Atomic-scale studies of catalysis
by spinel oxides

Subproject P04

The spinel class of metal oxides hosts diverse materials, some of which make excellent catalysts. Fe3O4 is already the industrial catalyst for the high-temperature water-gas shift reaction (CO+H2O -> H2+CO2), but research is needed to identify the optimal replacement for the toxic Cr promoter/stabilizer. Ternary MeFe2O4 compounds (Me=Fe, Ni, Co, Mn) are active and stable for the electrochemical oxygen evolution reaction (OER). However, the structure of the active catalyst and the reaction mechanisms are unknown. While these reactions appear different, both clearly benefit from a combination of multivalent cations in the surface layers.

In this project, we will seek to learn why, using a combination of atomic-scale imaging, a host of spectroscopies, and theory. We will dope the Fe3O4(001) surface with 3d transition metals and investigate how the adsorption energies, XPS binding energies, and IRAS frequencies of H2O, CO, CO2, O2, and H2 change with sample composition all the way from isolated dopants to ternary thin films. We will use the data obtained in tightly-controlled UHV experiments to:

i) Interpret the reactivity of our model catalysts under realistic HTWGS and OER conditions.

ii) Provide the benchmark data for experiments on nominally similar powder catalysts (P10 Föttinger).

iii) Support the development of theoretical modeling (P07 Franchini).

A joint postdoc (P04-P11) will facilitate the new collaboration with P11 Backus.

Gareth S. Parkinson
PI

Expertise

The group focuses on understanding mechanisms of catalytic reactions using a combination of experimental surface science and theoretical calculations. We have access to a total of seven ultrahigh-vacuum (UHV) chambers, which allows us to conduct the following experiments:
  • Scanning Tunneling Microscopy (STM) (in UHV 4K – 300 K, electrochemical STM)
  • Atomic Force Microscopy (AFM): UHV-based (q+ sensor) and in the ambient (cantilever-based)
  • Low-Energy Electron Diffraction (LEED)
  • Reflection High Energy Diffraction (RHEED)
  • X-ray Photoelectron Spectroscopy (XPS)
  • Ultraviolet Photoelectron Spectroscopy (UPS)
  • Auger Electron Spectroscopy (AES)
  • Low-energy He+ ion scattering (LEIS)
  • Thermal Programmed Desorption Spectroscopy (TPD)
Of particular use for TACO is our surface reactivity chamber, which is specifically designed to study single-crystal metal-oxide samples. Reactants are delivered to the sample by molecular beams, and products detected by a mass spectrometer. In addition to TPD, XPS, UPS, and LEIS, we will soon be able to perform infrared absorption spectroscopy (IRAS) experiments on these samples using an optimized beam geometry.

Team

Gareth S. Parkinson
PI

Jiří Pavelec
co-PI

Chunlei Wang
PostDoc

David Rath
PhD Student

Associates

Moritz Eder
PostDoc

Publications

Show all

43 entries « 2 of 5 »

2021

First-principles hydration free energies of oxygenated species at water–platinum interfaces

Jinnouchi, Ryosuke; Karsai, Ferenc; Verdi, Carla; Kresse, Georg

First-principles hydration free energies of oxygenated species at water–platinum interfaces

Journal Article

In: The Journal of Chemical Physics, vol. 154, no. 9, pp. 094107, 2021.

Abstract | Links | BibTeX | Tags: P03, pre-TACO

Unraveling CO adsorption on model single-atom catalysts

Hulva, Jan; Meier, Matthias; Bliem, Roland; Jakub, Zdenek; Kraushofer, Florian; Schmid, Michael; Diebold, Ulrike; Franchini, Cesare; Parkinson, Gareth S.

Unraveling CO adsorption on model single-atom catalysts

Journal Article

In: Science, vol. 371, no. 6527, pp. 375–379, 2021.

Abstract | Links | BibTeX | Tags: P02, P04, P07, pre-TACO

How the anisotropy of surface oxide formation influences the transient activity of a surface reaction

Winkler, Philipp; Zeininger, Johannes; Suchorski, Yuri; Stöger-Pollach, Michael; Zeller, Patrick; Amati, Matteo; Gregoratti, Luca; Rupprechter, Günther

How the anisotropy of surface oxide formation influences the transient activity of a surface reaction

Journal ArticleOpen Access

In: Nature Communications, vol. 12, no. 1, 2021.

