Carbon dioxide electrolytic reduction

Niobium Trichloride, NbCl3, is prepared by leading the vapour of niobium pentachloride through a heated tube.4 It is also formed in small quantity by the action of carbon tetrachloride vapour on niobium pentoxide contained in a hard-glass tube, and has probably been prepared in solution by the electrolytic reduction of the pentachloride.4 It forms a black, crystalline crust with an almost metallic lustre, which closely resembles the appearance of a film of sublimed iodine. It is not decomposed by water or ammonia, but is readily oxidised by dilute nitric add to niobium pentoxide. On being heated to a red heat in an atmosphere of carbon dioxide, a sublimate of niobium oxytrichloride, NbOCl3, is produced, the carbon dioxide undergoing reduction to the monoxide. 

New Synthesis. Many attempts have been made to synthesize oxaUc acid by electrochemical reduction of carbon dioxide in either aqueous or nonaqueous electrolytes (53—57). For instance, oxaUc acid is prepared from CO2 as its Zn salt in an undivided ceU with Zn anodes and stainless steel cathodes ia acetonitrile containing (C4H2)4NC104 and current efficiency of >90% (53). Micropilot experiments and a process design were also made. 

Carbon dioxide as additive improves the behavior of (Li02C0CH2)2 films formed above intercalation potentials in EC/DEC-based electrolytes due to increased formation of Li 2 CO 3 [200], It is interesting to note that SO2 reduction occurs at quite high potentials, before the reduction of other electrolyte components films contain inorganic and organic lithium salts [201]. 

Electrochemical reduction of carbon dioxide is usually conducted in aqueous or nonaqueous electrolyte solutions at cathodes made of various materials. As a result, various organic substances can form. The most common reactions are as follows ... 

Cathodic reduction is the most promising approach to the removal of carbon dioxide from a closed atmosphere. Methods developed so far provide for electrode materials, electrolytes, and electrolysis conditions where CO2 can be reduced to hquid organic products of low molecular weight such as formic acid. More complex systems are required to regenerate foodstuffs from the rejects of human vital activities during... 

A little later, Russell et al.19 tried to obtain methanol from carbon dioxide by electrolysis. Reduction of carbon dioxide to formate ion took place in a neutral electrolyte at a mercury electrode. On the other hand, formic acid was reduced to methanol either in a perchloric acid solution at a lead electrode or in a buffered formic acid solution at a tin electrode. The largest faradaic efficiency for methanol formation from formic acid was ca. 12%, with poor reproducibility, after passing 1900 C in the perchloric acid solution at Pb in a very narrow potential region (-0.9 to -1.0 V versus SCE). In the buffered formic acid solution (0.25 M HCOOH + 0.1 M... 

Recently, results of careful experiments were reported by Ito et a/.101 They claimed that formic acid, formaldehyde, and methanol, which had been previously reported as photoelectrochemical reduction products of carbon dioxide, were observed also by photolysis of cell materials, such as electrolytes, including 15-crown-5 ether, and epoxy resin, which has often been used as the molding material of semiconductor electrodes in aqueous solutions. Previously reported reduction products were obtained also under nitrogen with (Table 4) and without (Table 5) a p-GaP photocathode under illumination. These precise experiments under improved conditions, where no photolytic products were observed, gave the result that the main reduction product of carbon dioxide at a p-GaP photocathode in aqueous electrolytes was formic acid. Thus, many kinds of products reported in previous papers83,97,100 were suggested to be due to photolysis of cell materials. 

The solid is very reactive towards air, moisture or carbon dioxide, and tends to explode readily, also decomposing violently on heating. It is produced from sodium nitrate or sodium nitrite by electrolytic reduction, or action of sodium. 

The addition of carbanions, generated electrochemically by reduction of the carbon-halogen bond, to carbon dioxide has been examined under a variety of experimental conditions. Direct electrosynthesis of carboxylic acids in a divided cell using an aprotic solvent and a tetraalkylammonium salt as electrolyte is most sue-... 

