nanoparticles, although this has not been rigorously assessed and cannot be explained using bulk descriptors such as metal melting temperature. Here we utilize methanol synthesis reactivity, microscopy and in situ spectroscopy measurements to demonstrate that 1 atom% Pt addition to ~1–2-nm-diameter Cu (Pt1Cu100) nanoparticles supported on SiO2 dramatically decreases their sintering rates. Minimal sintering of Pt1Cu100 nanoparticles is observed during aging in H2 up to 700 °C versus 500 °C for Cu nanoparticles. Scanning tunnelling microscopy reveals that the addition of 0.01 monolayer of Pt to a Cu(110) surface decreases the detachment rate of undercoordinated atoms, demonstrating that dilute dopants can locally decrease the rate of the first step in nanoparticle sintering. Density functional theory calculations quantify the stabilization and predict other sinter-resistant dilute alloys. 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S.S. and B.W. appreciate financial support from the US Department of Energy, Office of Basic Energy Sciences, Catalysis Science program, under contract number DE-SC0018284. J.F. would like to acknowledge support from the National Science Foundation Graduate Research Fellowship Program (NSF GRFP) under grant number 1650114 and the US Department of Energy, Office of Science, Office of Workforce Development for Teachers and Scientists, Office of Science Graduate Student Research (SCGSR), program. The SCGSR program is administered by the Oak Ridge Institute for Science and Education for the Department of Energy under contract number DE-SC0014664. The use of the Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, is supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, under contract number DE-AC02-76SF00515. A.S.H. and S.R.B. would like to acknowledge Co-ACCESS, part of the SUNCAT Center for Interface Science and Catalysis, which is supported by the US Department of Energy, Office of Basic Energy Sciences, Chemical Sciences, Geosciences and Biosciences Division. Use was made of computational facilities purchased with funds from the National Science Foundation (CNS-1725797) and administered by the Center for Scientific Computing (CSC). Use of the CSC along with the ICP, transmission electron microscopy and STEM equipment in the UCSB MRL Shared Experimental Facilities is acknowledged, which are supported by the MRSEC Program of the National Science Foundation under award number DMR 2308708. This work also used Bridges-2 at Pittsburgh Supercomputing Center through allocation CHM230006 from the Advanced Cyberinfrastructure Coordination Ecosystem: Services and Support (ACCESS) program, which is supported by National Science Foundation grant numbers 2138259, 2138286, 2138307, 2137603 and 2138296, and supercomputer resources of the National Energy Research Scientific Computing Center (NERSC), a US Department of Energy, Office of Science User Facility. We thank G. Giannakakis and P. Deshlahra for discussions and G.G’s. assistance in the early stages of the project. A. Genc is acknowledged for assistance with the electron microscopy measurements and the development of particle size analysis methods.These authors contributed equally: Jordan Finzel, Audrey Dannar.Department of Chemical Engineering, University of California, Santa Barbara, Santa Barbara, CA, USAJordan Finzel & Phillip ChristopherDepartment of Chemistry, Tufts University, Medford, MA, USAAudrey Dannar & E. Charles H. SykesSchool of Sustainable Chemical, Biological and Materials Engineering, University of Oklahoma, Norman, OK, USAShoutian Sun & Bin WangStanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, Menlo Park, CA, USAAdam S. Hoffman & Simon R. BareSUNCAT Center for Sustainable Catalysis, SLAC National Accelerator Laboratory, Menlo Park, CA, USAAdam S. Hoffman & Simon R. BareDepartment of Chemical and Biological Engineering, Tufts University, Medford, MA, USAYogita Soni & E. Charles H. SykesSearch author on:PubMed Google ScholarSearch author on:PubMed Google ScholarSearch author on:PubMed Google ScholarSearch author on:PubMed Google ScholarSearch author on:PubMed Google ScholarSearch author on:PubMed Google ScholarSearch author on:PubMed Google ScholarSearch author on:PubMed Google ScholarSearch author on:PubMed Google ScholarJ.F. completed the reactivity experiments, XAS, microscopy, DFT calculations and subsequent analysis. A.S.H. facilitated the XAS measurements and analysis. J.F. and Y.S. synthesized the catalysts. A.D. completed all the surface science experiments and analysis. S.S. completed the molecular dynamics simulations and analysis. J.F. and A.D. wrote the initial draft. B.W., S.R.B., E.C.H.S. and P.C. were responsible for supervision, analysis, editing and funding acquisition. All authors discussed the results and commented on the manuscript.Correspondence to E. Charles H. Sykes or Phillip Christopher.The authors declare no competing interests.Nature Materials thanks Stefano Agnoli, Xin Zhang and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.Supplementary Sections 1–9, Figs. 1–17 and Tables 1–5.Vienna ab initio simulation package CONTCAR files of all structures discussed in the Article and Supplementary Information.Methanol synthesis production rates for Cu/SiO2 and Pt1Cu100/SiO2 catalysts following rapid thermal aging. Particle size distributions of fresh and spent catalyst samples.Programmed rapid thermal aging procedure, raw R-space EXAFS data for Cu/SiO2 and Pt1Cu100/SiO2 catalysts following rapid thermal aging and particle size estimates derived from EXAFS Cu–Cu first-shell fitting for Cu/SiO2 and Pt1Cu100/SiO2 catalysts following rapid thermal aging.Arrhenius plot data for the step-edge mobility of Cu(100) single crystal.Calculated step stabilization energies for Cu(211) surface with dopants and parity plot data for DFT step stabilization energy versus predicted step stabilization energy based on linear regression model for Cu, Ag and Au(211) hosts.Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.Reprints and permissionsFinzel, J., Dannar, A., Sun, S. et al. Metal hybridization in dilute-alloy catalysts promotes sintering resistance by decreasing surface mobility. Nat. Mater. (2026). https://doi.org/10.1038/s41563-026-02489-7Download citationReceived: 03 April 2024Accepted: 12 January 2026Published: 02 March 2026Version of record: 02 March 2026DOI: https://doi.org/10.1038/s41563-026-02489-7Anyone you share the following link with will be able to read this content:Sorry, a shareable link is not currently available for this article. Provided by the Springer Nature SharedIt content-sharing initiative