Ethanol and methanol oxidation

Arico AS, Creti P, Antonucci PL, Antonucci V. 1998. Comparison of ethanol and methanol oxidation in a liquid-feed solid polymer electrolyte fuel cell at high temperature. Electrochem Sol Lett 1 66-68. 

Matsumoto F (2012) Ethanol and methanol oxidation activity of PtPb, PtBi, and PtBi2 intermetallic compounds in alkaline media. Electrochemistry 80(3) 132-138... 

Pd NPs are commonly used in oxidations of alcohols and can be incorporated into an The morphology of the particles can be suited to different apphcations, e.g., flower-like particles, due to their concave tetrahedral subunits, exhibited a high electrocatalytic activity toward ethanol and methanol oxidation compared with that of the commercial Pd black catalyst.A Pd complex containing triphenylphosphine and a Schiffbase catalyst was used " for the study of the solvent efiect in carbonylation of primary and secondary alcohols to aldehydes and ketones, in the presence of NaOCl as an oxidant. By kinetic study of different proportions between the imidazolium-based IL ([C2mim][PF6]), it was shown that the acceleration of the reaction depends on the mixing proportion and that the best ratio was 1 1. 

Li Z, Gong H, Mu T, Luan Y. Ionic liquid-assisted synthesis of unusual Pd particles with enhanced electrocatalytic performance for ethanol and methanol oxidation. CrystEngComm. 2014 16 4038-4044. 

A. S. Aric6, P. Creti, P. L. Antonucci and V. Antonucci, Comparison of Ethanol and Methanol Oxidation in a Liquid-Feed SoUd Polymer Electrolyte Fuel Cell at High Temperature, Electrochem. Solid-State Lett., Vol. 1, No. 2, pp. 66-68, 1998. 

The same samples, after a pretreatment in flowing oxygen (10%) at 625 K, were used as catalysts for the oxidative dehydrogenation of ethanol and methanol in the same reactor. The reaction mixture consisted of O2 (3 or 5%), methanol vapor (3%) or ethanol vapor (5%) and He (balance), all delivered by Tylan mass flow controllers or vaporizer flow controllers. Products were analyzed by gas chromatography. The catalysts exhibited no induction period and their activities were stable over many days and over repeated temperature cycles. 

A similar biradical process has also been estabhshed for some mononuclear Cu complexes 17 (derived from ligand 16) and 18 that contain two iminosemiquinone radicals [156,160]. Complex 17 proved to be a good catalyst for the aerial oxidation of benzyl alcohol to benzaldehyde, while 18 even oxidizes ethanol and methanol. Primary kinetic isotope effects again confirm that H-atom abstraction from the substrate is the rate-determining step. 

A somewhat similar oxidation of terminal alkenes to methyl ketone and alcohol by 02 in the presence of Co(salMDPT) [salMDPT = bis(salicylideneiminopropyl)methylamine] and in ethanol solvent has recently been reported by Drago and coworkers (equation 244).560 Only terminal alkenes were found to be reactive with this catalytic system. The reaction is alcohol dependent and occurs in ethanol and methanol but not in t-butyl or isopropyl alcohols. The alcohol is concomitantly oxidized during the reaction, and may act as a coreducing agent and/or favor the formation of cobalt hydride. This oxidation might occur according to the mechanism of equation (243). 

Based on their experimental results concerning ethanol and methanol photooxidation by Au/Ti02 composites under visible-light illumination, Tatsuma et al. (Tian and Tatsuma 2005) proposed a plasmon-induced charge separation scheme. They observed a surprising phenomenon, in which the photoelectrons were excited from Au nanoparticles and transferred to the CB of Ti02 (Wood et al. 2001 Subramanian et al. 2004). Meanwhile, the oxidized Au species accepted electrons from the donor molecules present in the solution to recover the charge balance. The process is illustrated in Fig. 16.23. 

The treatment for methanol or ethylene glycol poisoning is the same. The patient is given intravenous infusions of diluted ethanol. The ADH enzyme is swamped by all the ethanol, allowing time for the kidneys to excrete most of the methanol (or ethylene glycol) before it can be oxidized to formic acid (or oxalic acid). This is an example of competitive inhibition of an enzyme. The enzyme catalyzes oxidation of both ethanol and methanol, but a large quantity of ethanol ties up the enzyme, allowing time for excretion of most of the methanol before it is oxidized. 

Figure 12. Cyclic voltammograms of methanol, ethanol and glycerol oxidation on a Pd/MWCNT electrode in 2 M KOH. Pd loading 17 tg cm. Scan rate 50 mV s". Reprinted from Ref. 29, Copyright (2009) with permission from Elsevier.

---