Abstract | Links | BibTeX | Tags: P08, pre-TACO

Sum frequency generation spectroscopy in heterogeneous model catalysis: a minireview of CO-related processes

Li, Xia; Rupprechter, Günther

Sum frequency generation spectroscopy in heterogeneous model catalysis: a minireview of CO-related processes

Journal ArticleOpen Access

In: Catalysis Science & Technology, vol. 11, no. 1, pp. 12–26, 2021.

Abstract | Links | BibTeX | Tags: P08, pre-TACO

2020

Interplay between CO Disproportionation and Oxidation: On the Origin of the CO Reaction Onset on Atomic Layer Deposition-Grown Pt/ZrO2 Model Catalysts

Pramhaas, Verena; Roiaz, Matteo; Bosio, Noemi; Corva, Manuel; Rameshan, Christoph; Vesselli, Erik; Grönbeck, Henrik; Rupprechter, Günther

Interplay between CO Disproportionation and Oxidation: On the Origin of the CO Reaction Onset on Atomic Layer Deposition-Grown Pt/ZrO2 Model Catalysts

Journal ArticleOpen Access

In: ACS Catalysis, vol. 11, no. 1, pp. 208–214, 2020.

Abstract | Links | BibTeX | Tags: P08, P10, pre-TACO

An ultrahigh vacuum-compatible reaction cell for model catalysis under atmospheric pressure flow conditions

Haunold, Thomas; Rameshan, Christoph; Bukhtiyarov, Andrey V; Rupprechter, Günther

An ultrahigh vacuum-compatible reaction cell for model catalysis under atmospheric pressure flow conditions

Journal ArticleOpen Access

In: Review of Scientific Instruments, vol. 91, no. 12, pp. 125101, 2020.

Abstract | Links | BibTeX | Tags: P08, P10, pre-TACO

High-throughput study of the static dielectric constant at high temperatures in oxide and fluoride cubic perovskites

van Roekeghem, Ambroise; Carrete, Jesús; Curtarolo, Stefano; Mingo, Natalio

High-throughput study of the static dielectric constant at high temperatures in oxide and fluoride cubic perovskites

Journal Article

In: Physical Review Materials, vol. 4, no. 11, pp. 113804, 2020.

Abstract | Links | BibTeX | Tags: P09, pre-TACO

IrO2 Surface Complexions Identified through Machine Learning and Surface Investigations

Timmermann, Jakob; Kraushofer, Florian; Resch, Nikolaus; Li, Peigang; Wang, Yu; Mao, Zhiqiang; Riva, Michele; Lee, Yonghyuk; Staacke, Carsten; Schmid, Michael; Scheurer, Christoph; Parkinson, Gareth S.; Diebold, Ulrike; Reuter, Karsten

IrO2 Surface Complexions Identified through Machine Learning and Surface Investigations

Journal Article

In: Physical Review Letters, vol. 125, no. 20, pp. 206101, 2020.

Abstract | Links | BibTeX | Tags: P02, P04, pre-TACO

Ab initio structure and thermodynamics of the RPBE-D3 water/vapor interface by neural-network molecular dynamics

Wohlfahrt, Oliver; Dellago, Christoph; Sega, Marcello

Ab initio structure and thermodynamics of the RPBE-D3 water/vapor interface by neural-network molecular dynamics

Journal ArticleOpen Access

In: The Journal of Chemical Physics, vol. 153, no. 14, pp. 144710, 2020.

Abstract | Links | BibTeX | Tags: P12, pre-TACO

Atomically resolved surface phases of La0.8Sr0.2MnO3(110) thin films

Franceschi, Giada; Schmid, Michael; Diebold, Ulrike; Riva, Michele

Atomically resolved surface phases of La0.8Sr0.2MnO3(110) thin films

Journal ArticleOpen Access

In: Journal of Materials Chemistry A, vol. 8, no. 43, pp. 22947–22961, 2020.

Abstract | Links | BibTeX | Tags: P02, pre-TACO

43 entries « 2 of 5 »