Propylene carbonate redox reactions

Water is involved in most of the photodecomposition reactions. Hence, nonaqueous electrolytes such as methanol, ethanol, N,N-d i methyl forma mide, acetonitrile, propylene carbonate, ethylene glycol, tetrahydrofuran, nitromethane, benzonitrile, and molten salts such as A1C13-butyl pyridium chloride are chosen. The efficiency of early cells prepared with nonaqueous solvents such as methanol and acetonitrile were low because of the high resistivity of the electrolyte, limited solubility of the redox species, and poor bulk and surface properties of the semiconductor. Recently, reasonably efficient and fairly stable cells have been prepared with nonaqueous electrolytes with a proper design of the electrolyte redox couple and by careful control of the material and surface properties [7], Results with single-crystal semiconductor electrodes can be obtained from table 2 in Ref. 15. Unfortunately, the efficiencies and stabilities achieved cannot justify the use of singlecrystal materials. Table 2 in Ref. 15 summarizes the results of liquid junction solar cells prepared with polycrystalline and thin-film semiconductors [15]. As can be seen the efficiencies are fair. Thin films provide several advantages over bulk materials. Despite these possibilities, the actual efficiencies of solid-state polycrystalline thin-film PV solar cells exceed those obtained with electrochemical PV cells [22,23]. 

Intercalation reactions of the dichalcogenides with alkali metals are redox reactions in which the host lattice is reduced by electron transfer from the alkali metal. Lithium and sodium intercalation reactions, for example, have been studied using cells of the type Li/LiC104-dioxolane/MX2 andNa/Nal-propylene carbonate/MX2. The reactions proceed spontaneously to form the intercalation compound if the cell is short circuited alternatively, a reverse potential can be apphed to control the composition of the final product. Apart from their application in synthesis, such electrochemical cells can be used to obtain detailed thermodynamic information and to establish phase relations by measuring the dependence of the equilibrium cell voltage on composition (see Figure 4). 

Hashmi and Upadhyaya compared the electrochemical properties of the electrochemically synthesized MnO /PPy composite electrodes, fabricated with different electrolytes, namely polymer electrolyte film (polyvinyl alcohol [PVA]-HjPO aqueous blend), aprotic liquid electrolyte (LiClO -propylene carbonate [PC]), and polymeric gel electrolyte (poly methyl methacrylate [PMMA]-ethylene carbonate [EC]-PC-NaClO ) [60]. The cell with aqueous PVA-H PO showed non-capacitive behavior owing to some reversible chemical reaction of MnO with water, while the MnO / PPy composite was found to be a suitable electrode material for redox supercapacitors with aprotic (non-aqueous) electrolytes. The solid-state supercapacitor based on the MnO /PPy composite electrodes with gel... 

Using this technique, Kwak et al. have studied the possible involvement of anion transport in Prussian blue in acetonitrile and propylene carbonate solutions. It is known that cation transport is dominant during the redox reaction of Prussian blue films and that the electroactivity and ion transport behaviour of Prussian blue films are highly limited by the pore size because Prussian blue films have a rigid zeolitic structure. The electroactivity in aqueous solutions... 

In the investigation of hydrocarbon partial oxidation reactions the study of the factors that determine selectivity has been of paramount importance. In the past thirty years considerable work relevant to this topic has been carried out. However, there is yet no unified hypothesis to address this problem. In this paper we suggest that the primary reaction pathway in redox type reactions on oxides is determined by the structure of the adsorbed intermediate. When the hydrocarbon intermediate (R) is bonded through a metal oxygen bond (M-O-R) partial oxidation products are likely, but when the intermediate is bonded through a direct metal-carbon bond (M-R) total oxidation products are favored. Results on two redox systems are presented ethane oxidation on vanadium oxide and propylene oxidation on molybdenum oxide. 

Replacement of carbon atoms in the propylene bridge of the complex 56 by heteroatoms, particularly by metal atoms as is represented by nickel in complex 65 [20], is interesting in view of the redox chemistry. Preparation of 65 succeeds also via a template reaction (Fig 13). 

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