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Licensed Unlicensed Requires Authentication Published by De Gruyter (O) October 12, 2016

Investigations on the growth of bismuth oxido clusters and the nucleation to give metastable bismuth oxide modifications

Marcus Weber, Maik Schlesinger, Markus Walther, Dirk Zahn, Christoph A. Schalley and Michael Mehring

Abstract

Investigations on bismuth oxido clusters are focused on the nucleation and growth processes towards large cluster motifs and their stability in the gas phase, which has been studied by electrospray ionization mass spectrometry (ESI-MS), molecular dynamics (MD) simulations and X-ray scattering experiments evaluated by pair distribution function (PDF) analysis. The formation of metastable bismuth(III) oxides was obtained by hydrolysis of polynuclear bismuth oxido clusters and subsequent thermal treatment under non-equilibrium conditions. Temperature dependent PXRD and Raman spectroscopic experiments gave insight into the formation process of metastable β-Bi2O3 starting from the amorphous hydrolysis products as-obtained from polynuclear bismuth oxido clusters. Furthermore, PXRD as well as energy-dispersive X-ray (EDX) spectroscopy confirmed the formation of several new ternary bismuth(III) rich oxides such as Bi14O20(MO4) (M=S, Se) as-obtained by hydrolysis of bismuth oxido clusters in the presence of diverse additives.

Acknowledgments

We gratefully acknowledge the German Research Foundation (DFG-Priority Program 1415 “Crystalline Non-equilibrium Phases – Preparation, Characterization and in-situ Investigation of Formation Mechanisms”) for financial support. Furthermore we acknowledge Dr. D. Mansfeld, Dr. L. Miersch and Dipl. Chem. Lydia Wrobel for synthetic procedures of bismuth oxido clusters. We like to thank Dr. R. Troff, Dr. S. Richter, Dr. D. Weimann and D. Sattler for performing ESI-MS studies. We like to thank Dr. K.M.Ø. Jensen (University of Copenhagen) for performing X-ray scattering experiments and the PDF analyses. We thank Prof. Dr. D. R.T. Zahn (TU Chemnitz, Professorship for Semiconductor Physics) for access to the LabRAM HR800 and Dr. O. Gordan and Dr. A. Villabona for Raman spectroscopic performances. We like to thank Dr. T. Rüffer and Prof. Dr. H. Lang (TU Chemnitz, Professorship for Inorganic Chemistry) for performing single crystal X-ray structure analysis. Furthermore we acknowledge Prof. Dr. S. Spange (TU Chemnitz, Professorship for Polymeric Chemistry) for access to diffuse reflectance UV-Vis spectroscopy and Spectromat FTS-165 spectrometer for ATR IR spectroscopy. We like to thank Prof. Dr. M. Hietschold (TU Chemnitz, Professorship for Analysis of Solid Surfaces) for access to the NanoNovaSEM for SEM and EDX studies, Dr. S. Schulze for performing TEM analysis and M.Sc. B. Büchter for performing SEM and EDX analysis.

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Received: 2016-6-7
Accepted: 2016-9-6
Published Online: 2016-10-12
Published in Print: 2017-2-1

©2017 Walter de Gruyter GmbH, Berlin/Boston

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