Mechanism of carbon dioxide reduction

The mechanism of carbon dioxide reduction in aqueous and nonaqueous solutions was investigated by several authors. It is now generally accepted that the reduction of carbon dioxide to formate ions is a multistep reaction with the intermediate formation of free radicals CO2 and HCO2 either in the solution or adsorbed on the electrode ... 

Mechanisms of carbon dioxide reduction in both aqueous and nonaqueous solutions have been studied mainly at metal electrodes. 

More complicated reactions that combine competition between first- and second-order reactions with ECE-DISP processes are treated in detail in Section 6.2.8. The results of these theoretical treatments are used to analyze the mechanism of carbon dioxide reduction (Section 2.5.4) and the question of Fl-atom transfer vs. electron + proton transfer (Section 2.5.5). A treatment very similar to the latter case has also been used to treat the preparative-scale results in electrochemically triggered SrnI substitution reactions (Section 2.5.6). From this large range of treated reaction schemes and experimental illustrations, one may address with little adaptation any type of reaction scheme that associates electrode electron transfers and homogeneous reactions. 

Major limitation associated with carbon dioxide reduction is the accuracy of the analytical measurements employed. The photocatalytic process is a multielectron transfer process, hence the reaction leads to the formation of a variety of products like carbon monoxide, methane, higher hydrocarbons, alcohol, aldehydes, carboxylic acid etc., with some intermediates. The identification and quantification of the products are needed for the best selection of photocatalyst, comparison and elucidation of reaction mechanisms. Currently there is no standard analysis method that has been developed for product analysis of carbon dioxide reduction. Hence the results of these measurements also include the products derived from the carbon contamination invariably present in the reaction sys-... 

Pearce, D.J. and D. Pletcher (1986). A study of the mechanism for the elecirocatalysis of carbon dioxide reduction by nickel and cobalt square planar eomplexes in solution, y. Electroanal. Chem. 197(1—2), 317—330. 

Great promise exists in the use of graphitic carbons in the electrochemical synthesis of hydrogen peroxide [reaction (15.21)] and in the electrochemical reduction of carbon dioxide to various organic products. Considering the diversity in structures and surface forms of carbonaceous materials, it is difficult to formulate generalizations as to the influence of their chemical and electron structure on the kinetics and mechanism of electrochemical reactions occurring at carbon electrodes. 

From a fundamental viewpoint, carbon dioxide reduction is a model reaction which can help us to understand better the mechanism of natural photosynthesis.11 Development of artificial photosynthetic systems, by mimicking functions of green plants, is one of... 

In one mechanism, Pd° generated by reduction of Pd2+ with formic acid forms hydridoformatopalladium complex 102, which reacts with isoprene to form formato(methylbutenyl)palladium complex 103. Then, insertion of the second molecule of isoprene takes place. Finally, reductive elimination and evolution of carbon dioxide give the dimers ... 

The most probable mechanism for the reduction requires the initial nucleophilic attack by the hydridometal complex on the nitro group, followed by intramolecular cyclization and extrusion of carbon dioxide. Repetition of the cyclization and extrusion sequence, followed by proton transfer, leads to aniline (Scheme 11.6). 

Biological. Four Pseudomonas sp., including Pseudomonas putida (ATCC culture 29607) isolated from soil, degraded chloropicrin by sequential reductive dechlorination. The proposed degradative pathway is chloropicrin -> nitrodichloromethane nitrochloromethane nitromethane + small amounts of carbon dioxide. In addition, a highly water soluble substance tentatively identified as a peptide was produced by a nonenzymatic mechanism (Castro et al., 1983). 

The photoreductive synthetic process that promotes the assimilation of carbon dioxide into carbohydrates, other reduced metabolites, as well as ATP (synthesis of the latter is termed photophosphorylation). Photosynthesis is the primary mechanism for transducing solar energy into biomass, and green plants utilize chlorophyll a to capture a broad spectrum of solar radiant energy reaching the Earth s surface. Photosynthetic bacteria typically produce NADPH, the reductive energy of which is converted to ATP. 

The mechanism of acid-catalyzed decarboxylation of hexuronic acids has been the subject of many investigations.231,232 The formation of carbon dioxide is accompanied by the formation of 2-furaldehyde, C5H402 (82) as the main product, along with considerable amounts of humins however, both 5-formyl-2-furoic acid (83) and reductic acid (84) have been isolated as end products from treatment of hexuronic acids with strong acid. 

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