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dc.contributor.author
Núñez‐Rico, José Luis
dc.contributor.author
Rellán‐Piñeiro, Marcos
dc.contributor.author
Puértolas, Begoña
dc.contributor.author
Vidal-Ferran, Anton
dc.contributor.author
López, Núria
dc.contributor.author
Perez-Ramirez, Javier
dc.contributor.author
Wershofen, Stefan
dc.date.accessioned
2020-12-18T12:36:51Z
dc.date.available
2020-11-17T06:19:18Z
dc.date.available
2020-12-18T12:36:51Z
dc.date.issued
2020-12-04
dc.identifier.issn
0947-6539
dc.identifier.issn
1521-3765
dc.identifier.other
10.1002/chem.202003201
en_US
dc.identifier.uri
http://hdl.handle.net/20.500.11850/451632
dc.description.abstract
The methoxycarbonylation of anilines stands as an attractive method for the phosgene‐free production of carbamates. Despite the high yields obtained for ceria catalysts, the reduction of the amount of side products and the prevention of catalyst deactivation still represent major hurdles in this chemistry. One advantage of ceria is the possibility of tuning its reactivity by doping its lattice with other metals. In the present work, a series of doped ceria‐based materials, prepared by substitution with metals, are evaluated in the methoxycarbonylation of 2,4‐diaminotoluene with dimethyl carbonate. Among all catalysts, containing Eu, Hf, La, Pr, Sm, Tb, Y or Zr, ceria promoted with 2 mol % Zr exhibited 96 % selectivity towards the desired carbamates, improving the pure CeO2 catalyst. Density functional theory demonstrates that two descriptors are needed: 1) a geometric factor that governs the reduction of energy barriers for carbamate formation through ureas; 2) catalyst basicity as N−H bonds need to be activated. Assessment in subsequent reaction cycles revealed that the CeO2–ZrO2 catalyst is more stable than bulk CeO2, along with the reduction of fouling processes. © 2020 Wiley‐VCH GmbH.
en_US
dc.language.iso
en
en_US
dc.publisher
Wiley
en_US
dc.subject
Carbamates
en_US
dc.subject
Ceria
en_US
dc.subject
Doping
en_US
dc.subject
Methoxycarbonylation
en_US
dc.subject
Zirconium
en_US
dc.title
Enhanced Performance of Zirconium‐Doped Ceria Catalysts for the Methoxycarbonylation of Anilines
en_US
dc.type
Journal Article
dc.date.published
2020-07-17
ethz.journal.title
Chemistry - A European Journal
ethz.journal.volume
26
en_US
ethz.journal.issue
68
en_US
ethz.journal.abbreviated
Chem. Eur. J.
ethz.pages.start
16129
en_US
ethz.pages.end
16137
en_US
ethz.identifier.wos
ethz.identifier.scopus
ethz.publication.place
Weinheim
en_US
ethz.publication.status
published
en_US
ethz.leitzahl
ETH Zürich::00002 - ETH Zürich::00012 - Lehre und Forschung::00007 - Departemente::02020 - Dep. Chemie und Angewandte Biowiss. / Dep. of Chemistry and Applied Biosc.::02516 - Inst. f. Chemie- und Bioingenieurwiss. / Inst. Chemical and Bioengineering::03871 - Pérez-Ramírez, Javier / Pérez-Ramírez, Javier
en_US
ethz.leitzahl.certified
ETH Zürich::00002 - ETH Zürich::00012 - Lehre und Forschung::00007 - Departemente::02020 - Dep. Chemie und Angewandte Biowiss. / Dep. of Chemistry and Applied Biosc.::02516 - Inst. f. Chemie- und Bioingenieurwiss. / Inst. Chemical and Bioengineering::03871 - Pérez-Ramírez, Javier / Pérez-Ramírez, Javier
en_US
ethz.date.deposited
2020-11-14T04:57:46Z
ethz.source
WOS
ethz.source
FORM
ethz.eth
yes
en_US
ethz.availability
Metadata only
en_US
ethz.rosetta.installDate
2020-12-18T12:36:59Z
ethz.rosetta.lastUpdated
2022-03-29T04:37:10Z
ethz.rosetta.versionExported
true
dc.identifier.olduri
http://hdl.handle.net/20.500.11850/451372
dc.identifier.olduri
http://hdl.handle.net/20.500.11850/451470
ethz.COinS
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