Long Term Performance Study of a Direct Methanol Fuel Cell Fed with Alcohol Blends

The use of alcohol blends in direct alcohol fuel cells may be a more environmentally friendly and less toxic alternative to the use of methanol alone in direct methanol fuel cells. This paper assesses the behaviour of a direct methanol fuel cell fed with aqueous methanol, aqueous ethanol and aqueous methanol/ethanol blends in a long term experimental study followed by modelling of polarization curves. Fuel cell performance is seen to decrease as the ethanol content rises, and subsequent operation with aqueous methanol only partly reverts this loss of performance. It seems that the difference in the oxidation rate of these alcohols may not be the only factor affecting fuel cell performance.

Conformation of coenzyme pyrroloquinoline quinone and role of Ca2+ in the catalytic mechanism of quinoprotein methanol dehydrogenase

The ab initio structures of 2,7,9-tricarboxypyrroloquinoline quinone (PQQ), semiquinone (PQQH), and dihydroquinone (PQQH2) have been determined and compared with ab initio structures of the (PQQ)Ca2+, (PQQH)Ca2+, and (PQQH2)Ca2+ complexes as well as the x-ray structure of (PQQ)Ca2+ bound at the active site of the methanol dehydrogenase (MDH) of methyltropic bacteria. Plausible mechanisms for the MDH oxidation of methanol involving the (PQQ)Ca2+ complex are explored via ab initio computations and discussed. Considering the reaction of methanol with PQQ in the absence of Ca2+, nucleophilic addition of methanol to the PQQ C-5 carbonyl followed by a retro-ene elimination is deemed unlikely due to large energy barrier. A much more favorable disposition of the methanol C-5 adduct to provide formaldehyde involves proton ionization of the intermediate followed by elimination of methoxide concerted with hydride transfer to the oxygen of the C-4 carbonyl. Much the same transition state is reached if one searches for the transition state beginning with Asp-303–CO2−general-base removal of the methanol proton of the (PQQ)Ca2+O(H)CH3 complex concerted with hydride transfer to the oxygen at C-4. For such a mechanism the role of the Ca2+ moiety would be to (i) contribute to the formation of the ES complex (ii) provide a modest decrease in the pKa of methanol substrate,; and (iii) polarize the oxygen at C-5.

Single-walled carbon nanotube buckypapers as electrocatalyst supports for methanol oxidation

This work studies the use of various single-walled carbon nanotube (SWCNT) buckypapers as catalyst supports for methanol electro-oxidation in acid media. Buckypapers were obtained by vacuum filtration from pristine and oxidized SWCNT suspensions in different liquid media. Pt–Ru catalysts supported on the buckypapers were prepared by multiple potentiostatic pulses using a diluted solution of Pt and Ru salts (2 mM H2PtCl6 + 2 mM RuCl3) in acid media. The resulting materials were characterized via SEM, TEM, EDX and ICP-OES analysis. Well dispersed rounded nanoparticles between 2 and 15 nm were successfully electrodeposited on the SWCNT buckypapers. The ruthenium content in the bimetallic deposits was between 32 and 48 at. %, while the specific surface areas of the catalysts were in the range of 72–113 m2 g−1. It was found that the solvent used to prepare the SWCNT buckypaper films has a strong influence on the catalyst dispersion, particle size and metal loading. Cyclic voltammetry and chronoamperometry experiments point out that the most active electrodes for methanol electro-oxidation were prepared with the buckypaper supports that were obtained from SWCNT dispersions in N-methyl-pyrrolidone.

X-Ray Imaging of SAPO-34 Molecular Sieves at the Nanoscale: Influence of Steaming on the Methanol-to-Hydrocarbons Reaction

