Understanding Heterolytic H2 Cleavage and Water-Assisted Hydrogen Spillover on Fe3O4(001)-Supported Single Palladium Atoms

Nassar Doudin, Simuck F. Yuk, Matthew D. Marcinkowski, Manh Thuong Nguyen, Jin Cheng Liu, Yang Wang, Zbynek Novotny, Bruce D. Kay, Jun Li, Vassiliki Alexandra Glezakou, Gareth Parkinson, Roger Rousseau, Zdenek Dohnálek

Research output: Contribution to journalArticle

Abstract

The high specific activity and cost-effectiveness of single-atom catalysts (SACs) hold great promise for numerous catalytic chemistries. In hydrogenation reactions, the mechanisms of critical steps such as hydrogen activation and spillover are far from understood. Here, we employ a combination of scanning tunneling microscopy and density functional theory to demonstrate that on a model SAC comprised of single Pd atoms on Fe3O4(001), H2 dissociates heterolytically between Pd and surface oxygen. The efficient hydrogen spillover allows for continuous hydrogenation to high coverages, which ultimately leads to the lifting of Fe3O4 reconstruction and Pd reduction and destabilization. Water plays an important role in reducing the proton diffusion barrier, thereby facilitating the redistribution of hydroxyls away from Pd. Our study demonstrates a distinct H2 activation mechanism on single Pd atoms and corroborates the importance of charge transport on reducible support away from the active site.

Original languageEnglish
Pages (from-to)7876-7887
Number of pages12
JournalACS Catalysis
DOIs
Publication statusAccepted/In press - Jan 1 2019

Fingerprint

Ferrosoferric Oxide
Diffusion barriers
Palladium
Scanning tunneling microscopy
Magnetite
Cost effectiveness
Iron oxides
Hydrogenation
Density functional theory
Hydrogen
Chemical activation
Atoms
Catalysts
Water
Hydroxyl Radical
Protons
Charge transfer
Oxygen
ferric oxide

Keywords

  • dissociative adsorption
  • FeO(001)
  • hydrogen
  • kinetic barriers
  • palladium
  • single-atom catalyst

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)

Cite this

Doudin, N., Yuk, S. F., Marcinkowski, M. D., Nguyen, M. T., Liu, J. C., Wang, Y., ... Dohnálek, Z. (Accepted/In press). Understanding Heterolytic H2 Cleavage and Water-Assisted Hydrogen Spillover on Fe3O4(001)-Supported Single Palladium Atoms. ACS Catalysis, 7876-7887. https://doi.org/10.1021/acscatal.9b01425

Understanding Heterolytic H2 Cleavage and Water-Assisted Hydrogen Spillover on Fe3O4(001)-Supported Single Palladium Atoms. / Doudin, Nassar; Yuk, Simuck F.; Marcinkowski, Matthew D.; Nguyen, Manh Thuong; Liu, Jin Cheng; Wang, Yang; Novotny, Zbynek; Kay, Bruce D.; Li, Jun; Glezakou, Vassiliki Alexandra; Parkinson, Gareth; Rousseau, Roger; Dohnálek, Zdenek.

In: ACS Catalysis, 01.01.2019, p. 7876-7887.

Research output: Contribution to journalArticle

Doudin, N, Yuk, SF, Marcinkowski, MD, Nguyen, MT, Liu, JC, Wang, Y, Novotny, Z, Kay, BD, Li, J, Glezakou, VA, Parkinson, G, Rousseau, R & Dohnálek, Z 2019, 'Understanding Heterolytic H2 Cleavage and Water-Assisted Hydrogen Spillover on Fe3O4(001)-Supported Single Palladium Atoms', ACS Catalysis, pp. 7876-7887. https://doi.org/10.1021/acscatal.9b01425
Doudin, Nassar ; Yuk, Simuck F. ; Marcinkowski, Matthew D. ; Nguyen, Manh Thuong ; Liu, Jin Cheng ; Wang, Yang ; Novotny, Zbynek ; Kay, Bruce D. ; Li, Jun ; Glezakou, Vassiliki Alexandra ; Parkinson, Gareth ; Rousseau, Roger ; Dohnálek, Zdenek. / Understanding Heterolytic H2 Cleavage and Water-Assisted Hydrogen Spillover on Fe3O4(001)-Supported Single Palladium Atoms. In: ACS Catalysis. 2019 ; pp. 7876-7887.
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