Exploring single electrode reactions in polymer electrolyte fuel cells

Utilising a pseudo-reference electrode in polymer electrolyte fuel cells allows for the separation of anodic and cathodic contributions to the entire cell impedance. Modelling the impedance responses by using equivalent circuits inhibits the investigation of kinetic parameters of the basic electrochemical reactions, which take place at single electrode-electrolyte interfaces. Therefore, we evaluate single electrode impedance measurements by a kinetic model, which is based on specific reaction pathways, either for the oxygen reduction reaction (ORR) or the hydrogen oxidation reaction (HOR). As a consequence, it is possible to obtain kinetic parameters for the specific reaction of interest. Furthermore, the information gained from the single electrode impedance measurements and the kinetic model can give insight into single reactions steps. In particular, the ORR has to include a chemical step in the reaction pathway.     

Proton Conductivity Measurements in Yttrium Barium Cerate by Impedance Spectroscopy

Proton-conducting solid-electrolyte perovskite ceramics based on acceptor-doped barium and strontium cerates have become the focus of extensive investigations as candidate materials for fuel cells that operate at moderate temperatures. To assess the suitability of a material for this application, it is necessary that bulk electrolyte conductivity be measured at the operating temperature. However, very little reliable published conductivity data exist above 600°C. Protonic conductivity in yttrium-doped barium cerate has been observed to be less at high temperatures than would be expected, based on the activation energy and preexponential for hydrogen transport at temperatures <300°C. Conductivity data obtained from impedance spectroscopy on BaCe_0.9Y_0.1O_3–α over the extended temperature range of 100°–900°C are presented. An Arrhenius plot of the data shows two distinct linear regions, suggesting that two different rate-limiting processes occur in series with a break-over transition at ∼250°C. The decrease in conductivity is apparently not due to dehydration. An activation energy for protonic transport of 0.26 eV, about one-half of the low-temperature value, is proposed, based on curve fitting of the high-temperature data.     

A novel high-performance counter electrode for dye-sensitized solar cells

A novel Pt counter electrode for dye-sensitized solar cells (DSC) was prepared by thermal decomposition of H₂PtCl₆ on NiP-plated glass substrate. The charge-transfer kinetic properties of the platinized NiP-plated glass electrode (Pt/NiP electrode) for triiodide reduction were studied by electrochemical impedance spectroscopy. Pt/NiP electrode has the advantage over the platinized FTO conducting glass electrode (Pt/FTO electrode) in increasing the light reflectance and reducing the sheet resistance leading to improve the light harvest efficiency and the fill factor of the dye-sensitized solar cells effectively. The photon-to-current efficiency and the overall conversion efficiency of DSC using Pt/NiP counter electrode is increased by 20% and 33%, respectively, compared to that of using Pt/FTO counter electrode. Examination of the anodic dissolution and the long-term test on the variation of charge-transfer resistance indicates the good stability of the Pt/NiP electrode in the electrolyte containing iodide/triiodide.     

Diamond-like carbon thin films by microwave surface-wave plasma CVD aimed for the application of photovoltaic solar cells

