Anatomically-precise Cluster Catalysis

Recently studied topics

  • CO and cyclohexane oxidation with thiloate-protected Au25, Au38 and Au144 on CeO2, TiO2, SiO2 and Al2O3 (XANES, XPS, ATR, TEM)    ACS Catalysis, 10 (2020) 6144−6148 ; Catalysis Today 336 (2019) 174-185; Catalysis Communications 130 (2019) 105768 (1-7); ChemCatChem 10 (2018) 5372-5376
     
  • metal doping, ligand exchange synthesis of Au16(2-PET)14 from Au15(SG)13 and ligand exchange of immobilized Au11(PPh3)7Br3 nanoclusters on surfaces: Journal of Chemical Physics, 155 (2021)161102; Journal of Physical Chemistry C, 124 (2020) 23626–23636; Journal of Physical Chemistry C, 124 (2020) 22304–22313 ; Nanoscale, 12 (2020) 12809-12816

 

Research Directions

(previous FWF funded projects: DK+ Solids4Fun, ComCat)

Metal clusters are synthesized with precise atomic number (< 100 atoms, e.g. Au25, Au38 or Au144) and, when deposited on a support (CeO2, TiO2, SiO2, Al2O3), comprise truly monodisperse catalysts. The catalytic properties of clusters are often unique, due to their quantized electronic structure and specific atomic structure, and may differ strongly from those of larger nanoparticles (> 100 atoms). The possibility of creating atomically precise and even doped nanoclusters should finally lead to improved catalysts and a better understanding of nanocatalysis. Operando XAS studies are performed at various synchrotron sources.

Instrumentation

DRIFTS, ATR, UV-Vis, PL, SEC, reactors, GC, MS, Langmuir-Blodgett, STEM

Group members

Dr. Noelia Barrabes (Habilitation), opens an external URL in a new window
Vera Truttmann (PhD Student)

Former Group members

Clara Garcia-Yago (PhD Student)
Stephan Pollitt (PhD Student)
Irene López (guest PhD from ITQ Valencia, Spain)
Ibuki Kobayashi (Negishi Group, Tokyo University of Science, Japan)
Yukari Imai (Negishi Group, Tokyo University of Science, Japan)
Thanaree Phongamwong (guest PhD, Kasetsart University, Bangkok, Thailand)

Collaboration Partners

Prof. Yuichi Negishi, opens an external URL in a new window (Department of Applied Chemistry, Tokyo University of Science, Japan): Synthesis and synchrotron studies of bi-/tri-metallic cluster catalysts

Profs. Fernando Rey, A. Eduardo Palomares, opens an external URL in a new window (Instituto de Tecnología Química, Universitat Politècnica de València, Valencia, España), Au/Ag Cluster Catalysis

Prof. Thomas Bürgi, opens an external URL in a new window (Department of Physical Chemistry, University of Geneva, Switzerland): PM-IRAS and synchrotron studies of cluster catalysts

Publications

Selective Ligand Exchange Synthesis of Au16(2-PET)14 from Au15(SG)13
V. Truttmann, S. Pollitt, H. Drexler, S. P. Nandan, D. Eder, N. Barrabés, G. Rupprechter
Journal of Chemical Physics, 155 (2021)161102
DOI: https://doi.org/10.1063/5.0062534, opens an external URL in a new window

AgAu nanoclusters supported on zeolites: structural dynamics during CO oxidation
I. López-Hernández, V. Truttmann, C. Garcia, C. W. Lopes, C. Rameshan, M. Stöger-Pollach, N. Barrabés, G. Rupprechter, F. Rey, A. E. Palomares
Catalysis Today (2021) in press
DOI: https://doi.org/10.1016/j.cattod.2021.04.016, opens an external URL in a new window      

Dynamics of Pd dopant atoms inside Au nanoclusters during catalytic CO oxidation
C. Garcia, V. Truttmann, I. Lopez, T. Haunold, C. Marini, C. Rameshan, E. Pittenauer, P. Kregsamer, Klaus Dobrezberger, M. Stöger-Pollach, N. Barrabés, G. Rupprechter
Journal of Physical Chemistry C, 124 (2020) 23626–23636
DOI: https://doi.org/10.1021/acs.jpcc.0c05735, opens an external URL in a new window    

Determining and controlling Cu-substitution sites in thiolate-protected gold-based 25-atom alloy nanoclusters
S. Hossain, D. Suzuki, T. Iwasa, R. Kaneko, T. Suzuki, S. Miyajima, Y. Iwamatsu, S. Pollitt, T. Kawawaki, N. Barrabés, G. Rupprechter, Y. Negishi
Journal of Physical Chemistry C, 124 (2020) 22304–22313
DOI: doi.org/10.1021/acs.jpcc.0c06858, opens an external URL in a new window;

