Influence of structure and copper electronic state on activity of in methanol synthesis from

2014
journal article
article
299
dc.abstract.enCu/ZrO2 catalysts obtained by impregnation of ZrO2 and complexation with citric acid were studied for CO2 hydrogenation to methanol. The catalyst structure, texture, and active copper surface were determined using XRD, BET, and reactive adsorption of N2O, respectively. The XPS and Auger spectroscopies were used to determine the surface structure and copper electronic state. FT-IR pyridine adsorption was studied to determine acidity of the catalysts. The results of quantum-chemical calculations concerning the formation of oxygen vacancies in monoclinic and tetragonal ZrO2 have been also presented. It was found that selection of the appropriate conditions of the catalyst preparation influences the degree of copper dispersion, its electronic state, and contents of the zirconia polymorphic phases (tetragonal and monoclinic). The presence of oxygen vacancies stabilizes both the thermodynamically unstable t-ZrO2 phase and Cu1+ cations, which are present in the vicinity of oxygen vacancies. Complexes formed preferentially on tetragonal ZrO2 built from Cu cations and oxygen vacancies are the acid centers active in methanol synthesis reaction; therefore the catalytic activity toward methanol increases with increasing t-ZrO2 content. The implications of the obtained results for the mechanism of the catalytic hydrogenation of CO2 are discussed.pl
dc.affiliationWydział Chemii : Zakład Chemii Nieorganicznejpl
dc.contributor.authorSamson, Katarzynapl
dc.contributor.authorŚliwa, Michałpl
dc.contributor.authorSocha, Robert P.pl
dc.contributor.authorGóra-Marek, Kinga - 128133 pl
dc.contributor.authorRutkowska-Żbik, Dorotapl
dc.contributor.authorPaul, J-Fpl
dc.contributor.authorRuggiero-Mikołajczyk, Małgorzatapl
dc.contributor.authorMucha, Dariuszpl
dc.contributor.authorGrabowski, Ryszardpl
dc.contributor.authorSłoczyński, Jerzypl
dc.date.accessioned2015-06-25T12:30:38Z
dc.date.available2015-06-25T12:30:38Z
dc.date.issued2014pl
dc.description.additionalBibliogr. 3740-3741pl
dc.description.number10pl
dc.description.physical3730-3741pl
dc.description.volume4pl
dc.identifier.doi10.1021/cs500979cpl
dc.identifier.eissn2155-5435pl
dc.identifier.urihttp://ruj.uj.edu.pl/xmlui/handle/item/10365
dc.languageengpl
dc.language.containerengpl
dc.rights.licencebez licencji
dc.subject.enCO2 hydrogenationpl
dc.subject.entetragonal and monoclinic ZrO2pl
dc.subject.enoxygen vacanciespl
dc.subject.encopper zirconia catalystspl
dc.subject.enmethanol synthesispl
dc.subtypeArticlepl
dc.titleInfluence of $ZrO_2$ structure and copper electronic state on activity of $Cu/ZrO_2$ in methanol synthesis from $CO_2$pl
dc.title.journalACS Catalysispl
dc.typeJournalArticlepl
dspace.entity.typePublication
dc.abstract.enpl
Cu/ZrO2 catalysts obtained by impregnation of ZrO2 and complexation with citric acid were studied for CO2 hydrogenation to methanol. The catalyst structure, texture, and active copper surface were determined using XRD, BET, and reactive adsorption of N2O, respectively. The XPS and Auger spectroscopies were used to determine the surface structure and copper electronic state. FT-IR pyridine adsorption was studied to determine acidity of the catalysts. The results of quantum-chemical calculations concerning the formation of oxygen vacancies in monoclinic and tetragonal ZrO2 have been also presented. It was found that selection of the appropriate conditions of the catalyst preparation influences the degree of copper dispersion, its electronic state, and contents of the zirconia polymorphic phases (tetragonal and monoclinic). The presence of oxygen vacancies stabilizes both the thermodynamically unstable t-ZrO2 phase and Cu1+ cations, which are present in the vicinity of oxygen vacancies. Complexes formed preferentially on tetragonal ZrO2 built from Cu cations and oxygen vacancies are the acid centers active in methanol synthesis reaction; therefore the catalytic activity toward methanol increases with increasing t-ZrO2 content. The implications of the obtained results for the mechanism of the catalytic hydrogenation of CO2 are discussed.
dc.affiliationpl
Wydział Chemii : Zakład Chemii Nieorganicznej
dc.contributor.authorpl
Samson, Katarzyna
dc.contributor.authorpl
Śliwa, Michał
dc.contributor.authorpl
Socha, Robert P.
dc.contributor.authorpl
Góra-Marek, Kinga - 128133
dc.contributor.authorpl
Rutkowska-Żbik, Dorota
dc.contributor.authorpl
Paul, J-F
dc.contributor.authorpl
Ruggiero-Mikołajczyk, Małgorzata
dc.contributor.authorpl
Mucha, Dariusz
dc.contributor.authorpl
Grabowski, Ryszard
dc.contributor.authorpl
Słoczyński, Jerzy
dc.date.accessioned
2015-06-25T12:30:38Z
dc.date.available
2015-06-25T12:30:38Z
dc.date.issuedpl
2014
dc.description.additionalpl
Bibliogr. 3740-3741
dc.description.numberpl
10
dc.description.physicalpl
3730-3741
dc.description.volumepl
4
dc.identifier.doipl
10.1021/cs500979c
dc.identifier.eissnpl
2155-5435
dc.identifier.uri
http://ruj.uj.edu.pl/xmlui/handle/item/10365
dc.languagepl
eng
dc.language.containerpl
eng
dc.rights.licence
bez licencji
dc.subject.enpl
CO2 hydrogenation
dc.subject.enpl
tetragonal and monoclinic ZrO2
dc.subject.enpl
oxygen vacancies
dc.subject.enpl
copper zirconia catalysts
dc.subject.enpl
methanol synthesis
dc.subtypepl
Article
dc.titlepl
Influence of $ZrO_2$ structure and copper electronic state on activity of $Cu/ZrO_2$ in methanol synthesis from $CO_2$
dc.title.journalpl
ACS Catalysis
dc.typepl
JournalArticle
dspace.entity.type
Publication
Affiliations

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