The nitrogen doped diamond-like carbon (DLC) thin films were deposited on quartz and silicon substrates by a newly developed microwave surface-wave plasma chemical vapor deposition, aiming the application of the films for photovoltaic solar cells. For film deposition, we used argon as carrier gas, nitrogen as dopant and hydrocarbon source gases, such as camphor (C₁₀H₁₆O) dissolved with ethyl alcohol (C₂H₅OH), methane (CH₄), ethylene (C₂H₄) and acetylene (C₂H₂). The optical and electrical properties of the films were studied using X-ray photoelectron spectroscopy, Nanopics 2100/NPX200 surface profiler, UV/VIS/NIR spectroscopy, atomic force microscope, electrical conductivity and solar simulator measurements. The optical band gap of the films has been lowered from 3.1 to 2.4 eV by nitrogen doping, and from 2.65 to 1.9 eV by experimenting with different hydrocarbon source gases. The nitrogen doped (flow rate: 5 sccm; atomic fraction: 5.16%) film shows semiconducting properties in dark (i.e. 8.1 × 10^{− 4} Ω^{− 1} cm^{− 1}) and under the light illumination (i.e. 9.9 × 10^{− 4} Ω^{− 1} cm^{− 1}). The surface morphology of the both undoped and nitrogen doped films are found to be very smooth (RMS roughness ≤ 0.5 nm). The preliminary investigation on photovoltaic properties of DLC (nitrogen doped)/p-Si structure show that open-circuit voltage of 223 mV and short-circuit current density of 8.3 × 10^{− 3} mA/cm². The power conversion efficiency and fill factor of this structure were found to be 3.6 × 10^{− 4}% and 17.9%, respectively. The use of DLC in photovoltaic solar cells is still in its infancy due to the complicated microstructure of carbon bondings, high defect density, low photoconductivity and difficulties in controlling conduction type. Our research work is in progress to realize cheap, reasonably high efficiency and environmental friendly DLC-based photovoltaic solar cells in the future.     

固定化紫草细胞生产紫草宁衍生物

用海藻胶包埋紫草细胞,在紫草色素生产培养基M_9中,常温、黑暗下培养不同时间,收集培养液并提取色素,进行紫外—可见全波长分光光度扫描和TLC分析。结果表明:固定化紫草细胞可连续分泌紫草色素,其主要成分与天然成分基本相同,产量已达到一定水平。此外对海藻胶包埋条件、固定化珠粒的稳定性以及1L固定化植物细胞反应器生产紫草色素工艺进行了讨论。     

Prediction of Experimental Methanol Decomposition Rates on Platinum from First Principles

A microkinetic model for methanol decomposition on platinum is presented. The model incorporates competitive decomposition pathways, beginning with both O–H and C–H bond scission in methanol, and uses results from density functional theory (DFT) calculations [Greeley and Mavrikakis, J. Am. Chem. Soc. 124 (2002) 7193, Greeley and Mavrikakis, J. Am. Chem. Soc. 126 (2004) 3910]. Results from reaction kinetics experiments show that the rate of H₂ production increases with increasing temperature and methanol concentration in the feed and is only nominally affected by the presence of CO or H₂ with methanol. The model, based on the values of binding energies, pre-exponential factors and activation energy barriers derived from first principles calculations, accurately predicts experimental reaction rates and orders. The model also gives insight into the most favorable reaction pathway, the rate-limiting step, the apparent activation energy, coverages, and the effects of pressure. It is found that the pathway beginning with the C–H bond scission (CH₃OH→H₂COH→HCOH→CO) is dominant compared with the path beginning with O–H bond scission. The cleavage of the first C–H bond in methanol is the rate-controlling step. The surface is highly poisoned by CO, whereas COH appears to be a spectator species.     

生物反应器细胞培养制备人用狂犬病疫苗

目的应用生物反应器培养细胞和病毒,大规模生产人用狂犬病疫苗。方法以巴斯德PV2061为毒种,以143代以内Vero细胞为培养基质,应用生物反应器,每升投放25g微载体,灌流式细胞培养,连续收获病毒液,经浓缩、灭活、纯化,制成Vero细胞狂犬病疫苗。结果细胞培养密度达1.2×107～1.5×107个/ml,病毒感染后可连续收获18～22d,病毒最高滴度8.5LogLD50/ml,平均滴度7.6LogLD50/ml。经柱层析纯化,杂蛋白去除率达99.95%以上,总蛋白含量≤80μg/g,DNA含量≤10pg/0.5ml,GP含量3.5～4.5IU/0.5ml,效力≥4.5IU/0.5ml。结论应用生物反应器细胞培养,可以大规模生产优质Vero细胞人用狂犬病疫苗。     

