DMFC阳极催化剂用GRQD-NiCo2O4复合物的制备与电催化活性分析

采用水热法制备GRQD-NiCo₂O₄复合物,利用XRD、SEM及TEM分析其微结构,并探讨其作为DMFC阳极催化剂使用时的电化学性能。微结构分析表明所得GRQD-NiCo₂O₄复合物皆为具NiCo₂O₄单一相的尖晶石结构,且GRQD质量浓度高于0.25 g/mL后表面形貌将转变GRQD与NiCo₂O₄相互结合的状态。电化学分析表明添加GRQD可有效增强NiCo₂O₄的导电性并提升其电化学稳定性,其中GRQD质量浓度为0.25 g/mL时所得样品经500次循环测试后电流密度约为77.5 A/g,与循环5次后相比其电流密度剩余量最大（约为69.7%）,该样品作为DMFC阳极催化剂使用时性价比最佳。     

Evaluation of a palladinized Nafion™ for direct methanol fuel cell application

Palladinized Nafion™ was prepared via ion-exchange and chemical reduction method. Palladium precursors and solvent systems determined the efficiency of the incorporation and distribution of nanoparticles. The tortuous thin Pd film was formed on the surface of membrane when Na⁺-Nafion™ and water were used. Pd nanoparticles enhanced the water uptake of Nafion™ and reduced its methanol uptake. And dispersed Pd nanoparticles in Nafion™ disturbed the proton conduction and methanol permeation simultaneously in Nafion™ cluster. In order to reduce methanol permeation of Nafion™ and keep its high conductivity, it was more efficient for Pd nanoparticles to distribute near the surface of membrane. Palladinized Nafion™ improved the performance of DMFC single cell operation by reducing the methanol permeation.     

Electrooxidation of methanol at platinum–ruthenium catalysts prepared from colloidal precursors: Atomic composition and temperature effects

The electrocatalytic oxidation of methanol was investigated on PtRu electrodes of different atomic compositions at several temperatures (from 25 to 110 °C). Very active catalyst nanoparticles supported on active carbon (Vulcan XC 72) were obtained using the colloidal synthesis developed by Bönnemann et al. [11], allowing easy variation of the atomic composition. These electrocatalysts were characterized by TEM, EDX and XRD; results indicate that they consist of platinum nanoparticles decorated by ruthenium. Methanol oxidation was studied as a function of composition, temperature and methanol concentration. Two effects were investigated: the effect of the working temperature and the effect of the atomic composition. It appeared that for lower methanol electrooxidation overvoltages, the best catalysts are ruthenium-rich, whereas at higher overvoltages the best one is the Pt + Ru (80:20)/C composition, irrespective of the working temperature, either in half-cell or in a single DMFC.     

Performance of Methanol Oxidation Catalysts with Varying Pt:Ru Ratio as a Function of Temperature

This paper describes the effects of varying the Pt to Ru ratio in carbon-supported catalysts for methanol oxidation as a function of temperature. Previously these effects were studied in isolation, but now it is shown that the composition of a given catalyst as a function of temperature is extremely important for its activity towards methanol oxidation. Platinum rich 3:2 atomic ratio catalysts perform better than a 1:1 catalyst at 25 °C, where only Pt is believed to be active towards methanol dehydrogenation, since this process is a highly thermally activated process on Ru sites. This result is reversed at 65 °C, where the 1:1 catalyst displays much higher currents across the entire range of polarization. This may result from methanol dehydrogenation occurring on both Ru and Pt sites at higher temperatures. At an intermediate temperature, 45 °C, the 3:2 catalyst is seen to perform better at lower current values, while the 1:1 catalyst is superior at higher current densities, with the crossover occurring at 62 A g^–1. As a consequence, when designing fuel cell catalysts, the composition of the catalyst employed should be tailored with respect to the exact operating conditions, in order to promote optimum fuel cell performance.     

Composite anion exchange membrane for alkaline direct methanol fuel cell: Structural and electrochemical characterization

A copolymer of 4‐vinylpyridine (4‐VP) and styrene was synthesized by radical mass polymerization using 2,2′‐azobisisobutyronitrile as initiator. An insoluble (linear) pyridinium‐type polymer was prepared by the reaction of P (4VP–St) with 1‐bromooctane. An anion exchange membrane was prepared using a composite of pyridinium‐type polymer and a fibrous woven structure for use in electrochemistry. The composite membrane was characterized by X‐ray diffraction, tensile strength, scanning electron microscopy, and electrochemistry measurements. The experimental results showed that the fibrous woven product had improved the tensile strength more than had the membrane made of a pyridinium‐type polymer alone. The composite membrane was used in alkaline fuel cells, and its properties were measured by electrochemical analysis. The ionic conductivity of the membrane was acceptable, but its performance as a direct methanol fuel cell (DMFC) was not. The primary reason for this was analyzed, and research is ongoing, with analysis to be discussed in later reports. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2248–2251, 2006     

The electrochemical behavior of cobalt phthalocyanine/platinum as methanol-resistant oxygen-reduction electrocatalysts for DMFC