The dynamic structure of Au38(SR)24 nanoclusters supported on CeO2 upon pretreatment and CO oxidation
S. Pollitt, V. Truttmann, T. Haunold, C. Garcia, W. Olszewski, J. Llorca, N. Barrabés, G. Rupprechter
ACS Catalysis, 10 (2020) 6144−6148
DOI: https://dx.doi.org/10.1021/acscatal.0c01621, opens an external URL in a new window 

Ligand engineering of immobilized nanoclusters on surfaces: Ligand exchange reactions with supported Au11(PPh3)7Br3
V. Truttmann, C. Herzig, I. Illes, A. Limbeck, E. Pittenauer, M. Stöger-Pollach, G. Allmaier, T. Bürgi, N. Barrabés, G. Rupprechter
Nanoscale, 12 (2020) 12809-12816
DOI: https://doi.org/10.1039/c9nr10353h, opens an external URL in a new window    

Evaluation of the silver species nature in Ag-ITQ2 zeolites by the CO oxidation reaction
I. López-Hernández, C. García, V. Truttmann, S. Pollitt, N. Barrabés, G. Rupprechter, F. Rey, A. E. Palomares
Catalysis Today, 345, opens an external URL in a new window (2020) 22-26
DOI: https://doi.org/10.1016/j.cattod.2019.12.001, opens an external URL in a new window

Ligand and support effects on the reactivity and stability of Au38(SR)24 catalysts in oxidation reactions
B. Zhang, C. García, A. Sels, G. Salassa, C. Rameshan, J. Llorca, K. Hradil, G. Rupprechter, N. Barrabés and T. Bürgi
Catalysis Communications 130 (2019) 105768 (1-7)
DOI: 10.1016/j.catcom.2019.105768, opens an external URL in a new window

Support effect on the reactivity and stability of Au25(SR)18 and Au144(SR)60 nanoclusters in liquid phase cyclohexane oxidation
C. García, S. Pollitt, M. van der Linden, V. Truttmann, M. Stöger-Pollach, N. Barrabés, G. Rupprechter
Catalysis Today 336 (2019) 174-185
DOI: https://doi.org/10.1016/j.cattod.2018.12.013 , opens an external URL in a new window

Ligand Engineering with Immobilized Nanoclusters on Surfaces: Ligand Exchange Reactions with Supported Au11(PPh3)7Br3
V. Truttmann, I. Illes, A. Limbeck, E. Pittenauer, M. Stöger-Pollach, G. Allmaier, T. Bürgi, N. Barrabés, G. Rupprechter
ACS Nano, submitted

Ligand migration from cluster to support: A crucial factor for catalysis by thiolate-protected gold clusters
B. Zhang, A. Sels, G. Salassa, S. Pollitt, V. Truttmann, C. Rameshan, J. Llorca, W. Olszewski, G. Rupprechter, T. Bürgi, N. Barrabés
ChemCatChem 10 (2018) 5372-5376
DOI: https://doi.org/10.1002/cctc.201801474, opens an external URL in a new window (Hybrid OA)
Cover, Cover Profile and Selected as Highly Important Paper: chemistry-europe.onlinelibrary.wiley.com/toc/18673899/2018/10/23, opens an external URL in a new window

On the mechanism of rapid metal exchange between thiolate-protected gold and gold/silver clusters: a time-resolved in situ XAFS study
B. Zhang, O. Safonova, S. Pollitt, G. Salassa, R. Kazan, Y. Wang, G. Rupprechter, N. Barrabés-Rabanal, T. Bürgi
Physical Chemistry Chemical Physics 20 (2018) 5312-5318
DOI: https://doi.org/10.1039/c7cp08272j, opens an external URL in a new window

Synthesis and Properties of monolayer protected Cox(SC2H4Ph)m nanoclusters
S. Pollitt, E. Pittenauer, C. Rameshan, T. Schachinger, O. Safonova, V. Truttmann, A. Bera, G. Allmaier, N. Barrabés, G. Rupprechter
Journal of Physical Chemistry C 121 (2017) 10948-10956
DOI: https://doi.org/10.1021/acs.jpcc.6b12076, opens an external URL in a new window (Green OA)

Structural investigation of ligand exchange reaction with rigid dithiol on doped (Pt, Pd) Au25 clusters
A. Sels, G. Salassa, S. Pollit, C. Guglieri, G. Rupprechter, N. Barrabés, T. Bürgi
Journal of Physical Chemistry C 121 (2017) 10919-10926
DOI: https://doi.org/10.1021/acs.jpcc.6b12066, opens an external URL in a new window