Research Directions

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

Rares Banu, opens an external URL in a new window
Sebastian Mößlacher, opens an external URL in a new window

Former Group members

Vera Truttmann (PhD Student)
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

Prof. Michael Stöger-Pollach, opens an external URL in a new window (USTEM, TU Wien, Austria), HRTEM, SEM, EBSD, EDX of cluster catalysts

Publications

Directing Intrinsic Chirality in Gold Nanoclusters: Preferential formation of stable enantiopure clusters in high yield and experimentally unveiling the “super” chirality of Au144
Vera Truttmann, Adea Loxha, Rareş Banu, Ernst Pittenauer, Sami Malola, María Francisca Matus, Yuchen Wang, Elizabeth A. Ploetz, Günther Rupprechter, Thomas Bürgi, Hannu Häkkinen, Christine Aikens, Noelia Barrabés
ACS Nano,17 (2023) 20376–20386
https://doi.org/10.1021/acsnano.3c06568, opens an external URL in a new window

Doped metal clusters as bimetallic AuCo nanocatalysts: insights into structural dynamics and correlation with catalytic activity by in situ spectroscopy
Noelia Barrabes, Jon Ostolaza, Sarah Reindl, Martin Mähr, Florian Schrenk, Hedda Drexler, Christoph Rameshan, Wojciech Olszewski, Günther Rupprechter
Faraday Discussions, 242 (2023) 94-105
https://doi.org/10.1039/D2FD00120A, opens an external URL in a new window                      (Hybrid OA)

Chlorophyll-modified Au₂₅(SR)₁₈-functionalized TiO₂ for photocatalytic degradation of rhodamine B
Thanaree Phongamwong, Noelia Barrabés, Waleeporn Donphai, Thongthai Witoon, Günther Rupprechter, Metta Chareonpanich
Applied Catalysis B : Environmental, 325 (2023) 122336
https://doi.org/10.1016/j.apcatb.2022.122336, opens an external URL in a new window      (Hybrid OA)

Gold nanoclusters supported on different materials as catalysts for the selective alkyne semihydrogenation
I. López-Hernández, V. Truttmann, N. Barrabés, G. Rupprechter, F. Rey, J. Mengual, A. E. Palomares
Catalysis Today, 394–396 (2022) 34-40
https://doi.org/10.1016/j.cattod.2022.02.014, opens an external URL in a new window

Ligand Effect on the CO Oxidation Activity of CeO₂ Supported Gold Nanocluster Catalysts
Vera Truttmann, Daiki Suzuki, Michael Stöger-Pollach, Hedda Drexler, Yuichi Negishi, Noelia Barrabés, and Günther Rupprechter
ChemCatChem, (2022) e202200322 (12 pages)
https://doi.org/10.1002/cctc.202200322, 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, 384–386 (2022) 166-176
https://doi.org/10.1016/j.cattod.2021.04.016, opens an external URL in a new window

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

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