The electrochemical behavior of cobalt phthalocyanine/platinum as methanol-resistant oxygen-reduction electrocatalyst for DMFC was investigated. Platinum was chemically deposited on the carbon-supported cobalt phthalocyanine (CoPc), and then it was heat-treated in high purity nitrogen at 300 °C, 635 °C and 980 °C. In order to evaluate the electrocatalytic behavior of CoPc-Pt/C, the PtCo/C and Pt/C as reference catalysts were employed. TGA, XRD, EDAX, XPS and electrochemical experiments were used to study the thermal stability, crystal structure, physical characterization and electrochemical behavior of these catalysts. These catalysts exhibited similar electrocatalytic activity for oxygen reaction in 0.5 M H₂SO₄ solution. In methanol tolerance experiments, Pt/C, PtCo/C and CoPc-Pt/C heated at 980 °C were active for the methanol oxidation reaction (MOR). The presence of Co did not improve resistance to methanol poisoning. However, the CoPc-Pt/C after 300 °C or 635 °C heat-treatment demonstrated significant inactivity for MOR, hence they have a good ability to resist methanol poisoning. The current study indicated that the macrocyclic structure of phthalocyanine is the most important factor to improve the methanol tolerance of CoPc-Pt/C as the oxygen-reduction reaction (ORR) electrocatalyst. The CoPc-Pt based catalyst should be a good alternation for oxygen electro-reduction reaction in DMFC.     

A glue method for fabricating membrane electrode assemblies for direct methanol fuel cells

We present a simple glue method for fabricating membrane electrode assemblies (MEA) for direct methanol fuel cells (DMFC). Rather than the conventional “dry” hot-pressing method that relies solely on hot-pressing at a high pressure and temperature to form a MEA, the “wet” method developed in this work introduces a binding agent, consisting of Nafion^® solution, between a polymer electrolyte membrane (PEM) and an anode/cathode. The introduced binding agent can provide a better adhesion and stronger binding force between a membrane and an electrode, thereby facilitating a better interfacial contact between the electrode and the Nafion^® membrane, which has been proved by scanning electron microscopy (SEM) analyses to the cross-sectional morphology of the MEA after long-term operation. The cell performance characterization showed the MEA fabricated by the glue method was more stable in cell performance than that fabricated by the conventional hot-pressing method. Cyclic voltammetry (CV) results also demonstrated the MEA fabricated by the glue method exhibited a higher electrochemical surface area (ESA) as a result of the improved interfacial contact between the Nafion^® membrane and the electrodes. Finally, the DMFC with the MEA fabricated by the glue method was characterized by the electrochemical impedance spectroscopy (EIS).     

Characterization of catalysts and membrane in DMFC lifetime testing

The lifetime and performance of a direct methanol fuel cell (DMFC) were investigated to understand the correlation between the structure of catalysts/membrane and cell performance versus time. The cell polarization and performance curves were obtained during the DMFC operation with the time. The catalysts and Nafion^® membrane of the membrane electrode assembly (MEA) from the lifetime test were comprehensively examined by XRD, HRTEM, FTIR and Raman spectroscopy techniques. The results revealed that there was significant performance degradation during the first 200 h operation; while the degradation was slowing down between 200 and 704 h operation. The degradation became worse after 1002 h operation. The increases of the catalyst particle size from both anode and cathode catalysts were observed after the DMFC lifetime test. The changes of microstructure, surface composition, the interfacial structure of the MEA, and the aging of Nafion^® under the DMFC lifetime tests were also observed.     

Pt/onion-like fullerenes as catalyst for direct methanol fuel cell

Onion-like fullerenes synthesized by arc discharge in water were used as support of Pt nanoparticles as electrocatalytic materials for direct methanol fuel cell. Uniform platinum nanoparticles with the average diameter of about 4.3 nm were well dispersed on the surface of onion-like fullerenes by impregnation-reduction method. The morphologies and microstructures of the as-prepared composites were studied by means of XRD and TEM. Electrochemical analysis shows that this kind of nano material may be an excellent candidate to be used as the support of catalyst for methanol electrochemical oxidation.     

Performance of Sewage Sludge Treatment and Electricity Generation by Different Configuration Microbial Fuel Cells

This paper compared the degradation efficiency of sludge organic matters and electric-production by two typical microbial fuel cells——dual-chamber microbial fuel cell(DMFC)and single chamber air cathode microbial fuel cell(SAMFC),and the variations of sludge protein,polysaccharide and ammonia nitrogen within the systems were also investigated.The results showed that the concentration of sludge soluble chemical oxygen demand,protein and carbohydrate of DMFC are higher than these of SAMFC during the systems operation,while DMFC can achieve a better ammonia nitrogen removal than SAMFC.Under the same operation condition,the stable voltage output of DMFC and SAMFC is 0.61 V and 0.37 V;the maximum power density of DMFC and SAMFC is 2.79 W/m3and 1.25 W/m3;TCOD removal efficiency of DMFC and SAMFC is 34.14%and 28.63%for 12 d,respectively.Meanwhile,DMFC has a higher coulomb efficiency than SAMFC,but both are less than5%.The results showed that DMFC present a better performance on sludge degradation and electric-production.