Materials and characterization techniques for high-temperature polymer electrolyte membrane fuel cells.

PubMed

Zeis, Roswitha

2015-01-01

The performance of high-temperature polymer electrolyte membrane fuel cells (HT-PEMFC) is critically dependent on the selection of materials and optimization of individual components. A conventional high-temperature membrane electrode assembly (HT-MEA) primarily consists of a polybenzimidazole (PBI)-type membrane containing phosphoric acid and two gas diffusion electrodes (GDE), the anode and the cathode, attached to the two surfaces of the membrane. This review article provides a survey on the materials implemented in state-of-the-art HT-MEAs. These materials must meet extremely demanding requirements because of the severe operating conditions of HT-PEMFCs. They need to be electrochemically and thermally stable in highly acidic environment. The polymer membranes should exhibit high proton conductivity in low-hydration and even anhydrous states. Of special concern for phosphoric-acid-doped PBI-type membranes is the acid loss and management during operation. The slow oxygen reduction reaction in HT-PEMFCs remains a challenge. Phosphoric acid tends to adsorb onto the surface of the platinum catalyst and therefore hampers the reaction kinetics. Additionally, the binder material plays a key role in regulating the hydrophobicity and hydrophilicity of the catalyst layer. Subsequently, the binder controls the electrode-membrane interface that establishes the triple phase boundary between proton conductive electrolyte, electron conductive catalyst, and reactant gases. Moreover, the elevated operating temperatures promote carbon corrosion and therefore degrade the integrity of the catalyst support. These are only some examples how materials properties affect the stability and performance of HT-PEMFCs. For this reason, materials characterization techniques for HT-PEMFCs, either in situ or ex situ, are highly beneficial. Significant progress has recently been made in this field, which enables us to gain a better understanding of underlying processes occurring during fuel cell operation. Various novel tools for characterizing and diagnosing HT-PEMFCs and key components are presented in this review, including FTIR and Raman spectroscopy, confocal Raman microscopy, synchrotron X-ray imaging, X-ray microtomography, and atomic force microscopy.

Materials and characterization techniques for high-temperature polymer electrolyte membrane fuel cells

PubMed Central

2015-01-01

Summary The performance of high-temperature polymer electrolyte membrane fuel cells (HT-PEMFC) is critically dependent on the selection of materials and optimization of individual components. A conventional high-temperature membrane electrode assembly (HT-MEA) primarily consists of a polybenzimidazole (PBI)-type membrane containing phosphoric acid and two gas diffusion electrodes (GDE), the anode and the cathode, attached to the two surfaces of the membrane. This review article provides a survey on the materials implemented in state-of-the-art HT-MEAs. These materials must meet extremely demanding requirements because of the severe operating conditions of HT-PEMFCs. They need to be electrochemically and thermally stable in highly acidic environment. The polymer membranes should exhibit high proton conductivity in low-hydration and even anhydrous states. Of special concern for phosphoric-acid-doped PBI-type membranes is the acid loss and management during operation. The slow oxygen reduction reaction in HT-PEMFCs remains a challenge. Phosphoric acid tends to adsorb onto the surface of the platinum catalyst and therefore hampers the reaction kinetics. Additionally, the binder material plays a key role in regulating the hydrophobicity and hydrophilicity of the catalyst layer. Subsequently, the binder controls the electrode–membrane interface that establishes the triple phase boundary between proton conductive electrolyte, electron conductive catalyst, and reactant gases. Moreover, the elevated operating temperatures promote carbon corrosion and therefore degrade the integrity of the catalyst support. These are only some examples how materials properties affect the stability and performance of HT-PEMFCs. For this reason, materials characterization techniques for HT-PEMFCs, either in situ or ex situ, are highly beneficial. Significant progress has recently been made in this field, which enables us to gain a better understanding of underlying processes occurring during fuel cell operation. Various novel tools for characterizing and diagnosing HT-PEMFCs and key components are presented in this review, including FTIR and Raman spectroscopy, confocal Raman microscopy, synchrotron X-ray imaging, X-ray microtomography, and atomic force microscopy. PMID:25671153

Vertically Aligned Carbon Nanotubes at Different Temperatures by Spray Pyrolysis Techniques

NASA Astrophysics Data System (ADS)

Afre, Rakesh A.; Soga, T.; Jimbo, T.; Kumar, Mukul; Ando, Y.; Sharon, M.

Vertically aligned arrays of multi-walled carbon nanotubes (VACNTs) were grown by spray pyrolysis of turpentine oil and ferrocene mixture at temperatures higher than 700°C. Using this simple method, we report the successful growth of vertically aligned nanotubes of ~300μm length and diameter in the range of ?20-80nm on Si(100) substrate. The ferrocene acts as an in situ Fe catalyst precursor, forming the nano-sized metallic iron particles for formation of VACNTs on the Si substrate. The morphological characteristics of VACNTs are confirmed by SEM, TEM and Raman spectroscopy and growth mechanism is discussed in short.

Sol-gel based oxidation catalyst and coating system using same

NASA Technical Reports Server (NTRS)

Leighty, Bradley D. (Inventor); Watkins, Anthony N. (Inventor); Patry, JoAnne L. (Inventor); Schryer, Jacqueline L. (Inventor); Oglesby, Donald M. (Inventor)

2010-01-01

An oxidation catalyst system is formed by particles of an oxidation catalyst dispersed in a porous sol-gel binder. The oxidation catalyst system can be applied by brush or spray painting while the sol-gel binder is in its sol state.

DEVELOPMENT OF ATTRITION RESISTANT IRON-BASED FISCHER-TROPSCH CATALYSTS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Adeyinka A. Adeyiga

2003-12-01

Fischer-Tropsch (FT) synthesis to convert syngas (CO + H{sub 2}) derived from natural gas or coal to liquid fuels and wax is a well-established technology. For low H{sub 2} to CO ratio syngas produced from CO{sub 2} reforming of natural gas or from gasification of coal, the use of Fe catalysts is attractive because of their high water gas shift activity in addition to their high FT activity. Fe catalysts are also attractive due to their low cost and low methane selectivity. Because of the highly exothermic nature of the FT reaction, there has been a recent move away frommore » fixed-bed reactors toward the development of slurry bubble column reactors (SBCRs) that employ 30 to 90 {micro}m catalyst particles suspended in a waxy liquid for efficient heat removal. However, the use of Fe FT catalysts in an SBCR has been problematic due to severe catalyst attrition resulting in fines that plug the filter employed to separate the catalyst from the waxy product. Fe catalysts can undergo attrition in SBCRs not only due to vigorous movement and collisions but also due to phase changes that occur during activation and reaction. The objectives of this research were to develop a better understanding of the parameters affecting attrition of Fe F-T catalysts suitable for use in SBCRs and to incorporate this understanding into the design of novel Fe catalysts having superior attrition resistance. The catalysts were prepared by co-precipitation, followed by binder addition and spray drying at 250 C in a 1 m diameter, 2 m tall spray dryer. The binder silica content was varied from 0 to 20 wt %. The results show that use of small amounts of precipitated SiO{sub 2} alone in spray-dried Fe catalysts can result in good attrition resistance. All catalysts investigated with SiO{sub 2} wt% {le} 12 produced fines less than 10 wt% during the jet cup attrition test, making them suitable for long-term use in a slurry bubble column reactor. Thus, concentration rather than type of SiO{sub 2} incorporated into catalyst has a more critical impact on catalyst attrition resistance of spray-dried Fe catalysts. Lower amounts of SiO{sub 2} added to a catalyst give higher particle densities and therefore higher attrition resistances. In order to produce a suitable SBCR catalyst, however, the amount of SiO{sub 2} added has to be optimized to provide adequate surface area, particle density, and attrition resistance. Two of the catalysts with precipitated and binder silica were tested in Texas A&M University's CSTR (Autoclave Engineers). Spray-dried catalysts with compositions 100 Fe/5 Cu/4.2 K/11 (P) SiO{sub 2} and 100 Fe/5 Cu/4.2 K/1.1 (B) SiO{sub 2} have excellent selectivity characteristics (low methane and high C{sub 5}{sup +} yields), but their productivity and stability (deactivation rate) need to be improved. Mechanical integrity (attrition strength) of these two catalysts was markedly dependent upon their morphological features. The attrition strength of the catalyst made out of largely spherical particles (1.1 (B) SiO{sub 2}) was considerably higher than that of the catalyst consisting of irregularly shaped particles (11 (P) SiO{sub 2}).« less

Healthy Cooking Techniques

MedlinePlus

... spray for this cooking method. Using herbs and spices Creating meals with herbs, spices and other natural flavorings is one of the ... vinegar or citrus juice, and add herbs and spices as desired. Fresh hot peppers. Remove the membranes ...

Sputter-deposited fuel cell membranes and electrodes

NASA Technical Reports Server (NTRS)

Narayanan, Sekharipuram R. (Inventor); Jeffries-Nakamura, Barbara (Inventor); Chun, William (Inventor); Ruiz, Ron P. (Inventor); Valdez, Thomas I. (Inventor)

2001-01-01

A method for preparing a membrane for use in a fuel cell membrane electrode assembly includes the steps of providing an electrolyte membrane, and sputter-depositing a catalyst onto the electrolyte membrane. The sputter-deposited catalyst may be applied to multiple sides of the electrolyte membrane. A method for forming an electrode for use in a fuel cell membrane electrode assembly includes the steps of obtaining a catalyst, obtaining a backing, and sputter-depositing the catalyst onto the backing. The membranes and electrodes are useful for assembling fuel cells that include an anode electrode, a cathode electrode, a fuel supply, and an electrolyte membrane, wherein the electrolyte membrane includes a sputter-deposited catalyst, and the sputter-deposited catalyst is effective for sustaining a voltage across a membrane electrode assembly in the fuel cell.

Application of green chemistry techniques to prepare electrocatalysts for direct methanol fuel cells.

PubMed

Shimizu, Kenichi; Wang, Joanna S; Wai, Chien M

2010-03-25

A series of green techniques for synthesizing carbon nanotube-supported platinum nanoparticles and their high electrocatalytic activity toward methanol fuel cell applications are reported. The techniques utilize either the supercritical fluid carbon dioxide or water as a medium for depositing platinum nanoparticles on surfaces of multiwalled or single-walled carbon nanotubes. The catalytic properties of the carbon nanotubes-supported Pt nanoparticle catalysts prepared by four different techniques are compared for anodic oxidation of methanol and cathodic reduction of oxygen using cyclic voltammetry. One technique using galvanic exchange of Pt(2+) in water with zerovalent iron present on the surfaces of as-grown single-walled carbon nanotubes produces a Pt catalyst that shows an unusually high catalytic activity for reduction of oxygen but a negligible activity for oxidation of methanol. This fuel-selective catalyst may have a unique application as a cathode catalyst in methanol fuel cells to alleviate the problems caused by crossover of methanol through the polymer electrolyte membrane.

Development of New Generation of Ceramics for Environmentally Focused Chemical Separations

NASA Astrophysics Data System (ADS)

Ramakrishnan, Girish

This dissertation focuses on the use of composite materials for environmental applications. For the first time, applications of both fresh and aged concrete as inexpensive adsorbents for nitrogen dioxide (NO2) removal is demonstrated. Concrete is the most widely used composite material of the modern era. Cement manufacturing (a major component of concrete) is considered to be one of the leading contributors to air pollution, resulting in 7% of the global carbon dioxide emissions along with a number of other harmful pollutants such as oxides, mercury and particulates. These emissions aide in the formation of acid rain, smog, and toxic ground level ozone, causing detrimental effects such as respiratory illnesses, visibility reduction, eutrification and global warming. This thesis offers a novel and sustainable solution in mitigating NOX emissions, by introducing the significant adsorption potential of recycled concrete. The work is based on both commercially available cement paste and already aged concrete samples, providing truly scalable solutions. The concrete samples aged for different periods of time were exposed to NO2 to measure their adsorption capacity. The results show that all of the concrete samples (fresh and aged) exhibited excellent NO2 adsorption capacity, with the fresh concrete samples removing almost 100% of the NO2. Furthermore, to compare the effects of long term aging, 12 year-old recently demolished concrete samples were obtained and its NOX removal was shown to be almost 60%. The experimental results provide evidence of nitrate and nitrite species formation from chemical reactions occurring between NO2 and surface alkaline species. This important discovery can be utilized for NO2 removal and subsequent NOX sequestered demolished concrete (NSDC) recycling in new concrete, either as a set accelerating admixture or as a corrosion inhibitor, a big leap towards better sustainability and longevity of the new reinforced concrete structures. The rest of this thesis focuses on development of a new generation of ceramic membranes utilizing thermal spray techniques to produce highly scalable and extremely cost effective filtration membranes. Thermal spray method of membrane manufacturing has the advantage of economic scalability (up to tens of square meters) along with performance enhancement as compared to conventional wet casting process. In addition to developing a proof of concept for this approach, several strategies on how to improve ceramic membranes' performance via spraying process optimization are also described. Specifically, several thermal sprayed Alumina membrane samples were prepared by varying different process parameters. These samples were characterized using known techniques and subjected to permeability and size exclusion tests to correlate spraying parameters with membranes' performance. The membrane samples showed excellent clean water flux comparable to commercially available membranes and had rejection rates up to 96%. These results show that the membranes produced in this research achieve outstanding performance at a fraction of the cost of commercially produced membrane, enabling the use of membrane filtrations units in developing countries.

