Alkaline fuel cells: contemporary advancement and limitations

ZeTek Power recently introduced mass manufacturable and cost effective alkaline fuel cells on the market. Today's research is focused on further improvement both in terms of performance increase and cost reduction. This research is classically performed using small (4 cm²) experimental electrodes in the half-cell configuration. This allows the primary electrochemical losses in an anode or cathode to be determined independently. Additional performance losses occur when one integrates large electrodes into a module of 24 cells and in a stack comprised of many modules. By comparing the performance of half-cell experiments to that of modules, these losses can be distinguished and addressed. The information thus obtained, both for the small electrodes and in up-scaling is vital if one is to identify the key areas in which improvement is possible and where to focus future research. Furthermore, the identification of the losses in a module and system allows us to predict the final performance from half-cell measurements of a new laboratory scale experimental electrode.     

Reaction pathways of ethane oxidative and non-oxidative dehydrogenation on γ-Al2O3 studied by temperature-programmed reaction (TP-reaction)

In this work, the reactions of ethane and ethene in an oxidizing and non-oxidizing atmosphere over γ-alumina were investigated under temperature-programmed conditions, in an attempt to estimate the possible contribution and functionality of the support in the reaction pathway of ethane ODH over MoO₃/Al₂O₃ catalysts. The results indicate that alumina contributes to the primary deep oxidation and dehydrogenation routes of ethane to CO_x and coke respectively, which proceed effectively over the acidic OH groups and the Al³⁺–O²⁻ acidic centers. On the contrary, the formation of ethylene seems to be coupled to the presence of redox sites on the catalytic surface and requires the presence of the molybdena phase. Moreover, the redox sites of the MoO_x species were found to unselectively activate the further overoxidation of the olefin to carbon oxides. Therefore, Al₂O₃ catalyzes the unselective primary oxidation of ethane to carbon oxides, whereas the molybdena phase is involved in the selective oxidative dehydrogenation (ODH) of ethane to ethene and the secondary overoxidation of ethene to CO_x.     

On the catalytic C-H activation of some silicon dioxide overlayers on thin metal film systems — An observation on the isokinetic effect

Kinetic data on the exchange reaction betwee hexane and deuterium have recently been reported by Maier and coworkers [1]. The reaction was catalysed by a series of platinum or rhodium systems, some of which had the property that the upper surface was shielded by a silica overlayer. The data are reinterpreted to indicate an isokinetic temperature of 580 K. This observation indicates that all the catalysts behave in a similar manner, which means that the exchange reaction does not require a free metal surface.     

Synthesis of Pseudoionones by Acid and Base Solid Catalysts

The preparation of pseudoionones by aldol condensation reaction between citral and acetone have been carried out in the presence of acid (HY and beta zeolites), an acid–base (amorphous aluminophosphate) and basic catalysts such as an aluminophosphate oxynitride, MgO and different activated hydrotalcites. The results showed that acid or acid–base catalysts were not successful for performing in one pot the preparation of ionones. MgO and calcined hydrotalcites showed excellent activity and selectivity to pseudoionones, with calcined hydrotalcite more selective than MgO. Moreover, the rate of reaction can be improved by activating the hydrotalcite through rehydration. This activation can be successfully done by simply adding the optimum amount of water to the calcined hydrotalcite before reaction. The inhibiting effect of the concentration citral on the catalytic activity of rehydrated hydrotalcites that has been reported to occur at 273 K can be avoided by working at a reaction temperature of 333 K.     

Adsorption and desorption kinetics of hydrocarbons in FCC catalysts studied using a tapered element oscillating microbalance (TEOM). Part 2: numerical simulations

The factors affecting the adsorption and desorption kinetics in a TEOM are reviewed in detail with particular attention given to the assumptions required to obtain physical transport parameters from the data. Two models are presented to simulate TEOM adsorption data in the case that concentration differences down the catalyst bed can be neglected, as is appropriate when the amount of catalyst used is small, the carrier gas flowrate is large, and/or the adsorbate partial pressure is low. In the first model, the effective diffusion coefficient, D_e, is taken to be constant. In the second model, the effective diffusion coefficient is assumed to obey the Darken equation, D_e=D₀/(1−θ). The TEOM results obtained on n-hexane, n heptane, n-octane, toluene and p-xylene on a commercial FCC catalyst and on pure rare-earth exchanged zeolite Y under non-reacting conditions (373-) are analysed in detail. It is found that intracrystalline diffusion is not the limiting factor affecting the overall rates of adsorption and desorption for the systems studied. Instead, it is the transport of molecules between the adsorbed and vapour phases at the edge of zeolite crystallites that is the limiting transport step affecting the overall kinetics. For the FCC catalyst, the limiting step is the transport of molecules at the zeolite-matrix interface rather than, say, the matrix-vapour interface. Local rate constants for the desorption of the hydrocarbons at the rate-controlling interface have been obtained.     

