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

15 entries « 1 of 2 »

2023

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

Quantum paraelectricity and structural phase transitions in strontium titanate beyond density functional theory

Verdi, Carla; Ranalli, Luigi; Franchini, Cesare; Kresse, Georg

Quantum paraelectricity and structural phase transitions in strontium titanate beyond density functional theory

Journal Article

In: Physical Review Materials, vol. 7, no. 3, pp. l030801, 2023.

Abstract | Links | BibTeX | Tags: P03, P07

Temperature-dependent anharmonic phonons in quantum paraelectric KTaO3 by first principles and machine-learned force fields

Ranalli, Luigi; Verdi, Carla; Monacelli, Lorenzo; Kresse, Georg; Calandra, Matteo; Franchini, Cesare

Temperature-dependent anharmonic phonons in quantum paraelectric KTaO3 by first principles and machine-learned force fields

Journal ArticleOpen Access

In: Advanced Quantum Technology, vol. 6, iss. 4, 2023.

Abstract | Links | BibTeX | Tags: P03, P07

Automated Real-Space Lattice Extraction for Atomic Force Microscopy Images

Corrias, Marco; Papa, Lorenzo; Sokolovíc, Igor; Birschitzky, Viktor; Gorfer, Alexander; Setvin, Martin; Schmid, Michael; Diebold, Ulrike; Reticcioli, Michele; Franchini, Cesare

Automated Real-Space Lattice Extraction for Atomic Force Microscopy Images

Journal ArticleOpen Access

In: Machine Learning: Science and Technology, vol. 4, pp. 015015, 2023.

Abstract | Links | BibTeX | Tags: P02, P07

2022

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

Competing electronic states emerging on polar surfaces

Reticcioli, Michele; Wang, Zhichang; Schmid, Michael; Wrana, Dominik; Boatner, Lynn A.; Diebold, Ulrike; Setvin, Martin; Franchini, Cesare

Competing electronic states emerging on polar surfaces

Journal ArticleOpen Access

In: Nature Communications, vol. 13, no. 4311, 2022.

Abstract | Links | BibTeX | Tags: P02, 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

Machine learning for exploring small polaron configurational space

Birschitzky, Viktor C; Ellinger, Florian; Diebold, Ulrike; Reticcioli, Michele; Franchini, Cesare

Machine learning for exploring small polaron configurational space

Journal ArticleOpen Access

In: npj Computational Materials, vol. 8, no. 125, 2022.

Abstract | Links | BibTeX | Tags: P02, P07

CO oxidation by Pt2/Fe3O4: Metastable dimer and support configurations facilitate lattice oxygen extraction

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

CO oxidation by Pt2/Fe3O4: Metastable dimer and support configurations facilitate lattice oxygen extraction

Journal ArticleOpen Access

In: ScienceAdvances, vol. 8, iss. 13, pp. eabn4580, 2022.

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

Modeling polarons in density functional theory: lessons learned from TiO2

Reticcioli, Michele; Diebold, Ulrike; Franchini, Cesare

Modeling polarons in density functional theory: lessons learned from TiO2

Journal ArticleOpen Access

In: Journal of Physics: Condensed Matter, vol. 34, no. 20, pp. 204006, 2022.

Abstract | Links | BibTeX | Tags: P02, P07

15 entries « 1 of 2 »