Y-junction carbon nanocoils: synthesis by chemical vapor deposition and formation mechanism

PubMed Central

Ding, Er-Xiong; Wang, Jing; Geng, Hong-Zhang; Wang, Wen-Yi; Wang, Yan; Zhang, Ze-Chen; Luo, Zhi-Jia; Yang, Hai-Jie; Zou, Cheng-Xiong; Kang, Jianli; Pan, Lujun

2015-01-01

Y-junction carbon nanocoils (Y-CNCs) were synthesized by thermal chemical vapor deposition using Ni catalyst prepared by spray-coating method. According to the emerging morphologies of Y-CNCs, several growth models were advanced to elucidate their formation mechanisms. Regarding the Y-CNCs without metal catalyst in the Y-junctions, fusing of contiguous CNCs and a tip-growth mechanism are considered to be responsible for their formation. However, as for the Y-CNCs with catalyst presence in the Y-junctions, the formation can be ascribed to nanoscale soldering/welding and bottom-growth mechanism. It is found that increasing spray-coating time for catalyst preparation generates agglomerated larger nanoparticles strongly adhering to the substrate, resulting in bottom-growth of CNCs and appearance of the metal catalyst in the Y-junctions. In the contrary case, CNCs catalyzed by isolated smaller nanoparticles develop Y-junctions with an absence of metal catalyst by virtue of weaker adhesion of catalyst with the substrate and tip-growth of CNCs. PMID:26063127

In-plane and through-plane non-uniform carbon corrosion of polymer electrolyte fuel cell cathode catalyst layer during extended potential cycles

NASA Astrophysics Data System (ADS)

Ghosh, Sourov; Ohashi, Hidenori; Tabata, Hiroshi; Hashimasa, Yoshiyuki; Yamaguchi, Takeo

2017-09-01

The impact of electrochemical carbon corrosion via potential cycling durability tests mimicking start-stop operation events on the microstructure of the cathode catalyst layer in polymer electrolyte fuel cells (PEFCs) is investigated using focused ion beam (FIB) fabrication without/with the pore-filling technique and subsequent scanning electron microscope (SEM) observations. FIB/SEM investigations without pore-filling reveals that the durability test induces non-uniform cathode shrinking across the in-plane direction; the thickness of the catalyst layer decreases more under the gas flow channel compared to the area under the rim of the flow field. Furthermore, FIB/SEM investigations with the pore-filling technique reveal that the durability test also induces non-uniform cathode shrinking in the through-plane direction; the pores in the area close to the membrane are more shrunken compared with those close to the microporous layer. In particular, a thin area (1-1.5 μm) close to the membrane is found to be severely damaged; it includes closed pores that hinder mass transport through the catalyst layer. It is suggested that uneven carbon corrosion and catalyst layer compaction are responsible for the performance loss during potential cycling operation of PEFCs.

Direct deposit of catalyst on the membrane of direct feed fuel cells

NASA Technical Reports Server (NTRS)

Chun, William (Inventor); Narayanan, Sekharipuram R. (Inventor); Jeffries-Nakamura, Barbara (Inventor); Valdez, Thomas I. (Inventor); Linke, Juergen (Inventor)

2001-01-01

An improved direct liquid-feed fuel cell having a solid membrane electrolyte for electrochemical reactions of an organic fuel. Catalyst utilization and catalyst/membrane interface improvements are disclosed. Specifically, the catalyst layer is applied directly onto the membrane electrolyte.

Investigating catalyst coated membrane equilibration time for polymer electrolyte membrane fuel cell manufacturing

NASA Astrophysics Data System (ADS)

Cote, Philippe

Mercedes-Benz Canada Inc., Fuel Cell Division, manufactures polymer electrolyte membrane fuel cell stacks for use in vehicles. The manufacturing line is being optimized for efficiency and quality control, in order to uphold the high standards of Mercedes-Benz Inc. vehicles. In an operating polymer electrolyte membrane fuel cell, the catalyst coated membrane facilitates the electrochemical reaction that generates electricity. This research examines the equilibration of catalyst coated membrane rolls to controlled temperature and humidity conditions, before they are used in the manufacturing of polymer electrolyte membrane fuel cells. Equilibration involves allowing the water content in the catalyst coated membrane to stabilize at the controlled conditions, in order to reduce mechanical stress in the material for better manufacturability. Initial equilibration measurements were conducted on discrete catalyst coated membrane samples using novel electronic conductivity measurements of the catalyst layer, and compared to ionic conductivity measurements of the membrane. Electronic conductivity measurements are easier to implement in the manufacturing environment than the more complex ionic conductivity measurements. When testing discrete catalyst coated membrane samples in an environmental chamber, the equilibration trends for the measured ionic and electronic conductivity signals were similar enough to permit us to adapt the electronic conductivity measurements for catalyst coated membrane in roll form. Equilibration measurements of catalyst coated membrane rolls were optimized to achieve a robust and repeatable procedure which could be used in the manufacturing environment at Mercedes-Benz Canada Inc., Fuel Cell Division.

Crumpled rGO-supported Pt-Ir bifunctional catalyst prepared by spray pyrolysis for unitized regenerative fuel cells

NASA Astrophysics Data System (ADS)

Kim, In Gyeom; Nah, In Wook; Oh, In-Hwan; Park, Sehkyu

2017-10-01

Three-dimensional (3D) crumpled reduced graphene oxide supported Pt-Ir alloys that served as bifunctional oxygen catalysts for use in untized regenerative fuel cells were synthesized by a facile spray pyrolysis method. Pt-Ir catalysts supported on rGO (Pt-Ir/rGOs) were physically characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and thermogravimetric analysis (TGA) to observe change in composition by heat treatment, alloying, and morphological transition of the catalysts. Their catalytic activities and stabilities for the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) conditions were electrochemically investigated using cyclic voltammetry (CV), linear sweep voltammetry (LSV), potential cycling and hold tests on the rotating disk electrode (RDE). Pt-Ir/rGO with no post heat-treatment (Pt-Ir/rGO_NP) showed a lower activity for ORR and OER although metal nanoparticles decorated on the support are relatively small. However, Pt-Ir/rGO showed remarkably enhanced activity following heat treatment, depending on temperature. Pt-Ir/rGO heat-treated at 600 °C after spray pyrolysis (Pt-Ir/rGO_P600) exhibited a higher activity and stability than a commercially available Pt/C catalyst kept under the ORR condition, and it also revealed a comparable OER activity and durability versus the commercial unsupported Ir catalyst.

A monolithic integrated micro direct methanol fuel cell based on sulfo functionalized porous silicon

NASA Astrophysics Data System (ADS)

Wang, M.; Lu, Y. X.; Liu, L. T.; Wang, X. H.

2016-11-01

In this paper, we demonstrate a monolithic integrated micro direct methanol fuel cell (μDMFC) for the first time. The monolithic integrated μDMFC combines proton exchange membrane (PEM) and Pt nanocatalysts, in which PEM is achieved by the functionalized porous silicon membrane and 3D Pt nanoflowers being synthesized in situ on it as catalysts. Sulfo groups functionalized porous silicon membrane serves as a PEM and a catalyst support simultaneously. The μDMFC prototype achieves an open circuit voltage of 0.3 V, a maximum power density of 5.5 mW/cm2. The monolithic integrated μDMFC offers several desirable features such as compatibility with micro fabrication techniques, an undeformable solid PEM and the convenience of assembly.

Attrition resistant bulk iron catalysts and processes for preparing and using same

DOEpatents

Jothimurugesan, Kandaswamy [Ponca City, OK; Goodwin, Jr., James G.; Gangwal, Santosh K [Cary, NC

2007-08-21

An attrition resistant precipitated bulk iron catalyst is prepared from iron oxide precursor and a binder by spray drying. The catalysts are preferably used in carbon monoxide hydrogenation processes such as Fischer-Tropsch synthesis. These catalysts are suitable for use in fluidized-bed reactors, transport reactors and, especially, slurry bubble column reactors.

New electrocatalysts for unitized regenerative fuel cell: Pt-Ir alloy deposited on the proton exchange membrane surface by impregnation-reduction method.

PubMed

Wan, Chieh-Hao; Wu, Chun-Lin; Lin, Meng-Tsun; Shih, Chihhsiong

2010-07-01

In this paper, a modified technique to prepare Pt-Ir catalyst layer on the proton exchange membrane (PEM) surface using the impregnation-reduction (IR) method is proposed to improve the electrocatalytic activity as well as the life cycle of the bifunctional oxygen electrode (BOE). The resulted electrocatalysts were characterized by the Scanning Electron Microscopy (SEM), X-ray Diffraction (XRD), Electron Probe Micro-Analysis (EPMA), and Transmission Electron Microscope (TEM). The electrocatalytic properties of the Pt-Ir layer on PEM surface for the oxygen reduction and water oxidation reactions as well as the life cycle of MEA were investigated. Experimental results showed that the Ir particles were dispersed densely in the platinum layer through the modified IR technique. The atomic ratio of Pt over Ir elements was 9:1, and the resulted thickness of the obtained Pt-Ir catalyst layer was about 1.0 microm. The Pt-Ir catalyst layer was composed of Pt layer doped with Ir nano-particles comprising nano Pt-Ir alloy phase. The large surface area of Ir core with Pt shell particles and the presence of nano Pt-Ir alloy phase led to a higher electrocatalytic activity of BOE. Due to the good binding between the Nafion membrane and the Pt-Ir alloy catalyst, as well as the composite structure of the resulted Pt-Ir, the life cycle of Unitized Regenerative Fuel Cell (URFC) is improved through this novel BOE.

Investigation of the spray characteristics for a secondary fuel injection nozzle using a digital image processing method

NASA Astrophysics Data System (ADS)

Jeong, Haeyoung; Lee, Kihyung; Ikeda, Yuji

2007-05-01

There are many ways to reduce diesel engine exhaust emissions. However, NOx emission is difficult to reduce because the hydrocarbon (HC) concentration in a diesel engine is not sufficient for NOx conversion. Therefore, in order to create stoichiometric conditions in the De-NOx catalyst, a secondary injection system is designed to inject liquid HC into the exhaust pipe. The atomization and distribution characteristics of the HC injected from a secondary injector are key technologies to obtain a high NOx conversion because inhomogeneous droplets of injected HC cause not only high fuel consumption but also deterioration of NOx emission. This paper describes the spray characteristics of a secondary injector including the spray angle, penetration length and breakup behaviour of the spray to optimize the reduction rate of the NOx catalyst. In this study, various optical diagnostics were applied to investigate these spray characteristics, the atomization mechanism and spray developing process. The visualization and image processing method for the spray pulsation were developed by high speed photography. The influence of the fuel supply pressure on the spray behaviour and a more detailed spray developing process have been analysed experimentally using image processing. Finally, the experimental results were used to correlate the spray structure to the injection system performance and to provide a design guide for a secondary injector nozzle.

INEL Spray-forming Research

NASA Technical Reports Server (NTRS)

Mchugh, Kevin M.; Key, James F.

1993-01-01

Spray forming is a near-net-shape fabrication technology in which a spray of finely atomized liquid droplets is deposited onto a suitably shaped substrate or mold to produce a coherent solid. The technology offers unique opportunities for simplifying materials processing without sacrificing, and oftentimes substantially improving, product quality. Spray forming can be performed with a wide range of metals and nonmetals, and offers property improvements resulting from rapid solidification (e.g., refined microstructures, extended solid solubilities and reduced segregation). Economic benefits result from process simplification and the elimination of unit operations. Researchers at the Idaho National Engineering Laboratory (INEL) are developing spray-forming technology for producing near-net-shape solids and coatings of a variety of metals, polymers, and composite materials. Results from several spray forming programs are presented to illustrate the range of capabilities of the technique as well as the accompanying technical and economic benefits. Low-carbon steel strip greater than 0.75 mm thick and polymer membranes for gas/gas and liquid/liquid separations that were spray formed are discussed; recent advances in spray forming molds, dies, and other tooling using low-melting-point metals are described.

A fully spray-coated fuel cell membrane electrode assembly using Aquivion ionomer with a graphene oxide/cerium oxide interlayer

NASA Astrophysics Data System (ADS)

Breitwieser, Matthias; Bayer, Thomas; Büchler, Andreas; Zengerle, Roland; Lyth, Stephen M.; Thiele, Simon

2017-05-01

A novel multilayer membrane electrode assembly (MEA) for polymer electrolyte membrane fuel cells (PEMFCs) is fabricated in this work, within a single spray-coating device. For the first time, direct membrane deposition is used to fabricate a PEMFC by spraying the short-side-chain ionomer Aquivion directly onto the gas diffusion electrodes. The fully sprayed MEA, with an Aquivion membrane 10 μm in thickness, achieved a high power density of 1.6 W/cm2 for H2/air operation at 300 kPaabs. This is one of the highest reported values for thin composite membranes operated in H2/air atmosphere. By the means of confocal laser scanning microscopy, individual carbon fibers from the gas diffusion layer are identified to penetrate through the micro porous layer (MPL), likely causing a low electrical cell resistance in the range of 150 Ω cm2 through the thin sprayed membranes. By spraying a 200 nm graphene oxide/cerium oxide (GO/CeO2) interlayer between two layers of Aquivion ionomer, the impact of the electrical short is eliminated and the hydrogen crossover current density is reduced to about 1 mA/cm2. The peak power density of the interlayer-containing MEA drops only by 10% compared to a pure Aquivion membrane of similar thickness.

Mesostructured platinum-free anode and carbon-free cathode catalysts for durable proton exchange membrane fuel cells.

PubMed

Cui, Xiangzhi; Shi, Jianlin; Wang, Yongxia; Chen, Yu; Zhang, Lingxia; Hua, Zile

2014-01-01

As one of the most important clean energy sources, proton exchange membrane fuel cells (PEMFCs) have been a topic of extensive research focus for decades. Unfortunately, several critical technique obstacles, such as the high cost of platinum electrode catalysts, performance degradation due to the CO poisoning of the platinum anode, and carbon corrosion by oxygen in the cathode, have greatly impeded its commercial development. A prototype of a single PEMFC catalyzed by a mesostructured platinum-free WO3/C anode and a mesostructured carbon-free Pt/WC cathode catalysts is reported herein. The prototype cell exhibited 93% power output of a standard PEMFC using commercial Pt/C catalysts at 50 and 70 °C, and more importantly, CO poisoning-free and carbon corrosion-resistant characters of the anode and cathode, respectively. Consequently, the prototype cell demonstrated considerably enhanced cell operation durability. The mesostructured electrode catalysts are therefore highly promising in the future development and application of PEMFCs. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis and characterization of Cu3(BTC)2 membranes by thermal spray seeding and secondary growth.

PubMed

Noh, Seung-Jun; Kwon, Hyuk Taek; Kim, Jinsoo

2013-08-01

Crack-free Cu3(BTC)2 membranes were successfully prepared by thermal spray seeding and secondary growth method. Thermal spray seeding method, combining thermal seeding and pressurized spraying, uniformly distributed seed solution on the support, anchoring seed crystals tightly on the support. After secondary growth of the seeded support in the autoclave, continuous crack-free membrane was obtained by controlling cooling and drying steps. The gas permeation test was conducted at various temperatures using H2, CO2, CH4 and N2 gases.