Visual learning and classification of human epithelial type 2 cell images through spontaneous activity patterns

Identifying the presence of anti-nuclear antibody (ANA) in human epithelial type 2 (HEp-2) cells via the indirect immunofluorescence (IIF) protocol is commonly used to diagnose various connective tissue diseases in clinical pathology tests. As it is a labour and time intensive diagnostic process, several computer aided diagnostic (CAD) systems have been proposed. However, the existing CAD systems suffer from numerous shortcomings due to the selection of features, which is commonly based on expert experience. Such a choice of features may not work well when the CAD systems are retasked to another dataset. To address this, in our previous work, we proposed a novel approach that learns a set of filters from HEp-2 cell images. It is inspired by the receptive fields in the mammalian's vision system, since the receptive fields can be thought as a set of filters for similar shapes. We obtain robust filters for HEp-2 cell classification by employing the independent component analysis (ICA) framework. Although, this approach may be held back due to one particular problem; ICA learning requires a sufficiently large volume of training data which is not always available. In this paper, we demonstrate a biologically inspired solution to address this issue via the use of spontaneous activity patterns (SAP). The spontaneous activity patterns, which are related to the spontaneous neural activities initialised by the chemical release in the brain, are found as the typical stimuli for the visual cell development of newborn animals. In the classification system for HEp-2 cells, we propose to model SAP as a set of small image patches containing randomly positioned Gaussian spots. The SAP image patches are generated and mixed with the training images in order to learn filters via the ICA framework. The obtained filters are adopted to extract the set of responses from a HEp-2 cell image. We then employ regions from this set of responses and stack them into “cubic regions”, and apply a classification based on the correlation information of the features. We show that applying the additional SAP leads to a better classification performance on HEp-2 cell images compared to using only the existing patterns for training ICA filters. The improvement on classification is particularly significant when there are not enough specimen images available in the training set, as SAP adds more variations to the existing data that makes the learned ICA model more robust. We show that the proposed approach consistently outperforms three recently proposed CAD systems on two publicly available datasets: ICPR HEp-2 contest and SNPHEp-2.     

Regeneration of zinc particles for zinc–air fuel cells in a spouted-bed electrode

Fuel cells wherein zinc particles form a negative electrode and a gas-diffusion electrode (air electrode) is the positive electrode, are under development. Such cells are dependent on the regeneration of the zinc particles (and electrolyte). This paper describes experiments on electrolytic cells equipped with spouted bed cathodes for use in this application. Experiments have been carried out on laboratory scale cells to determine the operability of cells for growing 'seed particles in the range from 0.4 to 1 mm to measure cell voltage and current efficiency (and thereby energy consumption rate), and to identify a suitable material that could be used as a diaphragm (separating the spouted bed from the oxygen evolving anode). A larger cell, capable of producing up to 10 kg Zn per day, was designed and built. The larger cell was run successfully fifteen times and showed cell voltages and energy consumption rates comparable with those of smaller cells.     

Electrochemical performance of gel-cast NiO-SDC composite anodes in low-temperature SOFCs

NiO-Ce_0.8Sm_0.2O_1.9 (SDC) composites were synthesized using gel-casting technique. The electrochemical performance of the gel-cast (GC) Ni-SDC cermet as anode was investigated contrast with that fabricated from traditional mechanical mixing (MM) technique using fuel cells with about 35 μm-thick SDC electrolyte and Sm_0.5Sr_0.5CoO₃-SDC cathode. Maximum power density of the cell with GC anode achieved 491 mW cm⁻² at 600 °C, over 100 mW cm⁻² larger than that with MM anode, inferring high catalytic activity of the GC anode. Impedance measurements on the fuel cell at open circuit showed that the anodic interfacial polarization resistance of the GC anode was 0.1 Ω cm² lower than that of the MM anode. Long-term stability of the cell with GC anode in hydrogen was also performed, which showed that it can stabilize at least 7 days.