Ethanol oxidation reaction products

From the mass spectrometric data and Eqs. (27) and (28), it is possible to calculate the relative current due to the formation of caibon dioxide, acetaldehyde and finally acetic acid from the ethanol oxidation reaction. These partial currents are shown in Fig. 36 for Pt/C, PtRu/C and PtsSn/C catalysts. " This figure clearly presents the efficiency of the three different catalysts towards the formation of reaction products resulting from the electro-oxidation of ethanol. This quantitative analysis allows us to evaluate the total number of exchanged electrons during the oxidation reaction and the global current efficiency (Aq) and product yield (Wq) of the reaction calculated from the total charge involved for each partial current (Table 4). 

This quantitative analysis allows a comparison in the product yield, Wq, for the ethanol oxidation reaction between different catalysts. In the discussed example, the three catalysts considered present close yields, with a low CO2 production (for Pt/C and PtRu/C catalysts CO2 is only produced during the positive going scan), whereas acetaldehyde and acetic acid both present a product yield of 60-70 % and 30-40 %, respectively. A shght increase in the acetaldehyde yield can be observed for the PtRu catalyst, leading to a lower Faradic efficiency for the ethanol oxidation reaction, compared to that obtained on Pt/C and PtsSn/C catalysts. 

Finally, the combined voltammetric and on-line differential electrochemical mass spectrometry measnrements allow a quantitative approach of the ethanol oxidation reaction, giving the partial current efficiency for each product, the total number of exchanged electrons and the global product yields of the reaction. But, it is first necessary to elucidate the reaction mechanism in order to propose a coherent analysis of the DBMS results. In the example exposed previously, it is necessary to state on the reaction products in order to evaluate the data relative to acetic acid production which cannot be directly detected by DBMS measurements. However, experiments carried out at high ethanol concentration (0.5 mol L" ) confirmed the presence of the ethyl acetate ester characterized by the presence of fragments at m/z = 61, 73 and 88 at ratios typical of the ethyl acetate mass spectrum. " This ethyl acetate ester is formed by the following chemical reaction between the electrochemically formed acetic acid and ethanol (Bq. 29) and confirms the formation of acetic acid. 

Some of the ethoxide species are converted to acetate (RCOO, where 1 =CH3) as demonstrated in Fig. 7.1 la. In the photo-oxidation of ethanol the reaction products are... 

Acetate is often the main product of the ethanol oxidation reaction. However, for concentrated alkaline solutions, side products are formed, including polymerized acetaldehyde and carbonate. Polyacetaldehyde is regarded as an unwanted by-product because it coats and blocks the catalyst layer. The complete oxidation of ethanol to carbonate is highly desired because it doubles the number of electrons per reagent molecule. The catalytic cleavage of the C-C bond in aqueous media is a challenging task in catalyst research. At DLR, this is a research topic in collaboration with the University of Diisseldorf [31, 32]. 

Fthanol is a nontoxic renewable energy source that can be produced from agricultural products its theoretical energy density (8.0 kWh/kg) is higher than that of methanol (6.1 kWh/kg). However, the commercialization of direct ethanol fuel cells (DFFCs) is considered more difficult than that of DMFCs, because the kinetics of ethanol oxidation reaction is slower than that of methanol oxidation even on the best available catalysts. 

Rao et al. studied ethanol oxidation reaction in a real fuel cell using 40% Pt/C as cathode and Pt/C (20% and 40%), PtRu/C, and PtaSn/C as anodes [51]. Their DBMS sensor consisted on a cylindrical detection volume through which anode outlet flow passes. This volume was separated from the vacuum system of the mass spectrometer by a microporous Teflon membrane (pore size 0.02 (im and thickness of 110 (im) supported by a Teflon disk. For Pt/C and 0.1 M ethanol the carbon dioxide selectivity increased with the reaction temperature. The selectivity was highest at 0.5-0.6V and doubled from 60°C (40%) to 90°C (ca. 85%). At higher potentials the CO2 selectivity decreased and increased the acetaldehyde production. CH3CHO formation also increased at lower temperatures (at 90 °C and low, ethanol concentration was almost absent). At high ethanol concentrations the selectivity to carbon dioxide decreased but this effect was less significant than temperature effect at least for ethanol concentrations lower than 1M. 

Eourth, incorporation of the synthesis of PtML electrocatalysts with the fuel-cell stack is predicted to further reduce the production cost and better accommodation of the catalysts on the electrode. These studies would substantially reduce the technical barriers to produce durable, economical fuel cells. The same stratagems may be true for realizing very high selectivity. Finally, in view of the limited availability of Pt, the concept of Pt L catalysts will have a broad impact on future catalysis research and technology. Indeed, most recently, we demonstrated that PtwL under the tensile strain (PtML/Au(lll)) has high activity for methanol and ethanol oxidation reactions."" ... 

Another pathway for the aromatization of the cr -adducts was found in the reactions of 3-pyrrolidino-l,2,4-triazine 4-oxide 81 with amines. Thus the treatment of 1,2,4-triazine 4-oxide 81 with ammonia leads to 5-amino-1,2,4-triazine 4-oxides 54—products of the telesubstitution reaction. In this case the cr -adduct 82 formed by the addition of ammonia at position 5 of the heterocycle undergoes a [l,5]sigmatropic shift resulting in 3,4-dihydro-1,2,4-triazine 83, which loses a molecule of pyrrolidine to yield the product 54. This mechanism was supported by the isolation of the key intermediates for the first time in such reactions—the products of the sigmatropic shift in the open-chain tautomeric form of tiiazahexa-triene 84. The structure of the latter was established by NMR spectroscopy and X-ray analysis. In spite of its open-chain character, 84 can be easily aromatized by refluxing in ethanol to form the same product 54 (99TL6099). 

