Understanding methanol dissociative adsorption and oxidation on amorphous oxide films

Padavala, Sri Murthy; Artyushkova, Kateryna; Boettcher, Shannon W; Nemšák, Slavomír; Stoerzinger, Kelsey A.

doi:10.1039/d1fd00109d

Title: Understanding methanol dissociative adsorption and oxidation on amorphous oxide films

Journal Article · 21 January 2022 · Faraday Discussions

DOI: https://doi.org/10.1039/d1fd00109d · OSTI ID:2281360

^[1]; Artyushkova, Kateryna ^[2];

^[3]; Nemšák, Slavomír ^[4];

^[5]

Oregon State University, Corvallis, OR (United States)
Physical Electronics Inc., Chanhassen, MN (United States)
University of Oregon, Eugene, OR (United States)
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
Oregon State University, Corvallis, OR (United States); Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Interactions between a transition metal (oxide) catalyst and a support can tailor the number and nature of active sites, for instance in the methanol oxidation reaction.In this report we use ambient pressure X-ray photoelectron spectroscopy (AP-XPS) to identify and compare the surface adsorbates that form on amorphous metal oxide films that maximize such interactions. Considering Al_(1−x)M_xO_y (M = Fe or Mn) films at a range of methanol : oxygen gas ratios and temperatures, we find that the redox-active transition metal site (characterized by methoxy formation) dominates dissociative methanol adsorption, while basic oxygen sites (characterized by carbonate formation) play a lesser role. Product detection, however, indicates complete oxidation to carbon dioxide and water with partial oxidation products (dimethyl ether) comprising a minor species. Comparing the intensity of methoxy and hydroxyl features at a fixed XPS chemical shift suggests methanol deprotonation during adsorption in oxygen rich conditions for high transition metal content. However, increasing methanol partial pressure and lower metal site density may promote oxygen vacancy formation and the dehydroxylation pathway, supported by a nominal reduction in the oxidation state of iron sites. These findings illustrate that AP-XPS and mass spectrometry together are powerful tools in understanding metal–support interactions, quantifying and probing the nature of catalytic active sites, and considering the link between electronic structure of materials and their catalytic activity.

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Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC); National Science Foundation (NSF)

Grant/Contract Number:: AC05-76RL01830; AC02-05CH11231

OSTI ID:: 2281360

Report Number(s):: PNNL-SA--180619

Journal Information:: Faraday Discussions, Journal Name: Faraday Discussions Vol. 236; ISSN 1359-6640

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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