The mathematical description of the electrosynthesis of composites of oxy-hydroxycompounds cobalt with polypyrrole overooxidazed

The electrosynthesis of the composite with of the overoxidized polypyrrole with cobalt oxy-hydroxide in strongly acidic media has been described mathematically, using linear stability theory and bifurcation analysis. The steadystates stability conditions and oscillatory and monotonic instability requirements have been described too. The system´s behavior was compared with behavior of other systems with overoxidation, electropolymerization of heterocyclic compounds and electrosynthesis of the cobalt oxy-hydroxides

Electrochemical synthesis of peroxomonophosphate using boron-doped diamond anodes

A new method for the synthesis of peroxomonophosphate, based on the use of boron-doped diamond electrodes, is described. The amount of oxidant electrogenerated depends on the characteristics of the supporting media (pH and solute concentration) and on the operating conditions (temperature and current density). Results show that the pH, between values of 1 and 5, does not influence either the electrosynthesis of peroxomonophosphate or the chemical stability of the oxidant generated. Conversely, low temperatures are required during the electrosynthesis process to minimize the thermal decomposition of peroxomonophosphate and to guarantee significant oxidant concentration. In addition, a marked influence of both the current density and the initial substrate is observed. This observation can be explained in terms of the contribution of hydroxyl radicals in the oxidation mechanisms that occur on diamond surfaces. In the assays carried out below the water oxidation potential, the generation of hydroxyl radicals did not take place. In these cases, peroxomonophosphate generation occurs through a direct electron transfer and, therefore, at these low current densities lower concentrations are obtained. On the other hand, at higher potentials both direct and hydroxyl radical-mediated mechanisms contribute to the oxidant generation and the process is more efficient. In the same way, the contribution of hydroxyl radicals may also help to explain the significant influence of the substrate concentration. Thus, the coexistence of both phosphate and hydroxyl radicals is required to ensure the generation of significant amounts of peroxomonophosphoric acid

Recent progress towards the electrosynthesis of ammonia from sustainable resources

Ammonia (NH3) is a key commodity chemical of vital importance for fertilisers. It is made on an industrial scale via the Haber Bosch process, which requires significant infrastructure to be in place such that ammonia is generally made in large, centralized facilities. If ammonia could be produced under less demanding conditions, then there would be the potential for smaller devices to be used to generate ammonia in a decentralized manner for local consumption. Electrochemistry has been proposed as an enabling technology for this purpose as it is relatively simple to scale electrolytic devices to meet almost any level of demand. Moreover, it is possible to envisage electrosynthetic cells where water could be oxidised to produce protons and electrons at the anode which could then be used to reduce and protonate nitrogen to give ammonia at the cathode. If this nitrogen were sourced from the air, then the only required infrastructure for this process would be supplies of water, air and electricity, the latter of which could be provided by renewables. Hence an electrosynthetic cell for ammonia production could allow NH3 to be generated sustainably in small, low-cost devices requiring only minimal facilities. In this review, we describe recent progress towards such electrosynthetic ammonia production devices, summarizing also some of the seminal literature in the field. Comparison is made between the various different approaches that have been taken, and the key remaining challenges in the electrosynthesis of ammonia are highlighted

Effect of electropolymerisation conditions on the permeability of polyphenol films deposited on a vitreous carbon electrode

Polymeric films were prepared from alkaline (NaOH) phenol aqueous solutions on a vitreous carbon (VC) electrode by potentiostatic or galvanostatic electro-oxidation. Permeation through such films was studied by rotating-disk electrode using the ferricyanide redox couple, and by cyclic voltammetry using phenate ions. The influence of the electropolymerisation controllable parameters such as NaOH and phenol concentrations, potential or current applied, electrosynthesis time, temperature and hydrodynamic conditions (electrode rotation + solution magnetic stirring) on the permeability of these polymeric films was examined. Conditions for the removal of phenol by electropolymerisation are discussed on the basis of the permeability of polyphenol films obtained by electrosynthesis. Permeable films were formed for a concentration of free hydroxyl anion larger of 0.1 M. An increase of the temperature to 85°C favours the formation of highly permeable films, thus avoiding electrode fouling

Electrocarboxylation in supercritical CO2 and CO2-expanded liquids

In this study, the electrocarboxylation of benzyl chloride in pressurized CO2, or pressurized mixtures of dimethylformamide (DMF) and CO2, was investigated in order to synthesize phenylacetic acid. A stainless steel cathode was used as the working electrode, whereas a sacrificial massive magnesium rod or a platinized platinum grid was used as the anode, tetrabutylammonium perchlorate (TBAP) or tetrakis(decyl)ammonium tetraphenylborate (TDATPhB) being the supporting electrolyte. The electrocarboxylation was carried out at 40 ◦C, at operating pressures of 1, 6, 7, 8, 9 and 12MPa, using current densities ranging from 0.1 to 150mAcm−2. It was found that a small amount of DMF was necessary to ensure the solubility of the supporting electrolyte, to obtain sufficient electrical conductivity of the medium. The best resultswere obtained using the magnesium sacrificial anode, at 6MPa. After consumption of the theoretical amount of electrical current (2F mol−1), 65.7% benzyl chloride conversion was reached, together with an 82.4% phenylacetic acid selectivity and a 54.2% faradaic yield. Detected by-productswere toluene, bibenzyle, benzyl alcohol and benzaldehyde

Electrochemical preparation of peroxodisulfuric acid using boron doped diamond thin film electrodes

We have investigated the electrochemical oxidation of sulfuric acid on boron-doped synthetic diamond electrodes (BDD) obtained by HF CVD on p-Si. The results have shown that high current efficiency for sulfuric acid oxidation to peroxodisulfuric acid can be achieved in concentrated H2SO4 (>2 M) at moderate temperatures (8–10 °C). The main side reaction is oxygen evolution. Small amounts of peroxomonosulfuric acid (Caro's acid) have also been detected. A reaction mechanism involving hydroxyl radicals, HSO4− and undissociated H2SO4 has been proposed. According to this mechanism electrogenerated hydroxyl radicals at the BDD anode react with HSO4− and H2SO4 giving peroxodisulfate

Perspectives in flow electrochemistry

Electrosynthesis is an old method currently moving again in the focus of organic synthesis. Some limitations of conventional electrosynthesis can be overcome by the use of electrochemical flow devices. This perspective indicates where the pitfalls, where the advantages and where the challenges are in implementing flow electrosynthesis as an alternative tool for the synthetic chemist

Reactors for microbial electrobiotechnology

From the first electromicrobial experiment to a sophisticated microbial electrochemical process - it all takes place in a reactor. Whereas the reactor design and materials used strongly influence the obtained results, there are no common platforms for MES reactors. This is a critical convention gap, as cross-comparison and benchmarking among MES as well as MES vs. conventional biotechnological processes is needed. Only knowledge driven engineering of MES reactors will pave the way to application and commercialization. In this chapter we first assess the requirements on reactors to be used for bioelectrochemical systems as well as potential losses caused by the reactor design. Subsequently, we compile the main types and designs of reactors used for MES so far, starting from simple H-cells to stirred tank reactors. We conclude with a discussion on the weaknesses and strengths of the existing types of reactors for bioelectrochemical systems that are scored on design criteria and draw conclusions for the future engineering of MES reactors. [GRAPHICS]