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

Segets D, Milek T, Kirschbaum R, von Gernler M, Lübbert C, Drewello T, Peukert W, Zahn D (2015)

Publication Language: English

Publication Status: Published

Publication Type: Journal article, Original article

Publication year: 2015

Journal

Journal of Chemical Physics AIP Publishing

Publisher: American Institute of Physics Inc.

Book Volume: 143

Article Number: 064501

Journal Issue: 6

DOI: 10.1063/1.4928190

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.

Authors with CRIS profile

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

Additional Organisation(s)

Exzellenz-Cluster Engineering of Advanced Materials

How to cite

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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