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

17 entries « 1 of 2 »

2024

Infrared Reflection Absorption Spectroscopy Setup with Incidence Angle Selection for Surfaces of Non-Metals

Rath, David; Mikerásek, Vojtěch; Wang, Chunlei; Eder, Moritz; Schmid, Michael; Diebold, Ulrike; Parkinson, Gareth S.; Pavelec, Jiří

Infrared Reflection Absorption Spectroscopy Setup with Incidence Angle Selection for Surfaces of Non-Metals

Journal ArticleOpen AccessAccepted Article

In: Review of Scientific Instruments, vol. 95, iss. 6, pp. 065106, 2024.

Abstract | Links | BibTeX | Tags: P02, P04

CO‐Induced Dimer Decay Responsible for Gem‐Dicarbonyl Formation on a Model Single‐Atom Catalyst

Wang, Chunlei; Sombut, Panukorn; Puntscher, Lena; Jakub, Zdenek; Meier, Matthias; Pavelec, Jiri; Bliem, Roland; Schmid, Michael; Diebold, Ulrike; Franchini, Cesare; Parkinson, Gareth S.

CO‐Induced Dimer Decay Responsible for Gem‐Dicarbonyl Formation on a Model Single‐Atom Catalyst

Journal ArticleOpen AccessIn Press

In: Angewandte Chemie - International Edition, no. e202317347, 2024, ISSN: 1521-3773.

Abstract | Links | BibTeX | Tags: P02, P04, P07

2023

Formation and stability of Fe-rich terminations of the Fe3O4(001) surface

Gamba, Oscar; Eder, Moritz; Poglitsch, Matthias; Pavelec, Jiri; Sombut, Panukorn; Meier, Matthias; Diebold, Ulrike; Schmid, Michael; Parkinson, Gareth S.

Formation and stability of Fe-rich terminations of the Fe3O4(001) surface

Journal ArticleOpen Access

In: Materials Research Express, vol. 10, iss. 44, no. 116517, 2023.

Abstract | Links | BibTeX | Tags: P02, P04

A Multitechnique Study of C2H4 Adsorption on Fe3O4(001)

Puntscher, Lena; Sombut, Panukorn; Wang, Chunlei; Ulreich, Manuel; Pavelec, Jiri; Rafsanjani-Abbasi, Ali; Meier, Matthias; Lagin, Adam; Setvin, Martin; Diebold, Ulrike; Franchini, Cesare; Schmid, Michael; Parkinson, Gareth S.

A Multitechnique Study of C2H4 Adsorption on Fe3O4(001)

Journal ArticleOpen Access

In: Journal of Physical Chemistry C, vol. 127, iss. 37, pp. 18378–18388, 2023.

Abstract | Links | BibTeX | Tags: P02, P04, P07

Hematite α-Fe2O3(0001) in Top and Side View: Resolving Long-Standing Controversies about Its Surface Structure

Redondo, Jesús; Michalička, Jan; Kraushofer, Florian; Franceschi, Giada; Šmid, Břetislav; Kumar, Nishant; Man, Ondřej; Blatnik, Matthias; Wrana, Dominik; Mallada, Benjamin; Švec, Martin; Parkinson, Gareth S.; Setvin, Martin; Riva, Michele; Diebold, Ulrike; Čechal, Jan

Hematite α-Fe2O3(0001) in Top and Side View: Resolving Long-Standing Controversies about Its Surface Structure

Journal ArticleOpen Access

In: Advanced Materials Interfaces, no. 2300602, 2023.

Abstract | Links | BibTeX | Tags: P02, P04

Real-space investigation of polarons in hematite Fe2O3

Redondo, Jesus; Reticcioli, Michele; Gabriel, Vit; Wrana, Dominik; Ellinger, Florian; Riva, Michele; Franceschi, Giada; Rheinfrank, Erik; Sokolovic, Igor; Jakub, Zdenek; Kraushofer, Florian; Alexander, Aji; Patera, Laerte L.; Repp, Jascha; Schmid, Michael; Diebold, Ulrike; Parkinson, Gareth S.; Franchini, Cesare; Kocan, Pavel; Setvin, Martin

Real-space investigation of polarons in hematite Fe2O3

Journal ArticleSubmittedarXiv

In: arXiv, 2023.

Abstract | Links | BibTeX | Tags: P02, P04, P07

Oxygen-Terminated (1 × 1) Reconstruction of Reduced Magnetite Fe3O4(111)

Kraushofer, Florian; Meier, Matthias; Jakub, Zdeněk; Hütner, Johanna; Balajka, Jan; Hulva, Jan; Schmid, Michael; Franchini, Cesare; Diebold, Ulrike; Parkinson, Gareth S.

Oxygen-Terminated (1 × 1) Reconstruction of Reduced Magnetite Fe3O4(111)

Journal ArticleOpen Access

In: vol. 14, no. 13, pp. 3258–3265, 2023.

Abstract | Links | BibTeX | Tags: P02, P04, P07

2022

Analysis of Temperature-Programmed Desorption via Equilibrium Thermodynamics

Schmid, Michael; Parkinson, Gareth S.; Diebold, Ulrike

Analysis of Temperature-Programmed Desorption via Equilibrium Thermodynamics

Journal ArticleOpen Access

In: ACS Physical Chemistry Au, vol. 3, iss. 1, pp. 44–62, 2022.

Abstract | Links | BibTeX | Tags: P02, P04

Surface chemistry on a polarizable surface: Coupling of CO with KTaO 3(001)

Wang, Zhichang; Reticcioli, Michele; Jakub, Zdenek; Sokolović, Igor; Meier, Matthias; Boatner, Lynn A; Schmid, Michael; Parkinson, Gareth S.; Diebold, Ulrike; Franchini, Cesare; Setvin, Martin

Surface chemistry on a polarizable surface: Coupling of CO with KTaO 3(001)

Journal ArticleOpen Access

In: Science Advances, vol. 8, iss. 33, 2022.

Abstract | Links | BibTeX | Tags: P02, P04, P07

Role of Polarons in Single-Atom Catalysts: Case Study of Me1[Au1,Pt1 and Rh1] on TiO2(110)

Sombut, Panukorn; Puntscher, Lena; Atzmüller, Marlene; Jakub, Zdenek; Reticcioli, Michele; Meier, Matthias; Parkinson, Gareth S.; Franchini, Cesare

Role of Polarons in Single-Atom Catalysts: Case Study of Me1[Au1,Pt1 and Rh1] on TiO2(110)

Journal ArticleOpen Access

In: Topics in Catalysis, vol. 65, pp. 1620–1630, 2022.

Abstract | Links | BibTeX | Tags: P04, P07

17 entries « 1 of 2 »