On-line FTIR spectroscopic investigations of methanol oxidation in a direct methanol fuel cell

A real-time Fourier transform infrared spectroscopy (FTIRS) analysis of the products of methanol oxidation in a prototype direct-methanol fuel cell operating at high temperatures (150 to 185°C) is reported here. The methanol oxidation products on platinum black and platinum-ruthenium catalyst surfaces were determined as a function of the fuel cell operating temperature, current density, and methanol/water mole ratio. Neither formaldehyde nor formic acid was detected in anode exhaust gas at all cell operating conditions. The product distributions of methanol oxidation obtained by on-line FTIRS are consistent with our previous results obtained by on-line mass spectroscopy under similar conditions. With pure methanol in anode feed, methanaldimethylacetal was found to be the main product, methyl formate and CO were also found. However, when water was present in the anode feed, the main product was CO , and the formation of methanaldimethylacetal and methyl formate decreased significantly with increase of the water/methanol mole ratio. Increase of cell operating temperature enhanced the formation of CO and decreased the formation of methanaldimethylacetal and methyl formate. Pt/Ru catalyst is more active for methanol oxidation and has a higher selectivity toward CO formation than Pt-black. Nearly complete methanol oxidation, i.e., the product was almost exclusively CO , was achieved using a Pt/Ru catalyst and a water/methanol mole ratio of 2 or higher in the anode feed at a temperature of 185°C or above.

Trimethoxymethane as an alternative fuel for a direct oxidation PBI polymer electrolyte fuel cell

The oxidation of trimethoxymethane (TMM) (trimethyl orthoformate) in a direct oxidation PBI fuel cell was examined by on-line mass spectroscopy and on-line FTIR spectroscopy. The results show that TMM was almost completely hydrolyzed in a direct oxidation fuel cell which employs an acid doped polymer electrolyte to form a mixture of methylformate, methanol and formic acid. It also found that TMM was hydrolyzed in the presence of water at 120°C even without acidic catalyst. The anode performance improves in the sequence of methanol, TMM, formic acid/methanol, and methylformate solutions. Since formic acid is electrochemically more active than methanol, these results suggest that formic acid is probably a key factor for the improvement of the anode performance by using TMM instead of methanol under these conditions. © 1998 Elsevier Science Ltd. All rights reserved.

In situ FTIR spectroscopic studies of the oxidation of CO adsorbates on Ru(0 0 0 1) electrodes under open circuit conditions

This paper reports the first observation, using in situ FTIR spectroscopy, of the oxidation of CO adsorbates on the Ru(0001) electrode to CO under open circuit (oc) conditions in both perchloric acid and sulphuric acid solution at 20 and 55 °C. While the significant oc oxidation of the adsorbed CO on the Ru(0001) electrode was observed in perchloric acid solution, much less oc oxidation took place in sulfuric acid solution due to the specific adsorption of bisulfate at the Ru surface which inhibits the surface oxidation and reduces the reactivity of the surface towards the oxidation of CO . The oc oxidation of the CO depends strongly on the oxygen concentration in the solution and the temperature. The data so obtained are compared to those observed at the gas|solid interface, as well as to those obtained from the electro-oxidation of CO , and possible new catalytic oxidation reaction mechanisms are discussed. In addition, it is shown that the C-O frequency of the adsorbed CO may be used as an effective probe of the open circuit potential. © 2003 Elsevier B.V. All rights reserved.

In situ FTIR studies on the effect of temperature on the electro-oxidation of small organic molecules at the Ru(0001) electrode

The adsorption and electro-oxidation of formaldehyde, formic acid and methanol at the Ru(0001) electrode in perchloric acid solution have been studied as a function of temperature, potential and time using in situ FTIR spectroscopy, and the results interpreted in terms of the surface chemistry of the Ru(0001) electrode and compared to those obtained during our previous studies on the adsorption of CO under the same conditions. It was found that no dissociative adsorption or electro-oxidation of methanol takes place at Ru(0001) at potentials 1000 mV, both the oxidation of formic acid to CO and the oxidation of formaldehyde to both CO and formic acid were significantly increased, and the oxidation of methanol to CO and methyl formate was observed, all of which were attributed to the formation of an active RuO phase on the Ru(0001) surface.

Pioglitazone protects HDL(2&3) against oxidation in overweight and obese men

The worldwide epidemic of obesity is a major public health concern and is persuasively linked to the rising prevalence of diabetes and cardiovascular disease. Obesity is often associated with an abnormal lipoprotein profile, which may be partly negated by pioglitazone intervention, as this can influence the composition and oxidation characteristics of low-density lipoprotein (LDL). However, as pioglitazone's impact on these parameters within high-density lipoprotein (HDL), specifically HDL(2&3), is absent from the literature, this study was performed to address this shortcoming.

