Abstract
The design of catalysts with desired chemical and thermal properties is viewed as a grand challenge for scientists and engineers1. For operation at high temperatures, stability against structural transformations is a key requirement. Although doping has been found to impede degradation, the lack of atomistic understanding of the pertinent mechanism has hindered optimization. For example, porous γ-Al2O3, a widely used catalyst and catalytic support2,3,4,5,6, transforms to non-porous α-Al2O3 at ∼1,100 °C (refs 7–10). Doping with La raises the transformation temperature8,9,10,11 to ∼1,250 °C, but it has not been possible to establish if La atoms enter the bulk, adsorb on surfaces as single atoms or clusters, or form surface compounds10,11,12,13,14,15. Here, we use direct imaging by aberration-corrected Z-contrast scanning transmission electron microscopy coupled with extended X-ray absorption fine structure and first-principles calculations to demonstrate that, contrary to expectations, stabilization is achieved by isolated La atoms adsorbed on the surface. Strong binding and mutual repulsion of La atoms effectively pin the surface and inhibit both sintering and the transformation to α-Al2O3. The results provide the first guidelines for the choice of dopants to prevent thermal degradation of catalysts and other porous materials.
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Acknowledgements
We thank Valeria V. Vavilova and Yanzhao Cao for their help and John W. Novak, Jr for his support. Access to the Novosibirsk Synchrotron Facility (Russian Academy of Sciences) and to the Florida State University supercomputers (csit1 and csit2) are also gratefully acknowledged. This work was supported in part by National Science Foundation Grant DMR-0111841, Department of Energy Grant at Drexel University DE-FC02-01CH11085, by the William A. and Nancy F. McMinn Endowment at Vanderbilt University, by the Division of Materials Sciences, by Laboratory Directed R&D Program for the US Department of Energy, under contract DE-AC05-00OR22725 managed by UT-Battelle, and by an appointment to ORNL Postdoctoral Research Program administered jointly by ORNL and Oak Ridge Institute for Science and Education (ORISE).
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Wang, S., Borisevich, A., Rashkeev, S. et al. Dopants adsorbed as single atoms prevent degradation of catalysts. Nature Mater 3, 143–146 (2004). https://doi.org/10.1038/nmat1077
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DOI: https://doi.org/10.1038/nmat1077
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