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Formation, Reactivity Tuning and Kinetic Investigations of Iron “Dioxygen” Intermediate Complexes and Derivatives in Multiphase Flow Reactions

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Reactive Bubbly Flows

Part of the book series: Fluid Mechanics and Its Applications ((FMIA,volume 128))

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Abstract

A dinuclear iron complex system had been developed that is capable to activate dioxygen in the protic solvent methanol forming a peroxido complex that is stable for a few seconds at room temperature. A full kinetic analysis of this reaction could be performed using stopped-flow techniques and furthermore by applying a SuperFocus mixer. Formation of the peroxido complex could be followed either by UV/VIS absorbance or by fluorescence. A reaction kit was developed that allowed to start with an air stable iron(III) complex that could be activated by reducing it with ascorbic acid prior to the reaction with dioxygen several times without decomposition of the complex. This reaction could be furthermore observed in bubbly flow columns. However, so far, the reaction rates were not in the necessary time window to perform accurate measurements. Ligand modification allowed to increase the solubility of the starting material to such an extent that it was possible to react it in water. Unfortunately, under these conditions the peroxido complex was not detected anymore. Still, from the results of this work, it seems likely that the iron system described herein can be further optimized to make it work as an oxygenation catalyst in aqueous solutions.

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Acknowledgements

This work was funded by the Deutsche Forschungsgemeinschaft (DFG, German Research Foundation)—priority program SPP1740 “Reactive Bubbly Flows” (237189010) for the project SCHI 377/13-1/2 (256663228).

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Authors and Affiliations

  1. Justus-Liebig University, Institute of Inorganic and Analytical Chemistry, Heinrich-Buff-Ring 17, 35392, Gießen, Germany

    Andreas Miska, Pascal Specht, Markus Lerch & Siegfried Schindler

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  1. Andreas Miska
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  2. Pascal Specht
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  3. Markus Lerch
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  4. Siegfried Schindler
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Correspondence to Siegfried Schindler .

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Editors and Affiliations

  1. Institute of Multiphase Flows, Hamburg University of Technology, Hamburg, Germany

    Michael Schlüter

  2. Mathematical Modeling and Analysis, Technical University of Darmstadt, Darmstadt, Germany

    Dieter Bothe

  3. Institute for Inorganic Chemistry, RWTH Aachen University, Aachen, Germany

    Sonja Herres-Pawlis

  4. Institute of Chemical Process Engineering, University of Stuttgart, Stuttgart, Germany

    Ulrich Nieken

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Miska, A., Specht, P., Lerch, M., Schindler, S. (2021). Formation, Reactivity Tuning and Kinetic Investigations of Iron “Dioxygen” Intermediate Complexes and Derivatives in Multiphase Flow Reactions. In: Schlüter, M., Bothe, D., Herres-Pawlis, S., Nieken, U. (eds) Reactive Bubbly Flows. Fluid Mechanics and Its Applications, vol 128. Springer, Cham. https://doi.org/10.1007/978-3-030-72361-3_5

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  • DOI: https://doi.org/10.1007/978-3-030-72361-3_5

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