The effect of a severe steaming treatment on the physicochemical properties and catalytic performance of H-SAPO-34 molecular sieves during the methanol-to-hydrocarbons (MTH) reaction has been investigated with a combination of scanning transmission X-ray microscopy (STXM), catalytic testing, and bulk characterization techniques, including ammonia temperature programmed desorption and 27Al and 29Si magic angle spinning nuclear magnetic resonance. For this purpose, two samples, namely a calcined and a steamed H-SAPO-34 catalyst powder, have been compared. It has been found that calcined H-SAPO-34 displays a high selectivity towards light olefins, yet shows a poor stability as compared to a zeolite H-ZSM-5 catalyst. Moreover, in situ STXM at the carbon K-edge during the MTH reaction allows construction of nanoscale chemical maps of the hydrocarbon species formed within the H-SAPO-34 aggregates as a function of reaction time and steam post-treatment. It was found that there is an initial preferential formation of coke precursor species within the core of the H-SAPO-34 aggregates. For longer times on stream the formation of the coke precursor species is extended to the outer regions, progressively filling the entire H-SAPO-34 catalyst particle. In contrast, the hydrothermally treated H-SAPO-34 showed similar reaction selectivity, but decreased activity and catalyst stability with respect to its calcined counterpart. These variations in MTH performance are related to a faster and more homogeneous formation of coke precursor species filling up the entire steamed H-SAPO-34 catalyst particle. Finally, the chemical imaging capabilities of the STXM method at the Al and Si K-edge are illustrated by visualizing the silicon islands at the nanoscale before and after steaming H-SAPO-34.

Sonochemical synthesis of graphene oxide supported Pt–Pd alloy nanocrystals as efficient electrocatalysts for methanol oxidation

Pt–Pd bimetallic nanoparticles supported on graphene oxide (GO) nanosheets were prepared by a sonochemical reduction method in the presence of polyethylene glycol as a stabilizing agent. The synthetic method allowed for a fine tuning of the particle composition without significant changes in their size and degree of aggregation. Detailed characterization of GO-supported Pt–Pd catalysts was carried out by transmission electron microscopy (TEM), AFM, XPS, and electrochemical techniques. Uniform deposition of Pt–Pd nanoparticles with an average diameter of 3 nm was achieved on graphene nanosheets using a novel dual-frequency sonication approach. GO-supported bimetallic catalyst showed significant electrocatalytic activity for methanol oxidation. The influence of different molar compositions of Pt and Pd (1:1, 2:1, and 3:1) on the methanol oxidation efficiency was also evaluated. Among the different Pt/Pd ratios, the 1:1 ratio material showed the lowest onset potential and generated the highest peak current density. The effect of catalyst loading on carbon paper (working electrode) was also studied. Increasing the catalyst loading beyond a certain amount lowered the catalytic activity due to the aggregation of metal particle-loaded GO nanosheets.

Biscarboxy-Functionalized Imidazole and Palladium as Highly Active Catalytic System in Protic Solvents: Methanol and Water

The coupling reaction between aryl bromides and boron reagents is efficiently catalyzed by an in situ generated palladium complex obtained from palladium(II) acetate (0.1 mol%) and 1,3-bis(carboxymethyl)imidazole (0.2 mol%). The catalytic system is very active in protic solvents, especially in methanol. Biaryl derivatives have been prepared in good isolated yields (up to >99%), and additionally styrene and stilbene derivatives have also been prepared by means of this protocol.

Production of methanol from CO2 electroreduction at Cu2O and Cu2O/ZnO-based electrodes in aqueous solution

In this study, we examine the performance of Cu2O and Cu2O/ZnO surfaces in a filter-press electrochemical cell for the continuous electroreduction of CO2 into methanol. The electrodes are prepared by airbrushing the metal particles onto a porous carbon paper and then are electrochemically characterized by cyclic voltammetry analyses. Particular emphasis is placed on evaluating and comparing the methanol production and Faradaic efficiencies at different loadings of Cu2O particles (0.5, 1 and 1.8 mg cm−2), Cu2O/ZnO weight ratios (1:0.5, 1:1 and 1:2) and electrolyte flow rates (1, 2 and 3 ml min−1 cm−2). The electrodes including ZnO in their catalytic surface were stable after 5 h, in contrast with Cu2O-deposited carbon papers that present strong deactivation with time. The maximum methanol formation rate and Faradaic efficiency for Cu2O/ZnO (1:1)-based electrodes, at an applied potential of −1.3 V vs. Ag/AgCl, were r = 3.17 × 10−5 mol m−2 s−1 and FE = 17.7 %, respectively. Consequently, the use of Cu2O–ZnO mixtures may be of application for the continuous electrochemical formation of methanol, although further research is still required in order to develop highly active, selective and stable catalysts the electroreduction of CO2 to methanol.

Properties and economics of methanol-gasoline blends with high methanol content.

Energy Department, Office of Vehicle and Engine Research and Development, Washington, D.C.

Methanol as an alternative transportation fuel : hearings before the Subcommittee on Fossil and Synthetic Fuels of the Committee on Energy and Commerce, House of Representatives, Ninety-seventh Congress, second session, August 13 and September 24, 1982.

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