First-principles design of a single-atom–alloy propane dehydrogenation catalyst

• Published in: Science (American Association for the Advancement of Science) 2021-06, Vol.372 (6549), p.1444-1447
• Main Authors: Hannagan, Ryan T., Giannakakis, Georgios, Réocreux, Romain, Schumann, Julia, Finzel, Jordan, Wang, Yicheng, Michaelides, Angelos, Deshlahra, Prashant, Christopher, Phillip, Flytzani-Stephanopoulos, Maria, Stamatakis, Michail, Sykes, E. Charles H.
• Format: Article
• Language: English
• Subjects: Alkanes; Carbon; Catalysts; Copper; Copper converters; Dehydrogenation; Design; Dispersion; First principles; High resistance; Hydrogen bonds; INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Joint ventures; Low temperature; Low temperature resistance; Metal oxides; Nanoparticles; Propane; Rhodium; Science Experiments; Selectivity; Single atom catalysts
• ISSN: 0036-8075; 1095-9203
• DOI: 10.1126/science.abg8389

Nanoparticles of rhodium dispersed on metal oxides are generally poor catalysts for alkane dehydrogenation because the reactants bind too strongly to the metal. Hannagan et al. performed first-principle calculations indicating that single rhodium atoms in a copper surface should be stable and selective for conversion of propane to propene and hydrogen. Model studies of single rhodium atoms embedded in a copper (111) surface revealed a very high selectivity to propene and high resistance to the formation of surface carbon that would deactivate the catalyst. Science , abg8389, this issue p. 1444 Single rhodium atoms on a copper surface enable facile carbon-hydrogen bond activation and coke-free propane dehydrogenation. The complexity of heterogeneous catalysts means that a priori design of new catalytic materials is difficult, but the well-defined nature of single-atom–alloy catalysts has made it feasible to perform unambiguous theoretical modeling and precise surface science experiments. Herein we report the theory-led discovery of a rhodium-copper (RhCu) single-atom–alloy catalyst for propane dehydrogenation to propene. Although Rh is not generally considered for alkane dehydrogenation, first-principles calculations revealed that Rh atoms disperse in Cu and exhibit low carbon-hydrogen bond activation barriers. Surface science experiments confirmed these predictions, and together these results informed the design of a highly active, selective, and coke-resistant RhCu nanoparticle catalyst that enables low-temperature nonoxidative propane dehydrogenation.