Anodic abatement of organic pollutants in water in micro reactors
The electrochemical oxidation of oxalic acid (OA) was performed in a micro flow cell equipped with a boron doped diamond (BDD) anode. This preliminary study demonstrates that a flow cell with a micrometric distance between the cathode and the anode can be used to perform the electrochemical treatment of waters contaminated by organic pollutants in the absence of added supporting electrolytes with high abatements. The effect of the distance between the cathode and the anode, the flow rate and the current density on the abatement of oxalic acid and on the current efficiency was in particular studied.
ELECTROCHEMICAL CONVERSION OF DICHLOROACETIC ACID TO CHLOROACETIC ACID IN A MICROFLUIDIC STACK AND IN A SERIES OF MICROFLUIDIC REACTORS
The electrochemical conversion of dichloroacetic acid to chloracetic acid was performed in three different micro devices: a simple micro fluidic cell; a microfluidic stack equipped with various electrode chambers in series and three micro fluidic cells in series. The electrochemical synthesis of chloracetic acid was performed successfully with high yields and selectivity under a single-pass mode without supporting electrolyte at low cell voltages. An increase of the productivity and of the final concentration of the target product was achieved by using a stack with two or three electrode chambers in series. The utilization of three micro reactors in series open interesting new perspectives,…
Mechanism of the palladium-catalysed electrosynthesis of diethyl carbonate from carbon monoxide and ethanol
Abstract A mechanism is proposed for the PdBr2(PPh3)2-catalysed electrosynthesis of diethyl carbonate from carbon monoxide and ethanol, proceeding at room temperature and atmospheric CO pressure. The mechanism is investigated by cyclic voltammetry and 31P NMR spectroscopy. The active Pd0 complex able to coordinate CO is generated by the chemical reduction of PdBr2(PPh3)2 by EtO– ions generated from EtOH at the cathode. After reaction of EtO– ions with Pd0(PPh3)2(CO), the ensuing anionic complex [(PPh3)2Pd0–COOEt]– is oxidized at the anode in a key step leading to BrPdII–COOEt(PPh3)2. A nucleophilic attack of ethoxide on the latter generates diethyl carbonate and the Pd0 complex active in th…
Electrocarboxylation of Benzyl Halides through Redox Catalysis on the Preparative Scale
The electrocarboxylation of benzyl halides to the corresponding carboxylic acids through homogeneous charge-transfer catalysis was investigated both theoretically and experimentally to determine the influence of the operative parameters on the yield of the process and on the catalyst consumption. Theoretical considerations, based on fast kinetics of redox catalysis, were confirmed by the electrocarboxylation of 1-phenyl-1-chloroethane catalyzed by 1,3-benzenedicarboxylic acid di methyl ester performed at a carbon cathode under different operative conditions. We obtained high yields of the target carboxylic acid and experienced a low catalyst consumption by operating with optimized [RX]bulk/…
CO2 as a C1-organic building block: Electrocarboxylation of aromatic ketones. A quantitative study of the effect of the concentration of substrate and of carbon dioxide on the selectivity of the process
The purpose of this work is to establish and discuss quantitative relationships between the selectivity in preparative scale electrolysis and intrinsic and operational parameters for the electrocarboxylation of aromatic ketones. For the investigated ketones, under appopriate experimental conditions the selectivity of the process is mainly determined by the competition between carboxylation and protonation, de-halogenation reactions (when an halogenated ketone is involved), and possibly dimerizations involving the electrogenerated radical anion. A simple model was proposed to account for these unwanted side paths which allows to predict the dependence of the selectivity as a function of the …
Electrochemical Conversion of Dichloroacetic Acid to Chloroacetic Acid in Conventional Cell and in Two Microfluidic Reactors
The electrochemical conversion of dichloroacetic acid to chloracetic acid is investigated in conventional cells and in microreactors. Two different microreactors are used: the first is a filter press cell equipped with PTFE micrometric spacers, easy to assemble and disassemble and available for a large variety of electrodes and solvents; the second is made using an adhesive spacer, micromilling and press and could easily be developed on an industrial scale. The electrochemical synthesis is performed successfully in the microreactors equipped with a graphite cathode under proper operative conditions. The performance of the process strongly depends on the nature of the cathode and, for micror…