On the mechanism of Zn4O-acetate precursors ripening to ZnO: How dimerization is promoted by hydroxide incorporation

Beitrag in einer Fachzeitschrift
(Originalarbeit)


Details zur Publikation

Autor(en): Segets D, Milek T, Kirschbaum R, von Gernler M, Lübbert C, Drewello T, Peukert W, Zahn D
Zeitschrift: Journal of Chemical Physics
Verlag: American Institute of Physics Inc.
Jahr der Veröffentlichung: 2015
Band: 143
Heftnummer: 6
ISSN: 0021-9606
Sprache: Englisch


Abstract

We report on a combined experimental and molecular modelling study on Zn4O ion clusters stabilized by acetate molecules (OAc). In particular, ab initio calculations of acetate substitution by hydroxide ions are compared with mass spectrometry data. Though quantum calculations in the gas phase indicate strong energetic preference, no experimental evidence of stable Zn4O(OAc)6−x(OH)x clusters in ethanolic solutions
could be observed. This apparent contradiction is rationalized by
identifying the supportive role of hydroxide ions for the association of
(OAc → OH substituted) Zn4O(OAc)6 and Zn4O(OAc)5+ clusters. Mass spectrometry and quantum calculations hint at the stability of (Zn4O)2(OAc)12−x(OH)x dimers with x = 1, 2. Therein, the hydroxide ions establish salt-bridges that allow for the formation of additional Zn3 motifs with the OH above the triangle center—a structural motif close to that of the ZnO-crystal. The association of Zn4O(OAc)6 clusters is thus suggested to involve OAc → OH substitution as an activation step, quickly followed by dimerization and the subsequent agglomeration of oligomers.


FAU-Autoren / FAU-Herausgeber

Drewello, Thomas Prof. Dr.
Professur für Physikalische Chemie
Lübbert, Christian Dr.-Ing.
Lehrstuhl für Feststoff- und Grenzflächenverfahrenstechnik
Milek, Theodor
Lehrstuhl für Theoretische Chemie
Peukert, Wolfgang Prof. Dr.-Ing.
Lehrstuhl für Feststoff- und Grenzflächenverfahrenstechnik
Segets, Doris Dr.-Ing.
Lehrstuhl für Feststoff- und Grenzflächenverfahrenstechnik
von Gernler, Marc
Lehrstuhl für Physikalische Chemie I
Zahn, Dirk Prof. Dr.
Professur für Theoretische Chemie


Zusätzliche Organisationseinheit(en)
Exzellenz-Cluster Engineering of Advanced Materials


Zitierweisen

APA:
Segets, D., Milek, T., Kirschbaum, R., von Gernler, M., Lübbert, C., Drewello, T.,... Zahn, D. (2015). On the mechanism of Zn4O-acetate precursors ripening to ZnO: How dimerization is promoted by hydroxide incorporation. Journal of Chemical Physics, 143(6). https://dx.doi.org/10.1063/1.4928190

MLA:
Segets, Doris, et al. "On the mechanism of Zn4O-acetate precursors ripening to ZnO: How dimerization is promoted by hydroxide incorporation." Journal of Chemical Physics 143.6 (2015).

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Zuletzt aktualisiert 2018-18-10 um 05:08