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Chemisorbed oxygen or surface oxides steer the selectivity in Pd electrocatalytic propene oxidation observed by operando Pd L-edge X-ray absorption spectroscopy

Journal Article · · Catalysis Science and Technology
DOI:https://doi.org/10.1039/d0cy02134b· OSTI ID:1808541
 [1];  [2];  [3];  [4];  [5];  [1];  [1];  [1];  [1];  [1];  [6];  [1];  [7];  [1]
  1. Stockholm Univ. (Sweden)
  2. Technical Univ. of Denmark, Lyngby (Denmark); Haldor Topsoe A/S, Lyngby (Denmark)
  3. Stockholm Univ. (Sweden); Carbyon B.V., Eindhoven (The Netherlands)
  4. Stockholm Univ. (Sweden); Uppsala Univ. (Sweden)
  5. Stockholm Univ. (Sweden); SLAC National Accelerator Lab., Menlo Park, CA (United States)
  6. Univ. of Copenhagen (Denmark)
  7. Technical Univ. of Denmark, Lyngby (Denmark)
+ Show Author Affiliations
Controlled electrochemical oxidation of hydrocarbons to desired products is an attractive approach in catalysis. Here we study the electrochemical propene oxidation under operando conditions using Pd L-edge X-ray absorption spectroscopy (XAS) as a sensitive probe to elucidate surface processes occurring during catalysis. Together with ab initio multiple-scattering calculations, our XAS results enable assignment of characteristic changes of the Pd L-edge intensity and energy position in terms of a mechanistic understanding of the selective oxidation of propene. The results, supported by electrochemical density functional theory DFT simulations, show that in the potential range of 0.8–1.0 V vs. the reversible hydrogen electrode (RHE), selective oxidation of propene to acrolein and acrylic acid occurs on the metallic Pd surface. Here, these reactions are proposed to proceed via the Langmuir–Hinshelwood mechanism. In contrast, for the potential range of 1.1–1.3 V vs. RHE, selective oxidation of propene to propylene glycol takes place on a Pd oxide surface.
Research Organization:
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); V-SUSTAIN
Grant/Contract Number:
AC02-76SF00515
OSTI ID:
1808541
Journal Information:
Catalysis Science and Technology, Journal Name: Catalysis Science and Technology Journal Issue: 10 Vol. 11; ISSN 2044-4753
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English

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