Study of superhydrophobic electrosprayed catalyst layers using a localized reference electrode technique

NASA Astrophysics Data System (ADS)

Chaparro, A. M.; Ferreira-Aparicio, P.; Folgado, M. A.; Brightman, E.; Hinds, G.

2016-09-01

The performance of electrosprayed cathode catalyst layers in a polymer electrolyte membrane fuel cell (PEMFC) is studied using a localized reference electrode technique. Single cells with an electrosprayed cathode catalyst layer show an increase of >20% in maximum power density under standard testing conditions, compared with identical cells assembled with a conventional, state-of-the-art, gas diffusion cathode. When operated at high current density (1.2 A cm-2) the electrosprayed catalyst layers show more homogeneous distribution of the localized cathode potential, with a standard deviation from inlet to outlet of <50 mV, compared with 79 mV for the conventional gas diffusion cathode. Higher performance and homogeneity of cell response is attributed to the superhydrophobic nature of the macroporous electrosprayed catalyst layer structure, which enhances the rate of expulsion of liquid water from the cathode. On the other hand, at low current densities (<0.5 A cm-2), the electrosprayed layers exhibit more heterogeneous distribution of cathode potential than the conventional cathodes; this behavior is attributed to less favorable kinetics for oxygen reduction in very hydrophobic catalyst layers. The optimum performance may be obtained with electrosprayed catalyst layers employing a high Pt/C catalyst ratio.

Hydrogen production from methane using oxygen-permeable ceramic membranes

NASA Astrophysics Data System (ADS)

Faraji, Sedigheh

Non-porous ceramic membranes with mixed ionic and electronic conductivity have received significant interest in membrane reactor systems for the conversion of methane and higher hydrocarbons to higher value products like hydrogen. However, hydrogen generation by this method has not yet been commercialized and suffers from low membrane stability, low membrane oxygen flux, high membrane fabrication costs, and high reaction temperature requirements. In this dissertation, hydrogen production from methane on two different types of ceramic membranes (dense SFC and BSCF) has been investigated. The focus of this research was on the effects of different parameters to improve hydrogen production in a membrane reactor. These parameters included operating temperature, type of catalyst, membrane material, membrane thickness, membrane preparation pH, and feed ratio. The role of the membrane in the conversion of methane and the interaction with a Pt/CeZrO2 catalyst has been studied. Pulse studies of reactants and products over physical mixtures of crushed membrane material and catalyst have clearly demonstrated that a synergy exists between the membrane and the catalyst under reaction conditions. The degree of catalyst/membrane interaction strongly impacts the conversion of methane and the catalyst performance. During thermogravimetric analysis, the onset temperature of oxygen release for BSCF was observed to be lower than that for SFC while the amount of oxygen release was significantly greater. Pulse injections of CO2 over crushed membranes at 800°C have shown more CO2 dissociation on the BSCF membrane than the SFC membrane, resulting in higher CO formation on the BSCF membrane. Similar to the CO2 pulses, when CO was injected on the samples at 800°C, CO2 production was higher on BSCF than SFC. It was found that hydrogen consumption on BSCF particles is 24 times higher than that on SFC particles. Furthermore, Raman spectroscopy and temperature programmed desorption studies of CO and CO2 showed a higher CO and CO2 adsorption (for temperatures ranging from room temperature to 600°C) on BSCF compared to the SFC membrane. CO2 reforming reactions on BSCF and SFC dense membranes in a membrane reactor showed higher methane conversion and H2/CO ratio on BSCF than SFC in the presence of the Pt/CeZrO2 catalyst. This high conversion and H2/CO ratio could be ascribed to higher CO, CO2, and H2 adsorption on BSCF than SFC, resulting in higher steam and CO2 reforming on the BSCF. The Pt-Ni/CeZrO2 catalyst exhibits promising performance for hydrogen production. Platinum enhances the reducibility of Ni/Al2O 3 and Ni/CeZrO2 catalysts resulting in improved catalysts for H2 production at moderate temperatures. TPR and Raman studies show an alloy formation in the Pt-Ni/Al2O3 catalyst. Further work is required to study the interaction between Pt and Ni in the bimetallic Pt-Ni/CeZrO2 and Pt-Ni/Al2O3 catalysts. Although the Pt-Ni/Al2O3 catalyst shows high methane conversion in the presence of the BSCF membrane at 800°C, the activity of this catalyst is low at 600°C. Pt-Ni/CeZrO2 bimetallic catalyst demonstrates superior performance compared to Pt-Ni/Al2O3 catalyst at 600°C. The thinner BSCF membrane (2.2 mm) demonstrates a higher methane conversion and H2:CO ratio than the thicker BSCF membrane (2.6 mm) because membrane oxygen flux is inversely proportional to thickness. Varying the pH of the precursor solution during membrane preparation has no significant effect on the oxygen flux or the reaction. The CH 4:CO2 feed ratio significantly affects the hydrogen production over the BSCF membrane. Altering the CH4:CO2 ratio has a direct impact on the oxygen flux, which in turn can influence the reaction pathway. These studies suggest that the Pt-Ni/CeZrO2 catalyst might be suitable for low-temperature hydrocarbon conversion reactions over thin BSCF ceramic membranes. Most importantly, the BSCF membrane can reduce the apparent activation energy of the CO2 reforming reaction by changing the reaction pathway to include more steam reforming.

Fabrication and characterization of anode catalyst layers with structural variations for DMFC

NASA Astrophysics Data System (ADS)

Wang, Dazhi; Shi, Peng; Zhou, Peng; Mao, Qing; Liang, Junsheng; Wang, Suli; Li, Yang; Ren, Tongqun; Sun, Gongquan

2018-04-01

In this work, the electrohydrodynamic jet (E-Jet) Layer-by-Layer (LbL) deposition technique was employed to produce anode catalyst layer (CL) structure for direct methanol fuel cells (DMFC). The CLs with different thickness and porosity were fabricated with the control of the E-Jet deposition parameters. Then, the deposited anode CLs with structural variations were assembled to membrane electrode assemblies (MEAs). The results showed that the anode CL with higher porosity contributed higher dispersed catalyst, which further induced greater electrochemical active surface area (ESA) and higher performance. At optimized working condition the anode CL with high-dispersed catalyst of was produced using the E-Jet LbL deposition technique. It was observed that the peak power density is 72.8 mW cm‑2 for the cell having a porosity of 0.63, which has an increase of about 33% after modification of the CL structure.

Catalytic ignitor for regenerative propellant gun

NASA Technical Reports Server (NTRS)

Voecks, Gerald E. (Inventor); Ferraro, Ned W. (Inventor)

1994-01-01

An ignitor initiates combustion of liquid propellant in a gun by utilizing a heated catalyst onto which the liquid propellant is sprayed in a manner which mitigates the occurrence of undesirable combustion chamber oscillations. The heater heats the catalyst sufficiently to provide the activation necessary to initiate combustion of the liquid propellant sprayed thereonto. Two embodiments of the ignitor and three alternative mountings thereof within the combustion chamber are disclosed. The ignitor may also be utilized to dispose of contaminated, excess, or waste liquid propellant in a safe, controlled, simple, and reliable manner.

Catalytic Ignitor for Regenerative Propellant Gun

NASA Technical Reports Server (NTRS)

Voecks, Gerald E. (Inventor); Ferraro, Ned W. (Inventor)

1997-01-01

An ignitor initiates combustion of liquid propellant in a gun by utilizing a heated catalyst onto which the liquid propellant is sprayed in a manner which mitigates the occurrence of undesirable combustion chamber oscillations. The heater heats the catalyst sufficiently to provide the activation necessary to initiate combustion of the liquid propellant sprayed thereonto. Two embodiments of the igniter and three alternative mountings thereof within the combustion chamber are disclosed. The ignitor may also be utilized to dispose of contaminated, excess, or waste liquid propellant in a safe, controlled, simple, and reliable manner.

Micro-Membrane Electrode Assembly Design to Precisely Measure the in Situ Activity of Oxygen Reduction Reaction Electrocatalysts for PEMFC.

PubMed

Long, Zhi; Li, Yankai; Deng, Guangrong; Liu, Changpeng; Ge, Junjie; Ma, Shuhua; Xing, Wei

2017-06-20

An in situ micro-MEA technique, which could precisely measure the performance of ORR electrocatalyst using Nafion as electrolyte, was designed and compared with regular thin-film rotating-disk electrode (TFRDE) (0.1 M HClO 4 ) and normal in situ membrane electrode assembly (MEA) tests. Compared to the traditional TFRDE method, the micro-MEA technique makes the acquisition of catalysts' behavior at low potential values easily achieved without being limited by the solubility of O 2 in water. At the same time, it successfully mimics the structure of regular MEAs and obtains similar results to a regular MEA, thus providing a new technique to simply measure the electrode activity without being bothered by complicated fabrication of regular MEA. In order to further understand the importance of in situ measurement, Fe-N-C as a typical oxygen reduction reaction (ORR) free-Pt catalyst was evaluated by TFRDE and micro-MEA. The results show that the half wave potential of Fe-N-C only shifted negatively by -135 mV in comparison with state-of-the-art Pt/C catalysts from TFRDE tests. However, the active site density, mass transfer of O 2 , and the proton transfer conductivity are found to strongly influence the catalyst activity in the micro-MEA, thereby resulting in a much lower limiting current density than Pt/C (8.7 times lower). Hence, it is suggested that the micro-MEA is better in evaluating the in situ ORR performance, where the catalysts are characterized more thoroughly in terms of intrinsic activity, active site density, proton transfer, and mass transfer properties.

CuCo 2O 4 ORR/OER Bi-functional catalyst: Influence of synthetic approach on performance

DOE PAGES

Serov, Alexey; Andersen, Nalin I.; Roy, Aaron J.; ...

2015-02-07

A series of CuCo 2O 4 catalysts were synthesized by pore forming, sol-gel, spray pyrolysis and sacrificial support methods. Catalysts were characterized by XRD, SEM, XPS and BET techniques. The electrochemical activity for the oxygen reduction and oxygen evolution reactions (ORR and OER) was evaluated in alkaline media by RRDE. Density Functional Theory was used to identify two different types of active sites responsible for ORR/OER activity of CuCo 2O 4 and it was found that CuCo 2O 4 can activate the O-O bond by binding molecular oxygen in bridging positions between Co or Co and Cu atoms. It wasmore » found that the sacrificial support method (SSM) catalyst has the highest performance in both ORR and OER and has the highest content of phase-pure CuCo 2O 4. It was shown that the presence of CuO significantly decreases the activity in oxygen reduction and oxygen evolution reactions. As a result, the half-wave potential (E 1/2) of CuCo 2O 4-SSM was found as 0.8 V, making this material a state-of-the-art, unsupported oxide catalyst.« less

Deposition of Lanthanum Strontium Cobalt Ferrite (LSCF) Using Suspension Plasma Spraying for Oxygen Transport Membrane Applications

NASA Astrophysics Data System (ADS)

Fan, E. S. C.; Kesler, O.

2015-08-01

Suspension plasma spray deposition was utilized to fabricate dense lanthanum strontium cobalt ferrite oxygen separation membranes (OSMs) on porous metal substrates for mechanical support. The as-sprayed membranes had negligible and/or reversible material decomposition. At the longer stand-off distance (80 mm), smooth and dense membranes could be manufactured using a plasma with power below approximately 81 kW. Moreover, a membrane of 55 μm was observed to have very low gas leakage rates desirable for OSM applications. This thickness could potentially be decreased further to improve oxygen diffusion by using metal substrates with finer surface pores.

Silymarin-loaded solid nanoparticles provide excellent hepatic protection: physicochemical characterization and in vivo evaluation

PubMed Central

Yang, Kwan Yeol; Hwang, Du Hyeong; Yousaf, Abid Mehmood; Kim, Dong Wuk; Shin, Young-Jun; Bae, Ok-Nam; Kim, Yong-II; Kim, Jong Oh; Yong, Chul Soon; Choi, Han-Gon

2013-01-01

Background The purpose of this study was to develop a novel silymarin-loaded solid nanoparticle system with enhanced oral bioavailability and an ability to provide excellent hepatic protection for poorly water-soluble drugs using Shirasu porous glass (SPG) membrane emulsification and a spray-drying technique. Methods A silymarin-loaded liquid nanoemulsion was formulated by applying the SPG membrane emulsification technique. This was further converted into solid state nanosized particles by the spray-drying technique. The physicochemical characteristics of these nanoparticles were determined by scanning electron microscopy, differential scanning calorimetry, and powder X-ray diffraction. Their dissolution, bioavailability, and hepatoprotective activity in rats were assessed by comparison with a commercially available silymarin-loaded product. Results Formulation of a silymarin-loaded nanoemulsion, comprising silymarin, castor oil, polyvinylpyrrolidone, Transcutol HP, Tween 80, and water at a weight ratio of 5/3/3/1.25/1.25/100 was accomplished using an SPG membrane emulsification technique at an agitator speed of 700 rpm, a feed pressure of 15 kPa, and a continuous phase temperature of 25°C. This resulted in generation of comparatively uniform emulsion globules with a narrow size distribution. Moreover, the silymarin-loaded solid nanoparticles, containing silymarin/castor oil/polyvinylpyrrolidone/Transcutol HP/Tween 80 at a weight ratio of 5/3/3/1.25/1.25, improved about 1,300-fold drug solubility and retained a mean size of about 210 nm. Silymarin was located in unaltered crystalline form in the nanoparticles. The drug dissolved rapidly from the nanoparticles, reaching nearly 80% within 15 minutes, indicating three-fold better dissolution than that of the commercial product. Further, the nanoparticles showed a considerably shorter time to peak concentration, a greater area under the concentration-time curve, and a higher maximum concentration of silymarin compared with the commercial product (P < 0.05). In particular, the area under the concentration-time curve of the drug provided by the nanoparticles was approximately 1.3-fold greater than that of the commercial product. In addition, the silymarin-loaded nanoparticles significantly reduced carbon tetrachloride-induced hepatotoxicity, indicating improved bioactivity compared with silymarin powder and the commercial product. Conclusion Silymarin-loaded nanoparticles developed using SPG membrane emulsification and spray-drying techniques could be a useful system for delivery of poorly water-soluble silymarin while affording excellent hepatic protection. PMID:24039417

Two component-three dimensional catalysis

DOEpatents

Schwartz, Michael; White, James H.; Sammells, Anthony F.