Selective hydrogenolysis of glycerol to propylene glycol on Cu–ZnO catalysts

Hydrogenolysis of biomass-derived glycerol is an alternative route to sustainable production of propylene glycol. Cu–ZnO catalysts were prepared by coprecipitation with a range of Cu/Zn atomic ratio (0.6–2.0) and examined in glycerol hydrogenolysis to propylene glycol at 453–513 K and 4.2 MPa H₂. These catalysts possess acid and hydrogenation sites required for bifunctional glycerol reaction pathways, most likely involving glycerol dehydration to acetol and glycidol intermediates on acidic ZnO surfaces, and their subsequent hydrogenation on Cu surfaces. Glycerol hydrogenolysis conversions and selectivities depend on Cu and ZnO particle sizes. Smaller ZnO and Cu domains led to higher conversions and propylene glycol selectivities, respectively. A high propylene glycol selectivity (83.6%), with a 94.3% combined selectivity to propylene glycol and ethylene glycol (also a valuable product) was achieved at 22.5% glycerol conversion at 473 K on Cu–ZnO (Cu/Zn = 1.0) with relatively small Cu particles. Reaction temperature effects showed that optimal temperatures (e.g. 493 K) are required for high propylene glycol selectivities, probably as a result of optimized adsorption and transformation of the reaction intermediates on the catalyst surfaces. These preliminary results provide guidance for the synthesis of more efficient Cu–ZnO catalysts and for the optimization of reaction parameters for selective glycerol hydrogenolysis to produce propylene glycol.     

Iron species incorporated over different silica supports for the heterogeneous photo-Fenton oxidation of phenol

Iron-containing catalysts have been prepared following different synthesis routes and silica supports (amorphous, zeolitic and mesostructured materials). Activity and stability of these materials were assessed on the photo-Fenton degradation of phenolic aqueous solutions using near UV irradiation (higher than 313 nm) at room temperature and initial neutral pH. Their catalytic performance was monitored in terms of phenol and total organic carbon (TOC) conversions. Aromatic compounds and carboxylic acids as by-products coming from incomplete mineralization of phenol as well as the efficiency of each catalytic system in the use of the oxidant were also studied. Stability of the materials throughout the photo-Fenton reaction was evaluated in terms of metal leachibility. Activity and stability depend on the environment of iron species and features of silica support. The evolution of pH with the reaction time and their relationship with TOC degradation and leaching degree has been discussed. A nanocomposite material of crystalline iron oxides supported over mesostructured SBA-15 material is shown the most successful catalyst for degradation of phenolic aqueous solutions by photo-Fenton processes, achieving an outstanding overall catalytic performance accompanied with a noteworthy stability.     

Effect of the metal oxide loading on the activity of silica supported MoO3 and V2O5 catalysts in the selective partial oxidation of methane

Precipitated silica catalysts loaded with either MoO₃ (0.2–4.0 wt%) or V₂O₅ (0.2–5.3 wt%) have been studied in the selective partial oxidation of methane to formaldehyde with molecular oxygen at 520 °C. The functionality of the SiO₂ surface towards the formation of HCHO is significantly promoted by V₂O₅, while it is depressed by the MoO₃.     

Use of Re(C5H7O2) in preparation of catalysts for olefin metathesis

New catalysts for olefin metathesis are obtained upon interaction between rhenium trisacetylacetonate and -Al₂O₃ surface. After high temperature treatment in flows of O₂ and N₂ and addition of organometallic compound as a cocatalyst the activity of the resulting catalyst exceeds that of known Re/Al₂O₃ catalysts prepared by impregnation. The catalysts exhibit maximal activity at a cocatalyst surface concentration of 3 × 10^–7 mol/m². Further increase of the cocatalyst concentration leads to deactivation.     

湿浸法制备活性组分非均匀分布负载型催化剂过程的计算机模拟

对活性组分非均匀分布的负载型催化剂的湿浸法制备过程进行了计算机模拟,其模拟程度可适用于任意多个活性组分的浸渍。发现单组分浸渍时,通过控制浸渍时间可获得活性组分由薄到厚的蛋壳型分布和均匀分布,但通过预浸渍吸附至一定分布后,再在空白溶液中浸渍洗脱,控制洗脱条件也可获得蛋黄、蛋白型的分布;加入竞争吸附剂,进行双组分及多组分浸渍,通过控制浸渍溶液性质及浸渍时间可获得各种类型的活性组分分布,诸如蛋壳型、蛋白型、蛋黄型和均匀型。通过对制备过程参数(如竞争吸附剂的选择、各组分有效扩散系数、初始浓度、吸脱附速率常数等)与活性组分分布形式之间关系的分析,可实现对任一分布形式的催化剂的制备过程参数的优化。这对实际制备催化剂具有指导意义。