UNODE- DFG Forschergruppe 2982

• TP1 – Electrocatalysts for low-overpotential HMF and alcohol oxidation. From catalyst development to flow-through micro-electrolyzers
• TP2 – Electrochemical generation of peroxodicarbonate as versatile and primary sustainable oxidizer to value added chemicals
• TP3 – Anodes for Methane Oxidation
• TP4 – Narrow gap flow electrolysis cells and the challenge of hydrogen bubbles – a combined approach via modelling and experiment
• TP5 – Tuning selectivity of oxide electrocatalysts towards electrolytic production of organic N-derivatives and H₂O₂
• TP6 – Electrochemical generation of storable organic oxidants for use in sustainable catalytic transformations
• TP7 – Operando ATR-IR spectroscopy applied to investigate the mechanisms of alternative anodic reactions
• TP8 – New 3d-transition metal-based materials for efficient anodic electrocatalysis
• TP9 – Stable immobilization of electrocatalysts and design of modified electrodes towards selective glycerol electrooxidation

TP2 – Electrochemical generation of peroxodicarbonate as versatile and primary sustainable oxidizer to value added chemicals

The central goal within this subproject is the efficient generation of the largely underexplored oxidant peroxodicarbonate, which can be obtained by the direct electrolysis of carbonate solutions in undivided cells at boron-doped diamond elec­trodes. In subsequent conversions, only aqueous carbonate or bicarbonate solutions are formed. For oxidative reactions using base equivalents, this reagent seems to be the oxidizer of choice. Since no halogens are present, typical and undesired side reaction such as chlorination of multiple bonds will not occur. The electrosynthesis of peroxodicar­bonate will be conducted in flow cells and our re­search will focus on the development of strategies to obtain high concentrations of the desired peroxo compound with moderate current density and good electric efficiency. In addition, the subsequent use of this strong oxidant will be explored in organic trans­formations to high-value products such as epoxides and many others. Due to the limited storage capa­bility of peroxodicarbonate, this oxidizer will be employed to regenerate high performance reagents which are commonly used in the synthesis of fine chemicals or active pharmaceutical ingredients. Such reagents have to be sufficiently stable, preferably for longer times and at elevated tem­peratures. This subproject will cover the regeneration of periodate and the corresponding appli­cations. In a tight collaboration with the Gooßen lab, the use of peroxodicarbonate will be exploited to generate N-oxides as suitable reagent for subsequent conversions. Although this work is complementary to the amine oxidation on metal oxides electrodes of Aliaksandr Bandarenka, the cooperation with his lab will provide valuable insights for a target oriented development.

Waldvogel, Siegfried R., Prof. Dr., born 09.06.1969, German; Wa1276
Institute of Organic Chemistry, Johannes Gutenberg University Mainz, Duesbergstr. 10-14, D‑55128 Mainz, Germany
Tel.: +49 (0)6131-39 26069; Email: waldvogel@uni-mainz.de