2002-01-01

This invention relates to catalytic reactor membranes having a gas-impermeable membrane for transport of oxygen anions. The membrane has an oxidation surface and a reduction surface. The membrane is coated on its oxidation surface with an adherent catalyst layer and is optionally coated on its reduction surface with a catalyst that promotes reduction of an oxygen-containing species (e.g., O.sub.2, NO.sub.2, SO.sub.2, etc.) to generate oxygen anions on the membrane. The reactor has an oxidation zone and a reduction zone separated by the membrane. A component of an oxygen containing gas in the reduction zone is reduced at the membrane and a reduced species in a reactant gas in the oxidation zone of the reactor is oxidized. The reactor optionally contains a three-dimensional catalyst in the oxidation zone. The adherent catalyst layer and the three-dimensional catalyst are selected to promote a desired oxidation reaction, particularly a partial oxidation of a hydrocarbon.

Spray-applied waterproofing membranes: effective solution for safe and durable tunnel linings?

NASA Astrophysics Data System (ADS)

Pisova, Barbora; Hilar, Matous

2017-09-01

What is the perfect tunnel lining? Cost efficient, easy and fast to build with acceptable environmental impact? How to construct a watertight and safe tunnel lining? Would it be possible to apply a waterproofing system directly onto the rock face just after the tunnel face opening? This might be the system of the future enabling all concrete applied to the rock face to remain permanent. For now though, we would like to focus on an optimisation and examination of currently available technologies and materials, such as tunnel linings with the use of spray-applied waterproofing membranes. In this paper, the failure mechanisms of a tunnel lining with a spray-applied waterproofing membrane are described, the behaviour of spray-applied waterproofing membrane under various conditions (dry, moist, wet) is challenged and the possibilities of interface numerical modelling are presented. Tunnel lining design is mainly dependent on the geological and hydrological conditions in the considered area. The application of tunnel linings with spray-applied waterproofing membrane in both hard rock and soft ground tunnelling, are studied.

Preparation and Analysis of Co-precipitated, Biodegradable Poly-(Lactide-co-Glycolide) and Polyethylene Glycol Microspheres Prepared by Spray Drying

NASA Astrophysics Data System (ADS)

Javiya, Curie

Biodegradable poly-(d,l-lactide-co-glycolide) (PLGA) based microspheres are commonly used for numerous clinical applications. PEG is a widely used polymer due to its hydrophilic, biocompatible, and nontoxic nature. In this study, different blends of PLGA/PEG microspheres were prepared using a spray drying technique. The microspheres were spherical with maximum yield found to be 60.3% and average particle size in the range of 2.4 to 3.1 microm. Under the spray drying processing conditions, the polymers showed full miscibility slightly below 15% w/w and partial miscibility up to 20% w/w of PEG in the blended microspheres. At higher temperatures, PLGA and PEG were miscible in all proportions used for the blended microspheres. Blending 10% w/w PEG in PLGA membranes showed significant reduction in attachment of macrophages compared to PLGA membranes. The in-vitro response of macrophage towards the miscible blends of PLGA/PEG microspheres was further characterized. Results showed some reduction in macrophage viability and activation, however, significant effects with PLGA/PEG microspheres were not observed.

Methanol-tolerant cathode catalyst composite for direct methanol fuel cells

DOEpatents

Zhu, Yimin; Zelenay, Piotr

2006-09-05

A direct methanol fuel cell (DMFC) having a methanol fuel supply, oxidant supply, and its membrane electrode assembly (MEA) formed of an anode electrode and a cathode electrode with a membrane therebetween, a methanol oxidation catalyst adjacent the anode electrode and the membrane, an oxidant reduction catalyst adjacent the cathode electrode and the membrane, comprises an oxidant reduction catalyst layer of Pt.sub.3Cr/C so that oxidation at the cathode of methanol that crosses from the anode through the membrane to the cathode is reduced with a concomitant increase of net electrical potential at the cathode electrode.

Methanol-Tolerant Cathode Catalyst Composite For Direct Methanol Fuel Cells

DOEpatents

Zhu, Yimin; Zelenay, Piotr

2006-03-21

A direct methanol fuel cell (DMFC) having a methanol fuel supply, oxidant supply, and its membrane electrode assembly (MEA) formed of an anode electrode and a cathode electrode with a membrane therebetween, a methanol oxidation catalyst adjacent the anode electrode and the membrane, an oxidant reduction catalyst adjacent the cathode electrode and the membrane, comprises an oxidant reduction catalyst layer of a platinum-chromium alloy so that oxidation at the cathode of methanol that crosses from the anode through the membrane to the cathode is reduced with a concomitant increase of net electrical potential at the cathode electrode.

Polymer nanocomposite membranes with hierarchically structured catalysts for high throughput dehalogenation

NASA Astrophysics Data System (ADS)

Crock, Christopher A.

Halogenated organics are categorized as primary pollutants by the Environmental Protection Agency. Trichloroethylene (TCE), which had broad industrial use in the past, shows persistence in the environment because of its chemical stability. The large scale use and poor control of TCE resulted in its prolonged release into the environment before the carcinogenic risk associated with TCE was fully understood. TCE pollution stemmed from industrial effluents and improper disposal of solvent waste. Membrane reactors are promising technology for treating TCE polluted groundwater because of the high throughput, relatively low cost of membrane fabrication and facile retrofitting of existing membrane based water treatment facilities with catalytic membrane reactors. Compared to catalytic fluidized or fixed bed reactors, catalytic membrane reactors feature minimal diffusional limitation. Additionally, embedding catalyst within the membrane avoids the need for catalyst recovery and can prevent aggregation of catalytic nanoparticles. In this work, Pd/xGnP, Pd-Au/xGnP, and commercial Pd/Al2O3 nanoparticles were employed in batch and flow-through membrane reactors to catalyze the dehalogenation of TCE in the presence of dissolved H2. Bimetallic Pd-Au/xGnP catalysts were shown to be more active than monometallic Pd/xGnP or commercial Pd/Al 2O3 catalysts. In addition to synthesizing nanocomposite membranes for high-throughput TCE dehalogenation, the membrane based dehalogenation process was designed to minimize the detrimental impact of common catalyst poisons (S2-, HS-, and H2S -) by concurrent oxidation of sulfide species to gypsum in the presence of Ca2+ and removal of gypsum through membrane filtration. The engineered membrane dehalogenation process demonstrated that bimetallic Pd-Au/xGnP catalysts resisted deactivation by residual sulfide species after oxidation, and showed complete removal of gypsum during membrane filtration.

New insights into proton surface mobility processes in PEMFC catalysts using isotopic exchange methods.

PubMed

Ferreira-Aparicio, Paloma

2009-09-01

The surface chemistry and the adsorption/desorption/exchange behavior of a proton-exchange membrane fuel cell catalyst are analyzed as a case study for the development of tailor-made support materials of enhanced performance and stability. By using H2, D2, and CO as probe molecules, the relevance of some surface functional groups of the catalyst support on several diffusion processes taking place during the adsorption is shown. Sulfonic groups associated with the vulcanized carbon black surface have been detected by means of spectroscopic techniques (X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy) and by analysis of the desorbed products during temperature-programmed desorption tests by mass spectrometry. Such hydrophilic species have been observed to favor proton surface mobility and exchange with Pt-adsorbed deuterium even in the presence of adsorbed CO. This behavior is relevant both for the proper characterization of these kinds of catalysts using adsorption probes and for the design of new surface-modified carbon supports, enabling alternative proton-transfer pathways throughout the catalytic layers toward the membrane.

V-doped TiO2 supported Pt as a promising oxygen reduction reaction catalyst: Synthesis, characterization and in-situ evaluation in proton exchange membrane fuel cell

NASA Astrophysics Data System (ADS)

Bharti, Abha; Cheruvally, Gouri

2017-09-01

This study deals with the synthesis and characterization of V-doped, TiO2 supported Pt catalyst (Pt/V-TiO2) for oxygen reduction reaction (ORR) and its in-situ performance investigation in proton exchange membrane (PEM) fuel cell. Pt/V-TiO2 nanocomposite catalyst is prepared via a facile sol-gel and microwave assisted, modified chemical reduction route and its performance is compared with the undoped TiO2 supported catalyst, Pt/TiO2 prepared in an identical way. The prepared Pt/V-TiO2 and Pt/TiO2 catalysts are employed as cathode catalyst in PEM fuel cell and compared with standard Pt/C catalyst. Their comparative studies are conducted with physical and electrochemical techniques. In-situ electrochemical characterization studies show improved ORR catalytic activity of Pt/V-TiO2 compared to Pt/TiO2. Furthermore, both Pt/TiO2 and Pt/V-TiO2 are more stable than Pt/C when subjected to 6000 voltammetric cycles in the range of 0.2-1.2 V vs. standard hydrogen electrode in operating fuel cell conditions, losing only <20% of its electrochemical surface area as compared to 50% loss exhibited by Pt/C. This study thus demonstrates Pt/V-TiO2 nanocomposite material as a potential cathode catalyst for PEM fuel cell with immense scope for further investigation.

PES Surface Modification Using Green Chemistry: New Generation of Antifouling Membranes.

PubMed

Nady, Norhan

2016-04-18

A major limitation in using membrane-based separation processes is the loss of performance due to membrane fouling. This drawback can be addressed thanks to surface modification treatments. A new and promising surface modification using green chemistry has been recently investigated. This modification is carried out at room temperature and in aqueous medium using green catalyst (enzyme) and nontoxic modifier, which can be safely labelled "green surface modification". This modification can be considered as a nucleus of new generation of antifouling membranes and surfaces. In the current research, ferulic acid modifier and laccase bio-catalyst were used to make poly(ethersulfone) (PES) membrane less vulnerable to protein adsorption. The blank and modified PES membranes are evaluated based on e.g., their flux and protein repellence. Both the blank and the modified PES membranes (or laminated PES on silicon dioxide surface) are characterized using many techniques e.g., SEM, EDX, XPS and SPM, etc. The pure water flux of the most modified membranes was reduced by 10% on average relative to the blank membrane, and around a 94% reduction in protein adsorption was determined. In the conclusions section, a comparison between three modifiers-ferulic acid, and two other previously used modifiers (4-hydroxybenzoic acid and gallic acid)-is presented.

PES Surface Modification Using Green Chemistry: New Generation of Antifouling Membranes

PubMed Central

Nady, Norhan

2016-01-01

A major limitation in using membrane-based separation processes is the loss of performance due to membrane fouling. This drawback can be addressed thanks to surface modification treatments. A new and promising surface modification using green chemistry has been recently investigated. This modification is carried out at room temperature and in aqueous medium using green catalyst (enzyme) and nontoxic modifier, which can be safely labelled “green surface modification”. This modification can be considered as a nucleus of new generation of antifouling membranes and surfaces. In the current research, ferulic acid modifier and laccase bio-catalyst were used to make poly(ethersulfone) (PES) membrane less vulnerable to protein adsorption. The blank and modified PES membranes are evaluated based on e.g., their flux and protein repellence. Both the blank and the modified PES membranes (or laminated PES on silicon dioxide surface) are characterized using many techniques e.g., SEM, EDX, XPS and SPM, etc. The pure water flux of the most modified membranes was reduced by 10% on average relative to the blank membrane, and around a 94% reduction in protein adsorption was determined. In the conclusions section, a comparison between three modifiers—ferulic acid, and two other previously used modifiers (4-hydroxybenzoic acid and gallic acid)—is presented. PMID:27096873

Recent advancements in supporting materials for immobilised photocatalytic applications in waste water treatment.

PubMed

Srikanth, B; Goutham, R; Badri Narayan, R; Ramprasath, A; Gopinath, K P; Sankaranarayanan, A R

2017-09-15

The aim of this paper is to provide a review on the usage of different anchoring media (supports) for immobilising commonly employed photocatalysts for degradation of organic pollutants. The immobilisation of nano-sized photocatalysts can eliminate costly and impractical post-treatment recovery of spent photocatalysts in largescale operations. Some commonly employed immobilisation aids such as glass, carbonaceous substances, zeolites, clay and ceramics, polymers, cellulosic materials and metallic agents that have been previously discussed by various research groups have been reviewed. The study revealed that factors such as high durability, ease of availability, low density, chemical inertness and mechanical stability are primary factors responsible for the selection of suitable supports for catalysts. Common techniques for immobilisation namely, dip coating, cold plasma discharge, polymer assisted hydrothermal decomposition, RF magnetron sputtering, photoetching, solvent casting, electrophoretic deposition and spray pyrolysis have been discussed in detail. Finally, some common techniques adopted for the characterisation of the catalyst particles and their uses are also discussed. Copyright © 2017 Elsevier Ltd. All rights reserved.

Chalcogen catalysts for polymer electrolyte fuel cell

DOEpatents

Alonso-Vante, Nicolas [Buxerolles, FR; Zelenay, Piotr [Los Alamos, NM; Choi, Jong-Ho [Los Alamos, NM; Wieckowski, Andrzej [Champaign, IL; Cao, Dianxue [Urbana, IL

2009-09-15

A methanol-tolerant cathode catalyst and a membrane electrode assembly for fuel cells that includes such a cathode catalyst. The cathode catalyst includes a support having at least one transition metal in elemental form and a chalcogen disposed on the support. Methods of making the cathode catalyst and membrane electrode assembly are also described.

Chalcogen catalysts for polymer electrolyte fuel cell

DOEpatents

Zelenay, Piotr; Choi, Jong-Ho; Alonso-Vante, Nicolas; Wieckowski, Andrzej; Cao, Dianxue

2010-08-24

A methanol-tolerant cathode catalyst and a membrane electrode assembly for fuel cells that includes such a cathode catalyst. The cathode catalyst includes a support having at least one transition metal in elemental form and a chalcogen disposed on the support. Methods of making the cathode catalyst and membrane electrode assembly are also described.

Aerosol processing: a wind of innovation in the field of advanced heterogeneous catalysts.

