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Redox dynamics and surface structures of an active palladium catalyst during methane oxidation

Journal Article · · Nature Communications
 [1];  [2];  [3];  [4];  [5];  [1];  [6];  [1];  [1];  [7];  [8]
  1. Fuzhou Univ. (China); Qingyuan Innovation Laboratory, Quanzhou (China)
  2. Cochin Univ. of Science and Technology (India)
  3. Lund Univ. (Sweden)
  4. Eidgenoessische Technische Hochschule (ETH), Zurich (Switzerland)
  5. JEOL (EUROPE) SAS, Croissy-sur-Seine (France)
  6. Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)
  7. Eidgenoessische Technische Hochschule (ETH), Zurich (Switzerland); Technische Univ. München, Garching (Germany)
  8. Fuzhou Univ. (China); Qingyuan Innovation Laboratory, Quanzhou (China); Eidgenoessische Technische Hochschule (ETH), Zurich (Switzerland)
+ Show Author Affiliations
Catalysts based on palladium are among the most effective in the complete oxidation of methane. Despite extensive studies and notable advances, the nature of their catalytically active species and conceivable structural dynamics remains only partially understood. Here, we combine operando transmission electron microscopy (TEM) with near-ambient pressure X-ray photoelectron spectroscopy (NAP-XPS) and density functional theory (DFT) calculations to investigate the active state and catalytic function of Pd nanoparticles (NPs) under methane oxidation conditions. We show that the particle size, phase composition and dynamics respond appreciably to changes in the gas-phase chemical potential. In combination with mass spectrometry (MS) conducted simultaneously with in situ observations, we uncover that the catalytically active state exhibits phase coexistence and oscillatory phase transitions between Pd and PdO. Aided by DFT calculations, we provide a rationale for the observed redox dynamics and demonstrate that the emergence of catalytic activity is related to the dynamic interplay between coexisting phases, with the resulting strained PdO having more favorable energetics for methane oxidation.
Research Organization:
Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)
Sponsoring Organization:
ETH Career Seed; Innovation In Science Pursuit For Inspired Research (INSPIRE); Swedish Agency for Innovation Systems (Vinnova); Swedish Research Council (VR); Swedish Research Council for Sustainable Development (Formas); USDOE National Nuclear Security Administration (NNSA)
Grant/Contract Number:
89233218CNA000001
OSTI ID:
2406662
Report Number(s):
LA-UR--24-23486
Journal Information:
Nature Communications, Journal Name: Nature Communications Journal Issue: 1 Vol. 15; ISSN 2041-1723
Publisher:
Nature Publishing GroupCopyright Statement
Country of Publication:
United States
Language:
English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Inorganic and Physical Chemistry