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

Fredersdorff, Philipp A. ; Smyczek, Jan ; Schröder, Carsten ; Fröhlich, Paul ; Kohlmorgen, Paul ; Appelfeller, Stephan LU ; Neyman, Konstantin and Schauermann, Swetlana (2026) In Angewandte Chemie - International Edition 65(5).
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 Al2O3/NiAl(110) support. Employing a unique combination of surface sensitive techniques – scanning tunneling microscopy (STM), infrared reflection absorption spectroscopy (IRAS), molecular beams... (More)

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 Al2O3/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.

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author
; ; ; ; ; ; and
organization
publishing date
type
Contribution to journal
publication status
published
subject
keywords
Materials gap, Model heterogeneous catalysis, Reaction mechanism in heterogeneous catalysis, Reversible hydrogen storage, Single atom alloy
in
Angewandte Chemie - International Edition
volume
65
issue
5
article number
e21885
publisher
John Wiley & Sons Inc.
external identifiers
  • scopus:105025209134
  • pmid:41413955
ISSN
1433-7851
DOI
10.1002/anie.202521885
language
English
LU publication?
yes
additional info
Publisher Copyright: © 2025 The Author(s). Angewandte Chemie International Edition published by Wiley-VCH GmbH.
id
dc5c3f2e-4483-4b06-98fe-b7bfbbe8f835
date added to LUP
2026-02-26 13:46:17
date last changed
2026-02-27 03:00:01
@article{dc5c3f2e-4483-4b06-98fe-b7bfbbe8f835,
  abstract     = {{<p>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<sub>2</sub>O<sub>3</sub>/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.</p>}},
  author       = {{Fredersdorff, Philipp A. and Smyczek, Jan and Schröder, Carsten and Fröhlich, Paul and Kohlmorgen, Paul and Appelfeller, Stephan and Neyman, Konstantin and Schauermann, Swetlana}},
  issn         = {{1433-7851}},
  keywords     = {{Materials gap; Model heterogeneous catalysis; Reaction mechanism in heterogeneous catalysis; Reversible hydrogen storage; Single atom alloy}},
  language     = {{eng}},
  month        = {{01}},
  number       = {{5}},
  publisher    = {{John Wiley & Sons Inc.}},
  series       = {{Angewandte Chemie - International Edition}},
  title        = {{Pd/Cu Single Atom Alloys for Selective Alcohol Dehydrogenation : From Single Crystalline to Nanostructured Model Catalysts}},
  url          = {{http://dx.doi.org/10.1002/anie.202521885}},
  doi          = {{10.1002/anie.202521885}},
  volume       = {{65}},
  year         = {{2026}},
}