PubMed

Debecker, Damien P; Le Bras, Solène; Boissière, Cédric; Chaumonnot, Alexandra; Sanchez, Clément

2018-06-05

Aerosol processing is long known and implemented industrially to obtain various types of divided materials and nanomaterials. The atomisation of a liquid solution or suspension produces a mist of aerosol droplets which can then be transformed via a diversity of processes including spray-drying, spray pyrolysis, flame spray pyrolysis, thermal decomposition, micronisation, gas atomisation, etc. The attractive technical features of these aerosol processes make them highly interesting for the continuous, large scale, and tailored production of heterogeneous catalysts. Indeed, during aerosol processing, each liquid droplet undergoes well-controlled physical and chemical transformations, allowing for example to dry and aggregate pre-existing solid particles or to synthesise new micro- or nanoparticles from mixtures of molecular or colloidal precursors. In the last two decades, more advanced reactive aerosol processes have emerged as innovative means to synthesise tailored-made nanomaterials with tunable surface properties, textures, compositions, etc. In particular, the "aerosol-assisted sol-gel" process (AASG) has demonstrated tremendous potential for the preparation of high-performance heterogeneous catalysts. The method is mainly based on the low-cost, scalable, and environmentally benign sol-gel chemistry process, often coupled with the evaporation-induced self-assembly (EISA) concept. It allows producing micronic or submicronic, inorganic or hybrid organic-inorganic particles bearing tuneable and calibrated porous structures at different scales. In addition, pre-formed nanoparticles can be easily incorporated or formed in a "one-pot" bottom-up approach within the porous inorganic or hybrid spheres produced by such spray drying method. Thus, multifunctional catalysts with tailored catalytic activities can be prepared in a relatively simple way. This account is an overview of aerosol processed heterogeneous catalysts which demonstrated interesting performance in various relevant chemical reactions like isomerisation, hydrogenation, olefin metathesis, pollutant total oxidation, selective oxidation, CO2 methanation, etc. A short survey of patents and industrial applications is also presented. Our objective is to demonstrate the tremendous possibilities offered by the coupling between bottom up synthesis routes and these aerosol processing technologies which will most probably represent a major route of innovation in the mushrooming field of catalyst preparation research.

Heterogeneous Electrocatalyst of Palladium-Cobalt-Phosphorus on Carbon Support for Oxygen Reduction Reaction in High Temperature Proton Exchange Membrane Fuel Cells.

PubMed

You, Dae Jong; Pak, Chanho; Jin, Seon-Ah; Lee, Kang Hee; Kwon, Kyungjung; Choi, Kyoung Hwan; Heo, Pil Won; Jang, Hongchul; Kim, Jun Young; Kim, Ji Man

2016-05-01

Palladium-cobalt-phosphorus (PdCoP) catalysts supported on carbon (Ketjen Black) were investigated as a cathode catalyst for oxygen reduction reaction (ORR) in high temperature proton exchange membrane fuel cells (HT-PEMFCs). The PdCoP catalyst was synthesized via a modified polyol process in teflon-sealed reactor by microwave-heating. From X-ray diffraction and transmission electron microscopic analysis, the PdCoP catalyst exhibits a face-centered cubic structure, similar to palladium (Pd), which is attributed to form a good solid solution of Co atoms and P atoms in the Pd lattice. The PdCoP nanoparticles with average diameter of 2.3 nm were uniformly distributed on the carbon support. The electrochemical surface area (ECSA) and ORR activity of PdP, PdCo and PdCoP catalysts were measured using a rotating disk electrode technique with cyclic voltammetry and the linear sweep method. The PdCoP catalysts showed the highest performances for ECSA and ORR, which might be attributed both to formation of small nanoparticle by phosphorus atom and to change in lattice constant of Pd by cobalt atom. Furthermore, The HT-PEMFCs single cell performance employing PdCoP catalyst exhibited an enhanced cell performance compared to a single cell using the PdP and PdCo catalysts. This result indicates the importance of electric and geometric control of Pd alloy nanoparticles that can improve the catalytic activity. This synergistic combination of Co and P with Pd could provide the direction of development of non-Pt catalyst for fuel cell system.

Direct methanol feed fuel cell with reduced catalyst loading

NASA Technical Reports Server (NTRS)

Kindler, Andrew (Inventor)

1999-01-01

Improvements to direct feed methanol fuel cells include new protocols for component formation. Catalyst-water repellent material is applied in formation of electrodes and sintered before application of ionomer. A membrane used in formation of an electrode assembly is specially pre-treated to improve bonding between catalyst and membrane. The improved electrode and the pre-treated membrane are assembled into a membrane electrode assembly.

Synthesis of flower-like molybdenum sulfide/graphene hybrid as an efficient oxygen reduction electrocatalyst for anion exchange membrane fuel cells

NASA Astrophysics Data System (ADS)

Arunchander, A.; Peera, S. Gouse; Sahu, A. K.

2017-06-01

Nanostructured transition metal chalcogenides (TMCs) have significant interest towards electrochemical devices such as fuel cells, metal-ion batteries, due to their unique physical and electrochemical properties. Herein, we report a facile hydrothermal synthesis of flower-like nanostructured molybdenum sulphide and its incorporation on to graphene as a potential oxygen reduction reaction catalyst in alkaline medium. The phase purity and morphological evolution of MoS2 is systematically studied through X-ray diffraction and scanning electron microscopic techniques. The electronic states of metal and non-metallic species are deeply studied by X-ray photoelectron spectroscopy. The effect of annealing temperatures and TMC concentrations are also investigated by electrochemical techniques such as cyclic and linear sweep voltammograms. The optimised electrocatalyst (MoS2/G-500) delivers significant ORR activity with onset and half-wave potentials of 0.91 and 0.80 V (vs. RHE), respectively. Superior durability compared to state-of-art Pt/C catalyst is ascertained by repeating potential cycles for about 5000 times and also by chronoamperometric technique. Finally, the hybrid catalyst is evaluated in AEMFC as cathode catalyst which delivers peak power density of about 29 mW cm-2 under ambient temperature and pressure. The present findings emphasis that MoS2/G catalyst is promising as cost-effective and alternative to noble metal-based catalysts for fuel cell applications.

Membrane catalyst layer for fuel cells

DOEpatents

Wilson, Mahlon S.

1993-01-01

A gas reaction fuel cell incorporates a thin catalyst layer between a solid polymer electrolyte (SPE) membrane and a porous electrode backing. The catalyst layer is preferably less than about 10 .mu.m in thickness with a carbon supported platinum catalyst loading less than about 0.35 mgPt/cm.sup.2. The film is formed as an ink that is spread and cured on a film release blank. The cured film is then transferred to the SPE membrane and hot pressed into the surface to form a catalyst layer having a controlled thickness and catalyst distribution. Alternatively, the catalyst layer is formed by applying a Na.sup.+ form of a perfluorosulfonate ionomer directly to the membrane, drying the film at a high temperature, and then converting the film back to the protonated form of the ionomer. The layer has adequate gas permeability so that cell performance is not affected and has a density and particle distribution effective to optimize proton access to the catalyst and electronic continuity for electron flow from the half-cell reaction occurring at the catalyst.

Investigation of carbon supported PtW catalysts as CO tolerant anodes at high temperature in proton exchange membrane fuel cell

NASA Astrophysics Data System (ADS)

Hassan, Ayaz; Paganin, Valdecir A.; Ticianelli, Edson A.

2016-09-01

The CO tolerance mechanism and the stability of carbon supported PtW electrocatalysts are evaluated in the anode of a proton exchange membrane fuel cell (PEMFC) at two different temperatures. The electrocatalysts are characterized by energy dispersive spectroscopy, X-ray diffraction, and transmission electron spectroscopy. Employed electrochemical techniques include cyclic voltammetry, CO stripping, fuel cell polarization, and online mass spectrometry. At a cell temperature of 85 °C, the PtW/C catalyst shows higher CO tolerance compared to Pt/C due an electronic effect of WOx in the Pt 5d band, which reduces the CO adsorption. An increase in hydrogen oxidation activity in the presence of CO is observed for both the catalysts at a higher temperature, due to the decrease of the Pt-CO coverage. A reduction in the current densities occurs for the PtW/C catalyst in both polarization curves and cyclic voltammograms after 5000 cycles of the anode in the range of 0.1-0.7 V vs. RHE at 50 mVs-1. This decrease in performance is assigned to the dissolution of W, with a consequent increase in the membrane resistivity. However, the observed decline of performance is small either in the presence of pure H2 or in the presence of H2/CO.

Performance evaluation of platinum-molybdenum carbide nanocatalysts with ultralow platinum loading on anode and cathode catalyst layers of proton exchange membrane fuel cells

NASA Astrophysics Data System (ADS)

Saha, Shibely; Cabrera Rodas, José Andrés; Tan, Shuai; Li, Dongmei

2018-02-01

An alternative catalyst platform, consisting of a phase-pure transition carbide (TMC) support and Pt nanoparticles (NPs) in the range of subnanometer to < 2.7 nm, is established that can be used in both anode and cathode catalyst layers. While some TMCs with low Pt loadings have demonstrated similar activity as commercial Pt catalyst in idealized disk electrode screening tests, few to none have been applied in a realistic fuel cell membrane electrode assembly (MEA). We recently reported that β-Mo2C hollow nanotubes modified with Pt NPs via atomic layer deposition (ALD) possess better activity and durability than 20% Pt/C. This paper presents systematic evaluation of the Pt/Mo2C catalysts in a MEA, investigating effects of different MEA preparation techniques, gas diffusion layers (GDL) and various Pt loadings in the ultralow range (<0.04 mg/cm2) on MEA performance. Most importantly, we demonstrate, for the first time, that Pt/Mo2C catalyst on both anode and cathode, with a loading of 0.02 mg (Pt) cm-2, generated peak power density of 414 mW cm-2 that corresponds to 10.35 kWgPt-1 using hydrogen (H2) and oxygen (O2). Accelerated degradation tests (ADT) on Pt/Mo2C catalysts show 111% higher power density than commercial 20% Pt/C after the vigorous ADT.

Influence of various carbon nano-forms as supports for Pt catalyst on proton exchange membrane fuel cell performance

NASA Astrophysics Data System (ADS)

Bharti, Abha; Cheruvally, Gouri

2017-08-01

In this study, we discuss the influence of various carbon supports for Pt on proton exchange membrane (PEM) fuel cell performance. Here, Pt supported on various carbon nano-forms [Pt/carbon black (Pt/CB), Pt/single-walled carbon nanotubes (Pt/SWCNT), Pt/multi-walled carbon nanotubes (Pt/MWCNT) and Pt/graphene (Pt/G)] are synthesized by a facile, single step, microwave-assisted, modified chemical reduction route. Their physical, chemical and electrochemical characteristics pertaining to oxygen reduction reaction (ORR) catalytic activity and stability in PEM fuel cell are studied in detail by various techniques and compared. The study shows that the different carbon supports does not significantly affect the Pt particle size during synthesis, but leads to different amount of defective sites in the carbon framework which influence both the availability of active metal nano-catalysts and metal-support interaction. In-situ electrochemical investigations reveal that the different carbon supports influence both ORR catalytic activity and stability of the catalyst. This is further corroborated by the demonstration of varying polarization characteristics on PEM fuel cell performance by different carbon supported Pt catalysts. This study reveals MWCNT as the most suitable carbon support for Pt catalyst, exhibiting high activity and stability for ORR in PEM fuel cell.

Characterization of the Ternary Compound Pd5Pt3Ni2 for PEMFC Cathode Electrocatalysts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jarvis, Karalee; Zhao, J; Allard Jr, Lawrence Frederick

2010-01-01

Research on proton exchange membrane fuel cells (PEMFC) has increased over the last decade due to an increasing demand for alternative energy solutions. Most PEMFCs use Pt on carbon support as electrocatalysts for oxygen reduction reactions (ORR) [1]. Due to the high cost of Pt, there is a strong drive to develop less expensive catalysts that meet or exceed the performance of Pt. Binary and ternary Pt alloys with less expensive metals are a possible route [1]. In this work, a ternary alloy with composition Pd5Pt3Ni2 was studied as a potential cathode material. Preliminary results showed similar catalytic performance tomore » pure Pt in single-cell tests. However, to enhance its performance, it is necessary to understand how this ternary catalyst behaves during fuel cell operation. Various electron microscopy techniques were used to characterize the ternary Pd5Pt3Ni2 catalysts within the membrane-electrode assembly (MEA) both before and after fuel cell operation.« less

Solvent-free Hydrodeoxygenation of Bio-oil Model Compounds Cyclopentanone and Acetophenone over Flame-made Bimetallic Pt-Pd/ZrO2 Catalysts

PubMed Central

Jiang, Yijiao; Büchel, Robert; Huang, Jun; Krumeich, Frank; Pratsinis, Sotiris E.; Baiker, Alfons

2013-01-01

Bimetallic Pt-Pd/ZrO2 catalysts with different Pt/Pd atomic ratio and homogeneous dispersion of the metal nanoparticles were prepared in a single step by flame-spray pyrolysis. The catalysts show high activity and tuneable product selectivity for the solvent-free hydrodeoxygenation of the bio-oil model compounds cyclopentanone and acetophenone. PMID:22674738

Formic acid fuel cells and catalysts

DOEpatents

Masel, Richard I.; Larsen, Robert; Ha, Su Yun

2010-06-22

An exemplary fuel cell of the invention includes a formic acid fuel solution in communication with an anode (12, 134), an oxidizer in communication with a cathode (16, 135) electrically linked to the anode, and an anode catalyst that includes Pd. An exemplary formic acid fuel cell membrane electrode assembly (130) includes a proton-conducting membrane (131) having opposing first (132) and second surfaces (133), a cathode catalyst on the second membrane surface, and an anode catalyst including Pd on the first surface.

Polarization loss correction derived from hydrogen local-resistance measurement in low Pt-loaded polymer-electrolyte fuel cells

DOE PAGES

Freiberg, Anna T. S.; Tucker, Michael C.; Weber, Adam Z.

2017-04-12

The reduction of platinum-loading on the cathode side of polymer-electrolyte fuel cells leads to a poorly understood increase in mass-transport resistance (MTR) at high current densities. This local resistance was measured using a facile hydrogen-pump technique with dilute active gases for membrane-electrode assemblies with catalyst layers of varying platinum-loading (0.03-0.40 mgPt/cm²). Furthermore, polarization curves in H 2/air were measured and corrected for the overpotential caused by the increased MTR for low loadings on the air side due to the reduced concentration of reactant gas at the catalyst surface. The difference in performance after correction for all resistances including the MTRmore » is minor, suggesting its origin to be diffusive in nature, and proving the meaningfulness of the facile hydrogen-pump technique for the characterization of the cathode catalyst layer under defined operation conditions.« less

Failure analysis of fuel cell electrodes using three-dimensional multi-length scale X-ray computed tomography

NASA Astrophysics Data System (ADS)

Pokhrel, A.; El Hannach, M.; Orfino, F. P.; Dutta, M.; Kjeang, E.

