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Title:Effect of Na, Cs and Ca on propylene epoxidation selectivity over CuOx/SiO2 catalysts studied by catalytic tests, in-situ XAS and DFT
Authors:ID Teržan, Janvit, KI (Author)
ID Huš, Matej, KI (Author)
ID Arčon, Iztok, UNG (Author)
ID Likozar, Blaž, KI (Author)
ID Djinović, Petar, KI (Author)
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Language:Slovenian
Work type:Not categorized
Typology:1.01 - Original Scientific Article
Organization:UNG - University of Nova Gorica
Abstract:This research focuses on epoxidation of propylene over pristine, Na, Ca and Cs modified CuOx/SiO2 catalysts using O2. The selectivity of the reaction is analyzed using a combination of catalytic tests, in-situ XAS and DFT calculations. The initially present subnanometer CuO clusters are present in all catalysts which re-disperse/flatten during reaction. During catalytic reaction, the Cu1+ becomes the predominant oxidation state. There is no correlation between propylene oxide (PO) selectivity and copper oxidation state. DFT analysis of the propylene reaction pathway revealed that Na, Cs, and Ca addition decreases the bonding strength of propylene to CuO and decreases the O2 activation barrier, while simultaneously increase the exothermicity of O2 dissociation. The Na induced Cu-O bond modification decreases the activation barrier from 0.87 to 0.71 eV for the oxametallacycle (OMC) ring closure (first step in the reaction pathway favoring selectivity towards PO) compared to pristine 5Cu catalyst. At the same time, we observed an increase (from 0.45 to 0.72 eV) of the barrier for the abstraction of allylic hydrogen. The opposite effect is achieved by Ca addition: the activation barrier for OMC ring closure increases to 1.08 eV and that for allylic hydrogen stripping decreases to 0.16 eV.
Keywords:Alkali modification, propylene epoxidation, reaction mechanism, copper oxide, activation barrier.
Publication version:Version of Record
Year of publishing:2020
Number of pages:30
Numbering:1
PID:20.500.12556/RUNG-5539-f4e021ed-9ad7-0807-3b82-d9b20515af64 New window
COBISS.SI-ID:18333187 New window
DOI:https://doi.org/10.1016/j.apsusc.2020.146854 New window
NUK URN:URN:SI:UNG:REP:N6ZFJTN0
Publication date in RUNG:05.06.2020
Views:2853
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Record is a part of a journal

Title:Applied Surface Science
Year of publishing:2020

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License:CC BY-NC-ND 4.0, Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International
Link:http://creativecommons.org/licenses/by-nc-nd/4.0/
Description:The most restrictive Creative Commons license. This only allows people to download and share the work for no commercial gain and for no other purposes.
Licensing start date:05.06.2020

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