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Title: Low-Temperature Oxidation of Methanol to Formaldehyde on a Model Single-Atom Catalyst: Pd Atoms on Fe3O4(001)

Abstract

Single atom catalysis has been a topic of increasing interest due to the potential for improved selectivity, reactivity, and catalyst cost. However, single atom catalysts are still difficult to characterize under realistic reaction conditions, leading to controversy regarding the capabilities of single atoms and a need for model studies. Herein, we examine the reaction of methanol on single Pd atoms supported on Fe3O4(001) under ultra-high vacuum conditions. On clean Fe3O4(001) a small fraction of methanol is converted to formaldehyde through a methoxy intermediate at 516 K. The addition of single Pd atoms lowers the barrier to C-H bond cleavage by a factor of two, resulting in formaldehyde desorption by 290 K. Furthermore, Pd atoms sinter by 300 K in the presence of methanol, and Pd clusters do not exhibit the same chemistry. Single atom sites significantly lower the barrier to the oxidation of methanol, although their stability remains an issue.

Authors:
 [1]; ORCiD logo [1];  [1]; ORCiD logo [1];  [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [2]
  1. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
  2. Pacific Northwest National Lab. (PNNL), Richland, WA (United States) ; Washington State Univ., Pullman, WA (United States)
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division; USDOE Office of Science (SC), Biological and Environmental Research (BER)
OSTI Identifier:
1615018
Report Number(s):
PNNL-SA-146242
Journal ID: ISSN 2155-5435
Grant/Contract Number:  
AC05-76RL01830
Resource Type:
Accepted Manuscript
Journal Name:
ACS Catalysis
Additional Journal Information:
Journal Volume: 9; Journal Issue: 12; Journal ID: ISSN 2155-5435
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; methanol; Fe3O4(001); palladium; partial oxidation; heterogeneous catalysis; single-atom catalysis

Citation Formats

Marcinkowski, Matthew D., Yuk, Simuck F., Doudin, Nassar, Smith, Ronald Scott, Nguyen, Manh-Thuong, Kay, Bruce D., Glezakou, Vassiliki-Alexandra, Rousseau, Roger J., and Dohnálek, Zdenek. Low-Temperature Oxidation of Methanol to Formaldehyde on a Model Single-Atom Catalyst: Pd Atoms on Fe3O4(001). United States: N. p., 2019. Web. doi:10.1021/acscatal.9b03891.
Marcinkowski, Matthew D., Yuk, Simuck F., Doudin, Nassar, Smith, Ronald Scott, Nguyen, Manh-Thuong, Kay, Bruce D., Glezakou, Vassiliki-Alexandra, Rousseau, Roger J., & Dohnálek, Zdenek. Low-Temperature Oxidation of Methanol to Formaldehyde on a Model Single-Atom Catalyst: Pd Atoms on Fe3O4(001). United States. https://doi.org/10.1021/acscatal.9b03891
Marcinkowski, Matthew D., Yuk, Simuck F., Doudin, Nassar, Smith, Ronald Scott, Nguyen, Manh-Thuong, Kay, Bruce D., Glezakou, Vassiliki-Alexandra, Rousseau, Roger J., and Dohnálek, Zdenek. Tue . "Low-Temperature Oxidation of Methanol to Formaldehyde on a Model Single-Atom Catalyst: Pd Atoms on Fe3O4(001)". United States. https://doi.org/10.1021/acscatal.9b03891. https://www.osti.gov/servlets/purl/1615018.
@article{osti_1615018,
title = {Low-Temperature Oxidation of Methanol to Formaldehyde on a Model Single-Atom Catalyst: Pd Atoms on Fe3O4(001)},
author = {Marcinkowski, Matthew D. and Yuk, Simuck F. and Doudin, Nassar and Smith, Ronald Scott and Nguyen, Manh-Thuong and Kay, Bruce D. and Glezakou, Vassiliki-Alexandra and Rousseau, Roger J. and Dohnálek, Zdenek},
abstractNote = {Single atom catalysis has been a topic of increasing interest due to the potential for improved selectivity, reactivity, and catalyst cost. However, single atom catalysts are still difficult to characterize under realistic reaction conditions, leading to controversy regarding the capabilities of single atoms and a need for model studies. Herein, we examine the reaction of methanol on single Pd atoms supported on Fe3O4(001) under ultra-high vacuum conditions. On clean Fe3O4(001) a small fraction of methanol is converted to formaldehyde through a methoxy intermediate at 516 K. The addition of single Pd atoms lowers the barrier to C-H bond cleavage by a factor of two, resulting in formaldehyde desorption by 290 K. Furthermore, Pd atoms sinter by 300 K in the presence of methanol, and Pd clusters do not exhibit the same chemistry. Single atom sites significantly lower the barrier to the oxidation of methanol, although their stability remains an issue.},
doi = {10.1021/acscatal.9b03891},
journal = {ACS Catalysis},
number = 12,
volume = 9,
place = {United States},
year = {Tue Oct 29 00:00:00 EDT 2019},
month = {Tue Oct 29 00:00:00 EDT 2019}
}

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