2016-10-01

X-ray computed tomography (XCT), a non-destructive technique, is proposed for three-dimensional, multi-length scale characterization of complex failure modes in fuel cell electrodes. Comparative tomography data sets are acquired for a conditioned beginning of life (BOL) and a degraded end of life (EOL) membrane electrode assembly subjected to cathode degradation by voltage cycling. Micro length scale analysis shows a five-fold increase in crack size and 57% thickness reduction in the EOL cathode catalyst layer, indicating widespread action of carbon corrosion. Complementary nano length scale analysis shows a significant reduction in porosity, increased pore size, and dramatically reduced effective diffusivity within the remaining porous structure of the catalyst layer at EOL. Collapsing of the structure is evident from the combination of thinning and reduced porosity, as uniquely determined by the multi-length scale approach. Additionally, a novel image processing based technique developed for nano scale segregation of pore, ionomer, and Pt/C dominated voxels shows an increase in ionomer volume fraction, Pt/C agglomerates, and severe carbon corrosion at the catalyst layer/membrane interface at EOL. In summary, XCT based multi-length scale analysis enables detailed information needed for comprehensive understanding of the complex failure modes observed in fuel cell electrodes.

High-efficiency and conveniently recyclable photo-catalysts for dye degradation based on urchin-like CuO microparticle/polymer hybrid composites

NASA Astrophysics Data System (ADS)

Liu, Xiong; Cheng, Yuming; Li, Xuefeng; Dong, Jinfeng

2018-05-01

In this work, we developed a new type of photo-catalysts composed of the urchin-like cupric oxide (CuO) microparticle and polyvinylidene fluoride (PVDF) hybrid composites by the convenient organic-inorganic hybrid strategy, which show high-efficiency and conveniently recyclable for dye degradation including methylene blue (MB), Congo red (CR), and malachite green (MG) by visible light irradiation. The micro-structural characteristics of urchin-like CuO microparticles are crucial and dominant over the photo-degrading efficiency of hybrid catalyst because of their highly exposed {0 0 2} facet and larger specific surface area. Simultaneously, the intrinsic porous framework of PVDF membrane not only remains the excellent photo-catalytic activity of urchin-like CuO microparticles but also facilitates the enrichment of dyes on the membrane, and thereby synergistically contributing to the photo-catalytic efficiency. The microstructures of both urchin-like CuO microparticles and hybrid catalysts are systematically characterized by various techniques including scanning electron microscopy (SEM), transmission electron microscope (TEM), high-resolution transmission electron microscope (HRTEM), powder X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR), and nitrogen adsorption/desorption isotherms, which evidently support the mentioned mechanism.

Study on corrosion migrations within catalyst-coated membranes of proton exchange membrane electrolyzer cells

DOE PAGES

Mo, Jingke; Steen, Stuart; Kang, Zhenye; ...

2017-10-09

The corrosion of low-cost, easily manufactured metallic components inside the electrochemical environment of proton exchange membrane electrolyzer cells (PEMECs) has a significant effect on their performance and durability. Here, 316 stainless steel (SS) mesh was used as a model liquid/gas diffusion layer material to investigate the migration of corrosion products in the catalyst-coated membrane of a PEMEC. Iron and nickel cation particles were found distributed throughout the anode catalyst layer, proton exchange membrane, and cathode catalyst layer, as revealed by scanning transmission electron microscopy and energy dispersive X-ray spectroscopy. Our results indicate the corrosion products of 316 SS are transportedmore » from anode to cathode through the nanochannels of the Nafion membrane, resulting in impeded proton transport and overall PEMEC performance loss.« less

Study on corrosion migrations within catalyst-coated membranes of proton exchange membrane electrolyzer cells

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mo, Jingke; Steen, Stuart; Kang, Zhenye

The corrosion of low-cost, easily manufactured metallic components inside the electrochemical environment of proton exchange membrane electrolyzer cells (PEMECs) has a significant effect on their performance and durability. Here, 316 stainless steel (SS) mesh was used as a model liquid/gas diffusion layer material to investigate the migration of corrosion products in the catalyst-coated membrane of a PEMEC. Iron and nickel cation particles were found distributed throughout the anode catalyst layer, proton exchange membrane, and cathode catalyst layer, as revealed by scanning transmission electron microscopy and energy dispersive X-ray spectroscopy. Our results indicate the corrosion products of 316 SS are transportedmore » from anode to cathode through the nanochannels of the Nafion membrane, resulting in impeded proton transport and overall PEMEC performance loss.« less

Anodic aluminium oxide membranes used for the growth of carbon nanotubes.

PubMed

López, Vicente; Morant, Carmen; Márquez, Francisco; Zamora, Félix; Elizalde, Eduardo

2009-11-01

The suitability of anodic aluminum oxide (AAO) membranes as template supported on Si substrates for obtaining organized iron catalyst for carbon nanotube (CNT) growth has been investigated. The iron catalyst was confined in the holes of the AAO membrane. CVD synthesis with ethylene as carbon source led to a variety of carbon structures (nanotubes, helices, bamboo-like, etc). In absence of AAO membrane the catalyst was homogeneously distributed on the Si surface producing a high density of micron-length CNTs.

A submerged ceramic membrane reactor for the p-nitrophenol hydrogenation over nano-sized nickel catalysts.

PubMed

Chen, R Z; Sun, H L; Xing, W H; Jin, W Q; Xu, N P

2009-02-01

The catalytic hydrogenation of p-nitrophenol to p-aminophenol over nano-sized nickel catalysts was carried out in a submerged ceramic membrane reactor. It has been demonstrated that the submerged ceramic membrane reactor is more suitable for the p-nitrophenol hydrogenation over nano-sized nickel catalysts compared with the side-stream ceramic membrane reactor, and the membrane module configuration has a great influence on the reaction rate of p-nitrophenol hydrogenation and the membrane treating capacity. The deactivation of nano-sized nickel is mainly caused by the adsorption of impurity on the surface of nickel and the increase of oxidation degree of nickel.

Uniformity index measurement technology using thermocouples to improve performance in urea-selective catalytic reduction systems

NASA Astrophysics Data System (ADS)

Park, Sangki; Oh, Jungmo

2018-05-01

The current commonly used nitrogen oxides (NOx) emission reduction techniques employ hydrocarbons (HCs), urea solutions, and exhaust gas emissions as the reductants. Two of the primary denitrification NOx (DeNOx) catalyst systems are the HC-lean NOx trap (HC-LNT) catalyst and urea-selective catalytic reduction (urea-SCR) catalyst. The secondary injection method depends on the type of injector, injection pressure, atomization, and spraying technique. In addition, the catalyst reaction efficiency is directly affected by the distribution of injectors; hence, the uniformity index (UI) of the reductant is very important and is the basis for system optimization. The UI of the reductant is an indicator of the NOx conversion efficiency (NCE), and good UI values can reduce the need for a catalyst. Therefore, improving the UI can reduce the cost of producing a catalytic converter, which are expensive due to the high prices of the precious metals contained therein. Accordingly, measurement of the UI is an important process in the development of catalytic systems. Two of the commonly used methods for measuring the reductant UI are (i) measuring the exhaust emissions at many points located upstream/downstream of the catalytic converter and (ii) acquisition of a reductant distribution image on a section of the exhaust pipe upstream of the catalytic converter. The purpose of this study is to develop a system and measurement algorithms to measure the exothermic response distribution in the exhaust gas as the reductant passes through the catalytic converter of the SCR catalyst system using a set of thermocouples downstream of the SCR catalyst. The system is used to measure the reductant UI, which is applied in real-time to the actual SCR system, and the results are compared for various types of mixtures for various engine operating conditions and mixer types in terms of NCE.

ATTRITION RESISTANT IRON-BASED FISCHER-TROPSCH CATALYSTS

DOE Office of Scientific and Technical Information (OSTI.GOV)

James G. Goodwin, Jr.; James J. Spivey; K. Jothimurugesan

1999-03-29

The Fischer-Tropsch (F-T) reaction provides a way of converting coal-derived synthesis gas (CO+H{sub 2}) to liquid fuels. Since the reaction is highly exothermic, one of the major problems in control of the reaction is heat removal. Recent work has shown that the use of slurry bubble column reactors (SBCRs) can largely solve this problem. Iron-based (Fe) catalysts are preferred catalysts for F-T when using low CO/H2 ratio synthesis gases derived from modern coal gasifiers. This is because in addition to reasonable F-T activity, the F-T catalysts also possess high water gas shift (WGS) activity. However, a serious problem with themore » use of Fe catalysts in a SBCR is their tendency to undergo attrition. This can cause fouling/plugging of downstream filters and equipment, making the separation of catalyst from the oil/wax product very difficult if not impossible, and results in a steady loss of catalyst from the reactor. The objectives of this research are to develop a better understanding of the parameters affecting attrition resistance of Fe F-T catalysts suitable for use in SBCRs and to incorporate this understanding into the design of novel Fe catalysts having superior attrition resistance. Catalyst preparations will be based on the use of spray drying and will be scalable using commercially available equipment. The research will employ among other measurements, attrition testing and F-T synthesis, including long duration slurry reactor runs in order to ascertain the degree of success of the various preparations. The goal is to develop an Fe catalyst which can be used in a SBCR having only an internal filter for separation of the catalyst from the liquid product, without sacrificing F-T activity and selectivity. The effect of silica addition via coprecipitation and as a binder to a doubly promoted Fischer-Tropsch synthesis iron catalyst (100 Fe/5 Cu/4.2 K) was studied. The catalysts were prepared by coprecipitation, followed by binder addition and drying in a 1 m diameter, 2 m tall spray dryer. The binder silica content was varied from 0 to 20 wt %. A catalyst with 12 wt % binder silica was found to have the highest attrition resistance. F-T reaction studies over 100 hours in a fixed-bed reactor showed that this catalyst maintained around 95 % CO conversion with a methane selectivity of less than 7 wt % and a C5 + selectivity of greater than 73 wt %. The effect of adding precipitated silica from 0 to 20 parts by weight to this catalyst (containing 12 wt % binder silica) was also studied. Addition of precipitated silica was found to be detrimental to attrition resistance and resulted in increased methane and reduced wax formation. An HPR series of proprietary catalysts was prepared to further improve the attrition resistance. Based on the experience gained, a proprietary HPR-43 catalyst has been successfully spray dried in 500 g quantity. This catalyst showed 95 % CO conversion over 125 h and had less than 4 % methane selectivity. Its attrition resistance was one of the highest among the catalyst tested.« less

Performance of EVA-Based Membranes for SCL in Hard Rock

NASA Astrophysics Data System (ADS)

Holter, Karl Gunnar

2016-04-01

The bonded property of multi-layered sprayed concrete tunnel linings (SCL) waterproofed with sprayed membranes means that the constituent materials will be exposed to the groundwater without any draining or mechanically separating measures. Moisture properties of the sprayed concrete and membrane materials are therefore important in order to establish the system properties of such linings. Ethyl-vinyl-acetate based sprayed membranes exhibit high water absorption potential under direct exposure to water, but are found to be significantly less hygroscopic and exhibit lower sorptivity (water absorption rate) than sprayed concrete. This material behavior explains the relatively dry in situ condition of the membrane that was observed. Measured in situ moisture content levels of the membrane material in tunnel linings have been found to vary within the range of 30-40 % of the maximum water absorption potential, and show a decreasing trend over the first 4 years after construction has been completed. A model for the mechanical loading, moisture condition and thermal exposure of the membrane and the resulting realistic parameters to be tested is presented. Laboratory testing methods for the membrane materials are evaluated considering possible loads, moisture and freezing exposure. Material testing of membrane materials was conducted with preconditioning to realistic moisture contents and under different temperature conditions including relevant freezing temperatures for tunnel linings. The main effects of the in situ moisture condition of the tested membrane materials are favorable tensile strengths in the range of 1.1-1.5 MPa and low risk of freeze-thaw damage. The crack bridging capacity of the tested membranes is found to be sensitive to temperature. With membrane thicknesses in the range of 3-4 mm, crack bridging capacity up to 4-6 mm opening of the crack width at 23 °C and approximately 1 mm opening at -3 °C was measured for the tested membranes. No significant reduction of the tensile bond strength could be demonstrated after 35 freeze-thaw cycles with -3 °C minimum temperature at the membrane location in the lining. Further work is required to verify the performance of the SCL system under exposure to high hydrostatic pressures and the effects of long term mechanical exposure.

Microemulsion flame pyrolysis for hopcalite nanoparticle synthesis: a new concept for catalyst preparation.

PubMed

Biemelt, T; Wegner, K; Teichert, J; Kaskel, S

2015-04-07

A new route to highly active hopcalite catalysts via flame spray pyrolysis of an inverse microemulsion precursor is reported. The nitrate derived nanoparticles are around 15 nm in diameter and show excellent conversion of CO under ambient conditions, outperforming commercial reference hopcalite materials produced by co-precipitation.

Mapping reactive flow patterns in monolithic nanoporous catalysts

DOE PAGES

Falcucci, Giacomo; Succi, Sauro; Montessori, Andrea; ...

2016-07-06

The development of high-efficiency porous catalyst membranes critically depends on our understanding of where the majority of the chemical conversions occur within the porous structure. This then requires mapping of chemical reactions and mass transport inside the complex nanoscale architecture of porous catalyst membranes which is a multiscale problem in both the temporal and spatial domains. In order to address this problem, we developed a multiscale mass transport computational framework based on the lattice Boltzmann method that allows us to account for catalytic reactions at the gas–solid interface by introducing a new boundary condition. In good agreement with experiments, themore » simulations reveal that most catalytic reactions occur near the gas-flow facing side of the catalyst membrane if chemical reactions are fast compared to mass transport within the porous catalyst membrane.« less

Direct liquid-feed fuel cell with membrane electrolyte and manufacturing thereof

NASA Technical Reports Server (NTRS)

Narayanan, Sekharipuram (Inventor); Surampudi, Subbarao (Inventor); Halpert, Gerald (Inventor)

1999-01-01

An improved direct liquid-feed fuel cell having a solid membrane electrolyte for electrochemical reactions of an organic fuel. Improvements in interfacing of the catalyst layer and the membrane and activating catalyst materials are disclosed.

High-performance Fuel Cell with Stretched Catalyst-Coated Membrane: One-step Formation of Cracked Electrode.