An investigation of the role of surface nitrate species in the oxidation of propene on a Pt-based diesel oxidation catalyst

Enhancing the low temperature activity of diesel oxidation catalysts is important for cold-start conditions and the possible importance of nitrate species in oxidation reactions has been proposed although definitive evidence has not been reported. To investigate the possible role of surface nitrates, their adsorption and reactivity on a Pt-based diesel oxidation catalyst have been investigated using the Short Time on Stream (STOS) transient kinetic technique. The results provide for the first time definitive evidence for the oxidation of propene by some of these nitrate-type species. © The Royal Society of Chemistry 2013.

Critical role of water in the direct oxidation of CO and hydrocarbons in diesel exhaust after treatment catalysis

CO and C3H6 oxidation have been carried out in the absence and presence of water over a Pd/Al2O3catalyst. It is clear that water promotes CO and, as a consequence, C3H6oxidation takes place at muchlower temperatures compared with the dry feed. The significant increase in the catalyst’s activity withrespect to CO oxidation is not simply associated with changes in surface concentration as a result ofcompetitive adsorption effects. Utilising18O2as the reactant allows the pathways whereby the oxidationdue to gaseous dioxygen and where the water activates the CO and C3H6to be distinguished. In thepresence of water, the predominant pathway is via water activation with C16O2and C16O18O being themajor species formed and oxidation with dioxygen plays a secondary role. The importance of wateractivation is further supported by the significant decrease in its effect when using D2O versus H2O.

Novel ruthenium-terpyridyl complex for direct oxidation of amines to nitriles

High catalytic activity and selectivity has been demonstrated for the oxidation of both aliphatic and aromatic amines to nitriles under benign conditions with dioxygen or air using the Ru2Cl4(az-tpy)(2) complex. The conversion was found to be strongly influenced by the alkyl chain length of the reactant with shorter chain amines found to have lower conversions than those with longer chains. Importantly, by using the ruthenium terpyridine complex functionalized with azulenyl moiety at the 4 position of central pyridine core provided a much higher reactivity catalyst compared with a series of ruthenium terpyridine-based ligand complexes reported. Mechanistic studies using deuterated benzylamine demonstrated the importance of RuOH in this reaction.

Low loading platinum nanoparticles on reduced graphene oxide-supported tungsten carbide crystallites as a highly active electrocatalyst for methanol oxidation

In this study, low loading platinum nanoparticles (Pt NPs) have been highly dispersed on reduced graphene oxide-supported WC nanocrystallites (Pt-WC/RGO) via program-controlled reduction-carburization technique and microwave-assisted method. The scanning electron microscopy and transmission electron microscopy results show that WC nanocrystallites are homogeneously decorated on RGO, and Pt NPs with a size of ca. 3 nm are dispersed on both RGO and WC. The prepared Pt-WC/RGO is used as an electrocatalyst for methanol oxidation reaction (MOR). Compared with the Pt/RGO, commercial carbon-supported Pt (Pt/C) and PtRu alloy (PtRu/C) electrocatalysts, the Pt-WC/RGO composites demonstrate higher electrochemical active surface area and excellent electrocatalytic activity toward the methanol oxidation, such as better tolerance toward CO, higher peak current density, lower onset potential and long-term stability, which could be attributed to the characterized RGO support, highly dispersed Pt NPs and WC nanocrystallites and the valid synergistic effect resulted from the increased interface between WC and Pt. The present work proves that Pt-WC/RGO composites could be a promising alternative catalyst for direct methanol fuel cells where WC plays the important role as a functional additive in preparing Pt-based catalysts because of its CO tolerance and lower price. 

Aerobic oxidation catalysis with stable radicals

Selective oxidation reactions are challenging when carried out on an industrial scale. Many traditional methods are undesirable from an environmental or safety point of view. There is a need to develop sustainable catalytic approaches that use molecular oxygen as the terminal oxidant. This review will discuss the use of stable radicals (primarily nitroxyl radicals) in aerobic oxidation catalysis. We will discuss the important advances that have occurred in recent years, highlighting the catalytic performance, mechanistic insights and the expanding synthetic utility of these catalytic systems.

