Pd/Cu Single Atom Alloys for Selective Alcohol Dehydrogenation: From Single Crystalline to Nanostructured Model Catalysts

Abstract Heterogeneous catalysts based on Single Atom Alloys (SAA) play a significant role in numerous technical processes. The fundamental working principles of these systems, however, remain poorly understood, especially the aspects related to the nanoscopic nature of bimetallic particles and the associated structure‐reactivity relationships. In this study, we developed for the first time well‐defined SAA catalysts consisting of Pd atomically dispersed in Cu nanoparticles prepared under ultra‐high vacuum (UHV) conditions on model Al 2 O 3 /NiAl(110) support. Employing a unique combination of surface sensitive techniques – scanning tunneling microscopy (STM), infrared reflection absorption spectroscopy (IRAS), molecular beams – and density functional theory (DFT) calculations, we performed detailed structural characterization of these systems at the microscopic level. We demonstrate that Pd disperses atomically in Cu nanoparticles and becomes partly negatively charged. Importantly, these Pd/Cu nanostructured systems show an outstanding catalytic performance in selective dehydrogenation of butanol and exhibit 100% selectivity toward butanal over a broad range of Pd loadings – the property that cannot be reproduced employing simplified single crystalline Pd/Cu(111) counterparts. The developed approach for preparation and characterization of these nanostructured SAA‐catalysts lays a foundation for further fundamental‐level catalytic studies on this important class of materials and their rational design for practical applications.