PubMed

Kim, Sang Moon; Ahn, Chi-Yeong; Cho, Yong-Hun; Kim, Sungjun; Hwang, Wonchan; Jang, Segeun; Shin, Sungsoo; Lee, Gunhee; Sung, Yung-Eun; Choi, Mansoo

2016-05-23

We have achieved performance enhancement of polymer electrolyte membrane fuel cell (PEMFC) though crack generation on its electrodes. It is the first attempt to enhance the performance of PEMFC by using cracks which are generally considered as defects. The pre-defined, cracked electrode was generated by stretching a catalyst-coated Nafion membrane. With the strain-stress property of the membrane that is unique in the aspect of plastic deformation, membrane electrolyte assembly (MEA) was successfully incorporated into the fuel cell. Cracked electrodes with the variation of strain were investigated and electrochemically evaluated. Remarkably, mechanical stretching of catalyst-coated Nafion membrane led to a decrease in membrane resistance and an improvement in mass transport, which resulted in enhanced device performance.

Flexible metallic ultrasonic transducers for structural health monitoring of pipes at high temperatures.

PubMed

Shih, Jeanne-Louise; Kobayashi, Makiko; Jen, Cheng-Kuei

2010-09-01

Piezoelectric films have been deposited by a sol-gel spray technique onto 75-μm-thick titanium and stainless steel (SS) membranes and have been fabricated into flexible ultrasonic transducers (FUTs). FUTs using titanium membranes were glued and those using SS membranes brazed onto steel pipes, procedures that serve as on-site installation techniques for the purpose of offering continuous thickness monitoring capabilities at up to 490 °C. At 150 °C, the thickness measurement accuracy of a pipe with an outer diameter of 26.6 mm and a wall thickness of 2.5 mm was estimated to be 26 μm and the center frequency of the FUT was 10.8 MHz. It is demonstrated that the frequency bandwidth of the FUTs and SNR of signals using glue or brazing materials as high-temperature couplant for FUTs are sufficient to inspect the steel pipes even with a 2.5 mm wall thickness.

Solid polymer electrolyte (SPE) fuel cell technology program, phase 2/2A. [testing and evaluations

NASA Technical Reports Server (NTRS)

1976-01-01

Test evaluations were performed on a fabricated single solid polymer electrolyte cell unit. The cell operated at increased current density and at higher performance levels. This improved performance was obtained through a combination of increased temperature, increased reactant pressures, improved activation techniques and improved thermal control over the baseline cell configuration. The cell demonstrated a higher acid content membrane which resulted in increased performance. Reduced catalyst loading and low cost membrane development showed encouraging results.

Synthesis, characterization and optimization of platinum-alloy nanoparticle catalysts in proton exchange membrane fuel cells

NASA Astrophysics Data System (ADS)

Srivastava, Ratndeep

Renewable hydrogen-fuelled proton exchange membrane (PEMFC) fuel cells have consistently demonstrated great promise as a future source of energy due to their high conversion efficiency, lower temperature of operation and lack of greenhouse emissions. One of the major impediments in the commercialization of polymer electrolyte membrane fuel cells is the insufficient catalytic reactivity and higher cost of Pt electrocatalysts which are utilized for the electroreduction of oxygen from air. This dissertation focuses primarily on a family of Pt alloy fuel cell electrocatalysts referred to as de-alloyed core-shell electrocatalysts. These materials are bimetallic or multimetallic nanoparticles, mostly supported on conductive supports which were first described in a dissertation by Dr. S. Koh earlier in 2009.1 De-alloyed Pt nanoparticle electrocatalysts are formed from base metal rich binary Pt-M and ternary Pt-M1-M 2 (M, M1, M2 = Cu, Co, Ni, Fe and Cr) alloy nanoparticle precursors. The precursors are transformed and activated by electrochemical selective dissolution of the less noble metal component of the precursors (de-alloying). They have shown exceptional activity for oxygen reduction reaction (ORR) in idealized electrochemical half cell measurements, in particular rotating disk electrode experiments. However, these materials were never tested or implemented in realistic Membrane Electrode Assemblies (MEA) and single PEM fuel cells. The objective of this work was to implement de-alloyed Pt particle catalysts in realistic fuel cell electrode layers as well as a detailed characterization of their behavior and stability. The major challenges of MEA implementation consists of the behavior of the new nanostructured electrocatalysts inside the complex three-phase interface of polymer membrane ionomer, liquid water, metal catalyst, support, and reactant gas. Activity measurements were followed by medium and long-term durability analysis by potential cycling of the membrane electrode assemblies to high potentials. These de-alloyed catalysts show improved resistance to electro-chemical surface area degradation as compared to state of the art available commercial Pt/C catalysts. TEM imaging with combination of electrochemical characterization helps in determining the mechanisms for particle growth and failures. Anomalous small angle x-ray scattering (ASAXS) and x-ray diffraction (XRD) techniques were also used in the characterization of these materials.

In situ characterization of catalysts and membranes in a microchannel under high-temperature water gas shift reaction conditions

NASA Astrophysics Data System (ADS)

Cavusoglu, G.; Dallmann, F.; Lichtenberg, H.; Goldbach, A.; Dittmeyer, R.; Grunwaldt, J.-D.

2016-05-01

Microreactor technology with high heat transfer in combination with stable catalysts is a very attractive approach for reactions involving major heat effects such as methane steam reforming and to some extent, also the high temperature water gas shift (WGS) reaction. For this study Rh/ceria catalysts and an ultrathin hydrogen selective membrane were characterized in situ in a microreactor specially designed for x-ray absorption spectroscopic measurements under WGS conditions. The results of these experiments can serve as a basis for further development of the catalysts and membranes.

Spray-loading: A cryogenic deposition method for diamond anvil cell

NASA Astrophysics Data System (ADS)

Scelta, Demetrio; Ceppatelli, Matteo; Ballerini, Riccardo; Hajeb, Ahmed; Peruzzini, Maurizio; Bini, Roberto

2018-05-01

An efficient loading technique has been developed for flammable, toxic, or explosive gases which can be condensed at liquid nitrogen temperature and ambient pressure in membrane diamond anvil cells (DACs). This cryogenic technique consists in a deposition of small quantities of the desired gas directly into the sample chamber. The deposition is performed using a capillary that reaches the space between the diamond anvils. The DAC is kept under inert gas overpressure during the whole process, in order to avoid contamination from atmospheric O2, CO2, and H2O. This technique provides significant advantages over standard cryo-loading and gas-loading when the condensation of dangerous samples at liquid nitrogen temperature raises safety concerns because it allows dealing with minimum quantities of condensed gases. The whole procedure is particularly fast and efficient. The "spray-loading" has been successfully used in our laboratory to load several samples including acetylene, ammonia, ethylene, and carbon dioxide/water or red phosphorus/NH3 mixtures.

High-performance Fuel Cell with Stretched Catalyst-Coated Membrane: One-step Formation of Cracked Electrode

PubMed Central

Kim, Sang Moon; Ahn, Chi-Yeong; Cho, Yong-Hun; Kim, Sungjun; Hwang, Wonchan; Jang, Segeun; Shin, Sungsoo; Lee, Gunhee; Sung, Yung-Eun; Choi, Mansoo

2016-01-01

We have achieved performance enhancement of polymer electrolyte membrane fuel cell (PEMFC) though crack generation on its electrodes. It is the first attempt to enhance the performance of PEMFC by using cracks which are generally considered as defects. The pre-defined, cracked electrode was generated by stretching a catalyst-coated Nafion membrane. With the strain-stress property of the membrane that is unique in the aspect of plastic deformation, membrane electrolyte assembly (MEA) was successfully incorporated into the fuel cell. Cracked electrodes with the variation of strain were investigated and electrochemically evaluated. Remarkably, mechanical stretching of catalyst-coated Nafion membrane led to a decrease in membrane resistance and an improvement in mass transport, which resulted in enhanced device performance. PMID:27210793

CeO2 nanocubes-graphene oxide as durable and highly active catalyst support for proton exchange membrane fuel cell

PubMed Central

Lei, M.; Wang, Z. B.; Li, J. S.; Tang, H. L.; Liu, W. J.; Wang, Y. G.

2014-01-01

Rapid degradation of cell performance still remains a significant challenge for proton exchange membrane fuel cell (PEMFC). In this work, we develop novel CeO2 nanocubes-graphene oxide nanocomposites as durable and highly active catalyst support for proton exchange membrane fuel cell. We show that the use of CeO2 as the radical scavenger in the catalysts remarkably improves the durability of the catalyst. The catalytic activity retention of Pt-graphene oxide-8 wt.% CeO2 nanocomposites reaches as high as 69% after 5000 CV-cycles at a high voltage range of 0.8–1.23 V, in contrast to 19% for that of the Pt-graphene oxide composites. The excellent durability of the Pt-CeO2 nanocubes-graphene oxide catalyst is attributed to the free radical scavenging activity of CeO2, which significantly slows down the chemical degradation of Nafion binder in catalytic layers, and then alleviates the decay of Pt catalysts, resulting in the excellent cycle life of Pt-CeO2-graphene oxide nanocomposite catalysts. Additionally, the performance of single cell assembled with Nafion 211 membrane and Pt-CeO2-graphene oxide catalysts with different CeO2 contents in the cathode as well as the Pt-C catalysts in the anode are also recorded and discussed in this study. PMID:25491655

CeO2 nanocubes-graphene oxide as durable and highly active catalyst support for proton exchange membrane fuel cell.

PubMed

Lei, M; Wang, Z B; Li, J S; Tang, H L; Liu, W J; Wang, Y G

2014-12-10

Rapid degradation of cell performance still remains a significant challenge for proton exchange membrane fuel cell (PEMFC). In this work, we develop novel CeO2 nanocubes-graphene oxide nanocomposites as durable and highly active catalyst support for proton exchange membrane fuel cell. We show that the use of CeO2 as the radical scavenger in the catalysts remarkably improves the durability of the catalyst. The catalytic activity retention of Pt-graphene oxide-8 wt.% CeO2 nanocomposites reaches as high as 69% after 5000 CV-cycles at a high voltage range of 0.8-1.23 V, in contrast to 19% for that of the Pt-graphene oxide composites. The excellent durability of the Pt-CeO2 nanocubes-graphene oxide catalyst is attributed to the free radical scavenging activity of CeO2, which significantly slows down the chemical degradation of Nafion binder in catalytic layers, and then alleviates the decay of Pt catalysts, resulting in the excellent cycle life of Pt-CeO2-graphene oxide nanocomposite catalysts. Additionally, the performance of single cell assembled with Nafion 211 membrane and Pt-CeO2-graphene oxide catalysts with different CeO2 contents in the cathode as well as the Pt-C catalysts in the anode are also recorded and discussed in this study.

CeO2 nanocubes-graphene oxide as durable and highly active catalyst support for proton exchange membrane fuel cell

NASA Astrophysics Data System (ADS)

Lei, M.; Wang, Z. B.; Li, J. S.; Tang, H. L.; Liu, W. J.; Wang, Y. G.

2014-12-01

Rapid degradation of cell performance still remains a significant challenge for proton exchange membrane fuel cell (PEMFC). In this work, we develop novel CeO2 nanocubes-graphene oxide nanocomposites as durable and highly active catalyst support for proton exchange membrane fuel cell. We show that the use of CeO2 as the radical scavenger in the catalysts remarkably improves the durability of the catalyst. The catalytic activity retention of Pt-graphene oxide-8 wt.% CeO2 nanocomposites reaches as high as 69% after 5000 CV-cycles at a high voltage range of 0.8-1.23 V, in contrast to 19% for that of the Pt-graphene oxide composites. The excellent durability of the Pt-CeO2 nanocubes-graphene oxide catalyst is attributed to the free radical scavenging activity of CeO2, which significantly slows down the chemical degradation of Nafion binder in catalytic layers, and then alleviates the decay of Pt catalysts, resulting in the excellent cycle life of Pt-CeO2-graphene oxide nanocomposite catalysts. Additionally, the performance of single cell assembled with Nafion 211 membrane and Pt-CeO2-graphene oxide catalysts with different CeO2 contents in the cathode as well as the Pt-C catalysts in the anode are also recorded and discussed in this study.

Development and characterization of membrane electrode assembly of direct methanol fuel cells using hydrocarbon membranes and supported catalysts

NASA Astrophysics Data System (ADS)

Huang, Xiaoming

Direct methanol fuel cell (DMFC) is an attractive power source for portable applications in the near future, due to the high energy density of liquid methanol. Towards commercialization of the DMFC, several technical and economic challenges need to be addressed though. The present study aims at developing and characterizing high performance membrane electrode assemblies (MEAs) for the DMFCs by using a hydrocarbon type membrane (PolyFuel 62) and supported catalysts (PtRu/C). First, methanol and water transport properties in the PolyFuel 62 membrane were examined by various material characterization methods. Compared with the currently used perflurosulfonated Nafion 212 membrane, the PolyFuel membrane has lower methanol crossover, especially at high testing temperature. In addition, based on results of water diffusivity test, water diffusion through the PolyFuel membrane was also lower compared with the Nafion membrane. In order to check the possible impacts of the low methanol and water diffusivities in the PolyFuel membrane, a MEA with this new type of membrane was developed and its performance was compared with a Nafion MEA with otherwise identical electrodes and GDLs. The results showed anode performance was identical, while cathode performance of the PolyFuel MEA was lower. More experiments combined with a transmission line model revealed that low water transport through the PolyFuel membrane resulted in a higher proton resistance in the cathode electrode and thus, leading to a low cathode performance. Thus increasing the water content in the cathode electrode is critical for using the PolyFuel membrane in the DMFC MEA. Then, a low loading carbon supported catalyst, PtRu/C, was prepared and tested as the anode electrode in a MEA of the DMFC. Compared with performance of an unsupported MEA, we could find that lower performance in the supported MEA was due to methanol transport limitation because of the denser and thicker supported catalyst layer. Accordingly, an addition of a pore former, Li 2CO3, was proposed during the catalyst ink preparation. This was proved to be very effective, largely improving anode performance with only 1/3 of catalyst loading. Finally, the PolyFuel membrane and supported catalysts were ready to be applied in the new MEA for the DMFCs. The new made MEA, with the catalyst loading of 2.6-time lower than a reference MEA, showed a very promising result, about only 10mV performance loss under the current density of 150mA/cm² compared with the reference MEA. Moreover, a short-term decay test indicated that the new MEA may have better durability and life because of its low methanol crossover on the cathode electrode due the PolyFuel membrane.