Ninety-eight grams of 6-chloro-2-chloromethyl-4-phenylquinazoline 3-oxide hydrochloride were introduced into 600 cc of ice cold 25% methanolic methylamine. The mixture was initially cooled to about 30°C and then stirred at room temperature. After 15 hours the reaction product which precipitated was filtered off. The mother liquor was concentrated in vacuo to dryness. The residue was dissolved in methylene chloride, washed with water and dried with sodium sulfate. The methylene chloride solution was concentrated in vacuo and the crystalline residue was boiled with a small amount of acetone to dissolve the more soluble impurities. The mixture was then cooled at 5°C for 10 hours and filtered. The crystalline product, 7-chloro-2-methylamino-5-phenyl-3H-1,4-benzodiazepine 4-oxide, was recrystallized from ethanol forming light yellow plates, MP 236° to 236.5°C. 

The production rate of acetic acid was 2kg-h 1, where the maximum acetic acid concentration was 12%. Air was pumped into the fermenter with a molar flow rate of 200 moMi-. The chemical reaction is presented in (E. 1.1) and flow diagram in Figure 9.5. Determine the minimum amount of ethanol intake and identify the required mass balance for the given flow sheet. The ethanol biochemical oxidation reaction using A. aceti is ... 

The above-described reverse reaction (viz. the Fe-catalyzed dehydrogenation of alcohols to ketones/aldehydes) has been reported by Williams in 2009 (Table 9) [58]. In this reaction, the bicyclic complex 16 shows a sluggish activity, whereas the dehydrogenation of l-(4-methoxyphenyl)ethanol catalyzed by the phenylated complex 17 affords the corresponding ketone in 79% yield when 1 equiv. (relative to 17) of D2O as an additive was used. For this oxidation reaction, l-(4-methoxyphenyl) ethanol is more suitable than 1-phenylethanol and the reaction rate and the yield of product are higher. 

Poisoning of platinum fuel cell catalysts by CO is undoubtedly one of the most severe problems in fuel cell anode catalysis. As shown in Fig. 6.1, CO is a strongly bonded intermediate in methanol (and ethanol) oxidation. It is also a side product in the reformation of hydrocarbons to hydrogen and carbon dioxide, and as such blocks platinum sites for hydrogen oxidation. Not surprisingly, CO electrooxidation is one of the most intensively smdied electrocatalytic reactions, and there is a continued search for CO-tolerant anode materials that are able to either bind CO weakly but still oxidize hydrogen, or that oxidize CO at significantly reduced overpotential. 

Gold is generally considered a poor electro-catalyst for oxidation of small alcohols, particularly in acid media. In alkaline media, however, the reactivity increases, which is related to that fact that no poisoning CO-hke species can be formed or adsorbed on the surface [Nishimura et al., 1989 Tremihosi-Filho et al., 1998]. Similar to Pt electrodes, the oxidation of ethanol starts at potentials corresponding to the onset of surface oxidation, emphasizing the key role of surface oxides and hydroxides in the oxidation process. The only product observed upon the electrooxidation of ethanol on Au in an alkaline electrolyte is acetate, the deprotonated form of acetic acid. The lack of carbon dioxide as a reaction product again suggests that adsorbed CO-like species are an essential intermediate in CO2 formation. 

In acidic media, the reactivity of ethanol on Au electrodes is much lower than in alkaline media. The main product of the oxidation of ethanol on Au in an acidic electrolyte was found to be acetaldehyde, with small amounts of acetic acid [Tremiliosi-FiUio et al., 1998]. The different reactivities and the product distributions in different media were explained by considering the interactions between the active sites on Au, ethanol, and active oxygen species absorbed on or near the electrode surface. In acidic media, surface hydroxide concentrations are low, leading to relatively slow dehydrogenation of ethanol to form acetaldehyde as the main oxidation pathway. In contrast, in alkaline media, ethanol, adsorbed as an ethoxy species, reacts with a surface hydroxide, forming adsorbed acetate, leading to acetate (acetic acid) as the main reaction product. 

Another metal that has attracted interest for use as electrode material is rhodium, inspired by its high activity in the catalytic oxidation of CO in automotive catalysis. It is found that Rh is a far less active catalyst for the ethanol electro-oxidation reaction than Pt [de Souza et al., 2002 Leung et al., 1989]. Similar to ethanol oxidation on Pt, the main reactions products were CO2, acetaldehyde, and acetic acid. Rh, however, presents a significant better CO2 yield relative to the C2 compounds than Pt, indicating a... 

H2 production technologies based on natural gas. Operating the reaction at relatively lower temperature, between 300 and 450 °C could minimize the CO formation because the equilibria for WGS and CO oxidation reactions are thermodynamically more favorable at lower temperatures. In order to achieve this goal, highly selective catalysts that are specific for reforming via acetaldehyde formation rather than ethanol decomposition to CH4 and/or ethylene are required. The success in the development of ethanol-based H2 production technology therefore relies on the development of a highly active, selective and stable catalyst. 

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