Methanol oxidation reaction acid media

These conclusions were supported by the results obtained in a study of the reactions of various types of acetylenes with TTN (94). Hydration of the C=C bond was found to occur to a very minor extent, if at all, with almost all of the compounds studied, and the nature of the products formed was dependent on the structure of the acetylene and the solvent employed. Oxidation of diarylacetylenes with two equivalents of TTN in either aqueous acidic glyme or methanol as solvent resulted in smooth high yield conversion into the corresponding benzils (Scheme 23). The mechanism of this oxidation in aqueous medium most probably involves oxythallation of the acetylene, ketonization of the initially formed adduct (XXXV) to give the monoalkylthallium(III) derivative (XXXVI), and conversion of this intermediate into a benzoin (XXXVII) by a Type 1 process. Oxidation of (XXXVII) to the benzil (XXXVIII) by the second equivalent of reagent would then proceed in exactly the same manner as described for the oxidation of chalcones, deoxybenzoins, and benzoins to benzils by TTN. The mechanism of oxidation in methanol solution is somewhat more complex and has not yet been fully elucidated. 

Changing the reaction medium from acetic acid to water does not reduce the efficiency of the oxidant and, indeed, gradual dilution of an acetic acid medium with water, methanol or benzene increases the rates of oxidation of several glycols of factors of 500 to 1000 (ref. 260). This effect raises the question of whether the catalysis by trichloracetic acid vide supra) is solely an effect of acidity. 

H, Cl, Br, NO2, Me, MeO) by bromamine-B, catalysed in the presence of HCl in 30% aqueous methanol by RuCls have been smdied and a biphasic Hammett a-relationship derived. A kinetic study of the ruthenium(in)-catalysed oxidation of aliphatic primary amines by sodium A-bromo-j -toluenesulfonamide (bromamine-T, BAT) in hydrochloric acid medium has been undertaken and the mechanism of the reaction discussed. A concerted hydrogen-atom transfer one-electron transfer mechanism is proposed for the ruthenium(in)-catalysed oxidation of 2-methylpentane-2,4-diol by alkaline hexacyanoferrate(III). The kinetics of the oxidation of propane-... 

Other bidentate N-heterocyclic carbenes were used to form stable chelate complexes. A fine example is the use of palladium NHC complex 24 in the catalytic conversion of methane to methanol (Fig. 10) [111]. In this case the stability of the complexes is a requirement, since the reaction takes place in an acidic medium (trifluoroacetic acid) at elevated temperatures (80 °C) mediated by strong oxidizing agents (potassium peroxodisulfate). 

PANI-NTs synthesized by a template method on commercial carbon cloth have been used as the catalyst support for Pt particles for the electro-oxidation of methanol [501]. The Pt-incorporated PANl-NT electrode exhibited excellent catalytic activity and stabUity compared to 20 wt% Pt supported on VulcanXC 72R carbon and Pt supported on a conventional PANI electrode. The electrode fabrication used in this investigation is particularly attractive to adopt in solid polymer electrolyte-based fuel cells, which arc usually operated under methanol or hydrogen. The higher thermal stabUity of y-Mn02 nanoparticles-coated PANI-NFs on carbon electrodes and their activity in formic acid oxidation pomits the realization of Pt-free anodes for formic acid fuel cells [260]. The exceUent electrocatalytic activity of Pd/ PANI-NFs film has recently been confirmed in the electro-oxidation reactions of formic acid in acidic media, and ethanol/methanol in alkaline medium, making it a potential candidate for direct fuel cells in both acidic and alkaline media [502]. 

Chapter 1 discusses the current status of electrocatalysts development for methanol and ethanol oxidation. Chapter 2 presents a systematic study of electrocatalysis of methanol oxidation on pure and Pt or Pd overlayer-modified tungsten carbide, which has similar catalytic behavior to Pt. Chapters 3 and 4 outline the understanding of formic acid oxidation mechanisms on Pt and non-Pt catalysts and recent development of advanced electrocatalysts for this reaction. The faster kinetics of the alcohol oxidation reaction in alkaline compared to acidic medium opens up the possibility of using less expensive metal catalysts. Chapters 5 and 6 discuss the applications of Pt and non-Pt-based catalysts for direct alcohol alkaline fuel cells. 

Alternatively, treatment of oxybisberberine with pyridine hydrochloride in pyridine led to oxidative scission, and the nature of the products was dictated by the nucleophiles present and by the pH of the medium during the work-up. When the reaction was quenched with methanolic and aqueous acids, the products were the 8,13-dioxoberbines 44 and 45, respectively. These compounds undergo rapid, reversible, interconversion in acidic media through an immonium quinoid species. On the other hand, neutral work-up with buffered systems gives rise to the aporhoeadane 46, which is also produced rapidly but irreversibly on treatment of 45 with ammonium hydroxide. Alkaline work-up invariably produced as the major product Perkin s anhydroberberilic acid 47 as well as its solvolysis product noroxyhydrastinine (see Scheme 19.7). 

The reaction mechanisms of methanol oxidation at platinum electrodes in acid medium, according to the overall reaction,... 

On the other hand, the loadings of Ru deposits were lower than those of Pt deposits at both deposition potentials. In addition, the Pt-Ru catalysts electrodeposited on CNT/CC formed solid solutions, as confirmed by XRD analyses [65]. Through the electrochemical tests of methanol oxidation on the working specimens, it was found that the specimens with Pt-Ru catalysts exhibited better electroactivity (current density of methanol oxidation per unit Pt loading mass) than the specimens with only Pt (Figure 20.13). Direct electrooxidation is a very complex reaction because many intermediate species are involved. In an acidic medium this reaction requires platinum-based catalysts, even though Pt exhibits rather low activity [66]. 

The anode electrode-catalyst is one of the important components of the alkaline fuel cell as it helps in the electro-oxidation of fuel. It is desirable that the anode electrode-catalyst provides faster reaction kinetics and 100% oxidation of fuels to CO2 and H2O. The most widely used catalyst, without doubt, is platinum. Platinum seems to be the best choice for acidic solutions, but other metallic alloy with platinum or other metals can match its performance in alkaline medium because of the favorable fuel oxidation in alkaline medium. Different anode materials based on Pt (Prabhuram et al. 1998, Moralldn et al. 1995, Tripkivic et al. 1996), Pt-Ru (Wang et al. 2003, Manoharan et al. 2001), Co-W alloys (Shobba et al. 2002), sintered Ag/ PdO (Koscher et al. 2003), spent carbon electrodes impregnated with Fe, Fe" or Ag (Verma 2000), nickel impregnated silicate-1 (Khalil et al. 2005) and nickel dimethylglyoxime complex (Golikand et al. 2005) are some of the catalysts studied for the electro-oxidation of methanol in alkaline medium. 

The Nenitzescu process is presumed to involve an internal oxidation-reduction sequence. Since electron transfer processes, characterized by deep burgundy colored reaction mixtures, may be an important mechanistic aspect, the outcome should be sensitive to the reaction medium. Many solvents have been employed in the Nenitzescu reaction including acetone, methanol, ethanol, benzene, methylene chloride, chloroform, and ethylene chloride however, acetic acid and nitromethane are the most effective solvents for the process. The utility of acetic acid is likely the result of its ability to isomerize the olefinic intermediate (9) to the isomeric (10) capable of providing 5-hydroxyindole derivatives. The reaction of benzoquinone 4 with ethyl 3-aminocinnamate 35 illustrates this effect. ... 

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