Significance of β-dehydrogenation in ethanol electro-oxidation on platinum doped with Ru, Rh, Pd, Os and Ir

In the exploration of highly efficient direct ethanol fuel cells (DEFCs), how to promote the CO₂ selectivity is a key issue which remains to be solved. Some advances have been made, for example, using bimetallic electrocatalysts, Rh has been found to be an efficient additive to platinum to obtain high CO₂ selectivity experimentally. In this work, the mechanism of ethanol electrooxidation is investigated using first principles method. It is found that CH₃CHOH* is the key intermediate during ethanol electrooxidation and the activity of β-dehydrogenation is the rate determining factor that affects the completeness of ethanol oxidation. In addition, a series of transition metals (Ru, Rh, Pd, Os and Ir) are alloyed on the top layer of Pt(111) in order to analyze their effects. The elementary steps, α-, β-C-H bond and C-C bond dissociations are calculated on these bimetallic M/Pt(111) surfaces and the formation potential of OH* from water dissociation is also calculated. We find that the active metals increase the activity of β-dehydrogenation but lower the OH* formation potential resulting in the active site being blocked. By considering both β-dehydrogenation and OH* formation, Ru, Os and Ir are identified to be unsuitable for the promotion of CO₂ selectivity and only Rh is able to increase the selectivity of CO₂ in DEFCs.

Copper(I)/ketoABNO Catalysed Aerobic Alcohol Oxidation

A Cu(I)/9-azabicyclo[3.3.1]nonan-3-one N-oxyl (ketoABNO) aerobic catalyst system is highly effective for the oxidation of secondary alcohols, including unactivated aliphatic substrates. The effects of pressure and gas composition on catalyst performance are examined. The radical can be employed at low loadings and is also amenable to immobilisation on to solid supports.

N,O-Ligated Pd(II) Complexes for Catalytic Alcohol Oxidation

N,O-ligated Pd(II) complexes show considerable promise for the oxidation of challenging secondary aliphatic alcohols. The crystal structures of the highly active complexes containing the 8-hydroxyquinoline-2-carboxylic acid (HCA) and 8-hydroxyquinoline-2-sulfonic acid (HSA) ligands have been obtained. The (HSA)Pd(OAc)2 system can effectively oxidise a range of secondary alcohols, including unactivated alcohols, within 4–6 h using loadings of 0.5 mol%, while lower loadings (0.2 mol%) can be employed with extended reaction times. The influence of reaction conditions on catalyst degradation was also examined in these studies.

Atmospheric pressure chemical vapour deposition of boron doped titanium dioxide for photocatalytic water reduction and oxidation

Boron-doped titanium dioxide (B-TiO) films were deposited by atmospheric pressure chemical vapour deposition of titanium(iv) chloride, ethyl acetate and tri-isopropyl borate on steel and fluorine-doped-tin oxide substrates at 500, 550 and 600 °C, respectively. The films were characterised using powder X-ray diffraction (PXRD), which showed anatase phase TiO at lower deposition temperatures (500 and 550 °C) and rutile at higher deposition temperatures (600 °C). X-ray photoelectron spectroscopy (XPS) showed a dopant level of 0.9 at% B in an O-substitutional position. The ability of the films to reduce water was tested in a sacrificial system using 365 nm UV light with an irradiance of 2 mW cm. Hydrogen production rates of B-TiO at 24 μL cm h far exceeded undoped TiO at 2.6 μL cm h. The B-TiO samples were also shown to be active for water oxidation in a sacrificial solution. Photocurrent density tests also revealed that B-doped samples performed better, with an earlier onset of photocurrent. © 2013 The Owner Societies.

Unraveling the synergy between gold nanoparticles and chromium- hydrotalcites in aerobic oxidation of alcohols

The combination of gold nanoparticles (AuNPs) with chromium-substituted hydrotalcite (Cr-HT) supports makes very efficient heterogeneous catalysts (Au/Cr-HT) for aerobic alcohol oxidation under soluble-base-free conditions. The Au-support synergy increases with increasing Cr content of the support and decreasing AuNP size. In situ UV-Raman, X-ray absorption and photoelectron spectroscopic studies firmly establish that the strong Au-Cr synergy is related to a Cr ↔ Cr redox cycle at the Au/Cr-HT interface, where O activation takes place accompanied by electron transfer from Cr-HT to Au. The interfacial Cr species can be reduced by surface Au-H hydride and negative-charged Au species to close the catalytic cycle. A study of kinetic isotope effect indicates that alcohol O-H cleavage is facilitated by the presence of Cr, making a-C-H bond cleavage step more rate-controlling. Accordingly, a dual synergistic effect of Au/Cr-HT catalysts on the activation of O2 and alcohol reactants is proposed.