Numerous methods for the synthesis of salicyl alcohol exist. These involve the reduction of salicylaldehyde or of salicylic acid and its derivatives. The alcohol can be prepared in almost theoretical yield by the reduction of salicylaldehyde with sodium amalgam, sodium borohydride, or lithium aluminum hydride by catalytic hydrogenation over platinum black or Raney nickel or by hydrogenation over platinum and ferrous chloride in alcohol. The electrolytic reduction of salicylaldehyde in sodium bicarbonate solution at a mercury cathode with carbon dioxide passed into the mixture also yields saligenin. It is formed by the electrolytic reduction at lead electrodes of salicylic acids in aqueous alcoholic solution or sodium salicylate in the presence of boric acid and sodium sulfate. Salicylamide in aqueous alcohol solution acidified with acetic acid is reduced to salicyl alcohol by sodium amalgam in 63% yield. Salicyl alcohol forms along with -hydroxybenzyl alcohol by the action of formaldehyde on phenol in the presence of sodium hydroxide or calcium oxide. High yields of salicyl alcohol from phenol and formaldehyde in the presence of a molar equivalent of ether additives have been reported (60). Phenyl metaborate prepared from phenol and boric acid yields salicyl alcohol after treatment with formaldehyde and hydrolysis (61). 

Transition-metal -phthalocyanines as catalysts in acid medium. To prevent carbonate formation by the carbon dioxide in the air or that produced by oxidation of carbonaceous fuels, an acid electrolyte is necessary hence it is important to find electrocatalysts for an acid medium. Independently of Jasinski, we were soon able to show 3>4> that under certain conditions the reduction of oxygen in dilute sulfuric acid proceeded better with phthalocyanines on suitable substrates than with platinum metal. The purified phthalocyanines were dissolved in concentrated sulfuric acid and precipitated on to the carbon substrate by addition of water. This coated powder was made into porous electrodes bound with polyethylene and having a geometrical surface of 5 cm2 (cf. Section 2.2.2.1.). The results obtained with compact electrodes of this type are shown in Fig. 6. 

The ECMS method has been used effectively in such studies as electrolytic reduction of carbon dioxide and electrolytic oxidation of methanol. The example in Fig. 9.8 is for the electrolytic oxidation of propylene carbonate (PC) in the electrolyte solution... 

Reduction of add solutions of vanadium pentoxide to the tetravalent state also takes place with bismuth amalgam 5 magnesium gives the trivalent salts of vanadium, while by using zinc, zinc coated with cadmium, electrolytically deposited cadmium, or sodium amalgam in the absence of air, divalent vanadium salts are obtained in solution.7 Vanadous salts and hypovanadous salts are, however, much more conveniently prepared by electrolytic reduction of acid solutions of vanadium pentoxide in an atmosphere of carbon dioxide.8... 

By the electrolytic reduction of a solution of niobium pentoxide in (a) concentrated hydrochloric acid and (b) dilute hydrochloric acid, and subsequent evaporation in vacuo or in an atmosphere of carbon dioxide, two compounds having the following compositions have been reported 3... 

Many attempts have been made to synthesize oxalic acid by electrochemical reduction of carbon dioxide in either aqueous or nonaqueous electrolytes. 

Aluminum is manufactured by the electrolytic reduction of pure alumina (A1203) in a bath of fused cryolite (Na3AlF6). It is not possible to reduce alumina with carbon because aluminum carbide (A14C3) is formed and a back-reaction between aluminum vapor and carbon dioxide in the condenser quickly reforms the original aluminum oxide again. 

Ito K, Yoshida M, Ohta S, IidaT. On the reduction products of carbon dioxide at a p-type gallium phosphide photocathode in aqueous electrolytes. Bull Chern Soc Jpn 1984 57 583-4. 

Mahmood et al. [117] studied the electrochemical reduction of carbon dioxide using gas diffusion electrodes. The reduction was performed on metal (lead, indium, and tin)-impregnated Teflon -bonded carbon gas diffusion electrodes in a sulfuric acid electrolyte over a 1 - 5 pH range. A schematic of the cell is shown in Fig. 24. The following reactions occurred ... 

The electrocatalytic behavior of cathodes appears to play a crucial role in the reduction of carbon dioxide. To find more efficient catalysts, detailed mechanistic studies of CO2 reduction are needed. Further studies could also concentrate on the investigation of different electrolytes as well as different catalysts delivering products of choice, such as alcohols. 

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