Plasma Spray Synthesis Of Nanostructured V2O5 Films For Electrical Energy Storage

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nanda, Jagjit

We demonstrate for the first time, the synthesis of nanostructured vanadium pentoxide (V2O5) films and coatings using plasma spray technique. V2O5 has been used in several applications such as catalysts, super-capacitors and also as an electrode material in lithium ion batteries. In the present studies, V2O5 films were synthesized using liquid precursors (vanadium oxychloride and ammonium metavanadate) and powder suspension. In our approach, the precursors were atomized and injected radially into the plasma gun for deposition on the substrates. During the flight towards the substrate, the high temperature of the plasma plume pyrolyzes the precursor particles resulting into the desiredmore » film coatings. These coatings were then characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), Transmission electron microscopy (TEM) and Differential Scanning Calorimetry (DSC). Among the precursors, vanadium oxychloride gave the best results in terms of nanocrystalline and monophasic films. Spraying of commercial powder suspension yielded multi-phasic mixture in the films. Our approach enables deposition of large area coatings of high quality nanocrystalline films of V2O5 with controllable particle morphology. This has been optimized by means of control over precursor composition and plasma spray conditions. Initial electrochemical studies of V2O5 film electrodes show potential for energy storage studies.« less

Nanostructured catalyst supports

DOEpatents

Zhu, Yimin; Goldman, Jay L.; Qian, Baixin; Stefan, Ionel C.

2012-10-02

The present invention relates to SiC nanostructures, including SiC nanopowder, SiC nanowires, and composites of SiC nanopowder and nanowires, which can be used as catalyst supports in membrane electrode assemblies and in fuel cells. The present invention also relates to composite catalyst supports comprising nanopowder and one or more inorganic nanowires for a membrane electrode assembly.

In-Plane Channel-Structured Catalyst Layer for Polymer Electrolyte Membrane Fuel Cells.

PubMed

Lee, Dong-Hyun; Jo, Wonhee; Yuk, Seongmin; Choi, Jaeho; Choi, Sungyu; Doo, Gisu; Lee, Dong Wook; Kim, Hee-Tak

2018-02-07

In this study, we present a novel catalyst layer (CL) with in-plane flow channels to enhance the mass transports in polymer electrolyte membrane fuel cells. The CL with in-plane channels on its surface is fabricated by coating a CL slurry onto a surface-treated substrate with the inverse line pattern and transferring the dried CL from the substrate to a membrane. The membrane electrode assembly with the in-plane channel-patterned CL has superior power performances in high current densities compared with an unpatterned, flat CL, demonstrating a significant enhancement of the mass-transport property by the in-plane channels carved in the CL. The performance gain is more pronounced when the channel direction is perpendicular to the flow field direction, indicating that the in-plane channels increase the utilization of the CL under the rib area. An oxygen-transport resistance analysis shows that both molecular and Knudsen diffusion can be facilitated with the introduction of the in-plane channels. The direct CL patterning technique provides a platform for the fabrication of advanced CL structures with a high structural fidelity and design flexibility and a rational guideline for designing high-performance CLs.

A micro alkaline direct ethanol fuel cell with platinum-free catalysts

NASA Astrophysics Data System (ADS)

Verjulio, R. W.; Alcaide, F.; Álvarez, G.; Sabaté, N.; Torres-Herrero, N.; Esquivel, J. P.; Santander, J.

2013-11-01

This paper presents the fabrication and characterization of a micro alkaline direct ethanol fuel cell. The device has been conceived as a feasibility demonstrator, using microtechnologies for the fabrication of the current collectors and traditional techniques for the membrane electrode assembly production. The fuel cell works in passive mode, as expected for the simplicity required for micro power systems. Non-noble catalysts have been used in order to implement the main advantage of alkaline systems, showing the feasibility of such a device as a potential very-low-cost power device at mini- and micro scales.

Molecularly imprinted polymer (MIP) membrane assisted direct spray ionization mass spectrometry for agrochemicals screening in foodstuffs.

PubMed

Pereira, Igor; Rodrigues, Marcella Ferreira; Chaves, Andréa Rodrigues; Vaz, Boniek Gontijo

2018-02-01

Paper spray ionization (PSI) has some limitations such as low sensitivity and ionization suppression when complex samples are analyzed. The use of sample preparation devices directly coupled to MS can avoid these restrictions. Molecularly imprinted polymers (MIPs) are materials widely used as adsorbent in sample preparation methods such as solid-phase extraction and solid-phase microextraction, and they can provide specifics cavities with affinity to a target molecule. Here, we introduce a new MIP membrane spray ionization method combining MIP and PSI. MIP was synthesized directly on a cellulose membrane. Monuron and 2,4,5-T (2,4,5-trichlorophenoxyacetic acid) were used as template molecules in MIP synthesis for diuron and 2,4-D (2,4-dichlorophenoxyacetic acid) analyte sequesters, respectively. Apple, banana and grape methanolic extracts were used as matrices. The MIP membrane spray showed signal intensities of diuron and 2,4-D that were much higher compared to those obtained by non-imprinted polymers(NIP). Calibration curves exhibited R 2 > 0.99 for diuron and 2,4-D in all fruit extracts analyzed. LODs were found less than 0.60µgL -1 and LLOQs were found less than 2.00µgL -1 . The coefficients of variation and relative errors were less than 15% for almost all analyses. The apparent recovery test results ranged between 92,5% and 116.9%. Finally, the MIP membrane spray method was employed for the quantification of diuron and 2,4-D in real samples. Diuron contents were only found in three bananas (4.0, 6.5, and 9.9µgL -1 ). The proposed MIP membrane spray ionization method was straightforward, fast to carry out and provided satisfactory results for analyses of diuron and 2,4-D in apple, banana and grape samples. Copyright © 2017 Elsevier B.V. All rights reserved.

High-throughput screening of nanoparticle catalysts made by flame spray pyrolysis as hydrocarbon/NO oxidation catalysts.

PubMed

Weidenhof, B; Reiser, M; Stöwe, K; Maier, W F; Kim, M; Azurdia, J; Gulari, E; Seker, E; Barks, A; Laine, R M

2009-07-08

We describe here the use of liquid-feed flame spray pyrolysis (LF-FSP) to produce high surface area, nonporous, mixed-metal oxide nanopowders that were subsequently subjected to high-throughput screening to assess a set of materials for deNO(x) catalysis and hydrocarbon combustion. We were able to easily screen some 40 LF-FSP produced materials. LF-FSP produces nanopowders that very often consist of kinetic rather than thermodynamic phases. Such materials are difficult to access or are completely inaccessible via traditional catalyst preparation methods. Indeed, our studies identified a set of Ce(1-x)Zr(x)O(2) and Al(2)O(3)-Ce(1-x)Zr(x)O(2) nanopowders that offer surprisingly good activities for both NO(x) reduction and propane/propene oxidation both in high-throughput screening and in continuous flow catalytic studies. All of these catalysts offer activities comparable to traditional Pt/Al(2)O(3) catalysts but without Pt. Thus, although Pt-free, they are quite active for several extremely important emission control reactions, especially considering that these are only first generation materials. Indeed, efforts to dope the active catalysts with Pt actually led to lower catalytic activities. Thus the potential exists to completely change the materials used in emission control devices, especially for high-temperature reactions as these materials have already been exposed to 1500 degrees C; however, much research must be done before this potential is verified.

Optimum concentration gradient of the electrocatalyst, Nafion® and poly(tetrafluoroethylene) in a membrane-electrode-assembly for enhanced performance of direct methanol fuel cells.

PubMed

Liu, Jing Hua; Jeon, Min Ku; Lee, Ki Rak; Woo, Seong Ihl

2010-12-14

A combinatorial library of membrane-electrode-assemblies (MEAs) which consisted of 27 different compositions was fabricated to optimize the multilayer structure of direct methanol fuel cells. Each spot consisted of three layers of ink and a gradient was generated by employing different concentrations of the three components (Pt catalyst, Nafion® and polytetrafluoroethylene (PTFE)) of each layer. For quick evaluation of the library, a high-throughput optical screening technique was employed for methanol electro-oxidation reaction (MOR) activity. The screening results revealed that gradient layers could lead to higher MOR activity than uniform layers. It was found that the MOR activity was higher when the concentrations of Pt catalyst and Nafion ionomer decreased downward from the top layer to the bottom layer. On the other hand, higher MOR activity was observed when PTFE concentration increased downward from the top to the bottom layer.

Process for recycling components of a PEM fuel cell membrane electrode assembly

DOEpatents

Shore, Lawrence [Edison, NJ

2012-02-28

The membrane electrode assembly (MEA) of a PEM fuel cell can be recycled by contacting the MEA with a lower alkyl alcohol solvent which separates the membrane from the anode and cathode layers of the assembly. The resulting solution containing both the polymer membrane and supported noble metal catalysts can be heated under mild conditions to disperse the polymer membrane as particles and the supported noble metal catalysts and polymer membrane particles separated by known filtration means.

Solid-State Water Electrolysis with an Alkaline Membrane

DOE Office of Scientific and Technical Information (OSTI.GOV)

Leng, YJ; Chen, G; Mendoza, AJ

2012-06-06

We report high-performance, durable alkaline membrane water electrolysis in a solid-state cell. An anion exchange membrane (AEM) and catalyst layer ionomer for hydroxide ion conduction were used without the addition of liquid electrolyte. At 50 degrees C, an AEM electrolysis cell using iridium oxide as the anode catalyst and Pt black as the cathode catalyst exhibited a current density of 399 mA/cm(2) at 1.80 V. We found that the durability of the AEM-based electrolysis cell could be improved by incorporating a highly durable ionomer in the catalyst layer and optimizing the water feed configuration. We demonstrated an AEM-based electrolysis cellmore » with a lifetime of > 535 h. These first-time results of water electrolysis in a solid-state membrane cell are promising for low-cost, scalable hydrogen production.« less

Synthesis of an un-supported, high-flow ZSM-22 zeolite membrane

DOEpatents

Thoma, Steven G [Albuquerque, NM; Nenoff, Tina M [Albuquerque, NM

2006-10-10

Novel methods for synthesizing wholly un-supported, high-flow catalytic membranes consisting of 100% crystalline ZSM-22 crystals with no binder phase, having sufficient porosity to allow high Weight Hourly Space Velocities of feedstock to pass through without generating back pressure. The ZSM-22 membranes perform favorably to existing bulk ZSM-22 catalysts (e.g., via 1-butene conversion and selectivity). The method of membrane synthesis, based on Vapor Phase Transport, allows free-standing, binder-less membranes to be fabricated in varied geometries and sizes so that membranes can be tailor-made for particular geometries applications. The ZSM-22 precursor gel may be consolidated into a semi-cohesive body prior to vapor phase crystallization, for example, by uniaxial pressing. These crystalline membranes may be modified by ion exchange, pore ion exchange, framework exchange, synthesis modification techniques to incorporate other elements into the framework, such as K, H, Mg, Zn, V, Ga, and Pt.

Modification of tubular ceramic membranes with carbon nanotubes using catalytic chemical vapor deposition.

PubMed

Tran, Duc Trung; Thieffry, Guillemette; Jacob, Matthieu; Batiot-Dupeyrat, Catherine; Teychene, Benoit

2015-01-01

In this study, carbon nanotubes (CNTs) were successfully grown on tubular ceramic membranes using the catalytic chemical vapor deposition (CCVD) method. CNTs were synthesized at 650°C for 3-6 h under a 120 mL min(-1) flow of C2H6 on ceramic membranes impregnated with iron salt. The synthesis procedure was beforehand optimized in terms of catalyst amount, impregnation duration and reaction temperature, using small pieces of tubular ceramic membranes. The yield, size and structure of the CNTs produced were characterized using thermogravimetric analysis and microscopic imaging techniques. Afterwards, preliminary filtration tests with alginate and phenol were performed on two modified tubular membranes. The results indicate that the addition of CNTs on the membrane material increased the permeability of ceramic membrane and its ability to reject alginate and adsorb phenol, yet decreased its fouling resistance.

Electrical enhancement of direct methanol fuel cells by metal-plasma ion implantation Pt-Ru/C multilayer catalysts.

PubMed

Weng, Ko-Wei; Chen, Yung-Lin; Chen, Ya-Chi; Lin, Tai-Nan

2009-02-01

Direct methanol fuel cells (DMFC) have been widely studied owing to their simple cell configuration, high volume energy density, short start-up time, high operational reliability and other favorable characteristics. However, major limitations include high production cost, poisoning of the catalyst and methanol crossover. This study adopts a simple technique for preparing Pt-Ru/C multilayer catalysts, including magnetron sputtering (MS) and metal-plasma ion implantation (MPII). The Pt catalysts were sputtered onto the gas diffusion layer (GDL), followed by the implantation of Ru catalysts using MPII (at an accelerating voltage of 20 kV and an implantation dose of 1 x 10(16) ions/cm2). Pt-Ru is repeatedly processed to prepare Pt-Ru/C multilayer catalysts. The catalyst film structure and microstructure were analyzed by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and scanning electronic microscopy (SEM), respectively. The cell performance was tested using a potential stat/galvano-stat. The results reveal that the membrane electrode assembly (MEA) of four multilayer structures enhances the cell performance of DMFC. The measured power density is 2.2 mW/cm2 at a methanol concentration of 2 M, with an OCV of 0.493 V.

Investigation of Oxygen Reduction Activity of Catalysts Derived from Co and Co/Zn Methyl-Imidazolate Frameworks in Proton Exchange Membrane Fuel Cells

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chong, Lina; Goenaga, Gabriel A.; Williams, Kia

We demonstrated that the oxygen reduction reaction (ORR) activity over the catalysts derived from pyrolyzed cobalt zeolitic imidazolate frameworks depends strongly on the imidazole ligand structure and cobalt content. The activity and durability of these catalysts were tested in the proton exchange membrane fuel cell for the first time. The membrane electrode assembly containing a catalyst derived from Co/Zn bimetallic ZIF at cathode achieved an open circuit voltage of 0.93 V, a current density of 28 mA cm-2 at 0.8 ViR-free and a peak power density of 374 mW cm-2.

Unraveling micro- and nanoscale degradation processes during operation of high-temperature polymer-electrolyte-membrane fuel cells

NASA Astrophysics Data System (ADS)

Hengge, K.; Heinzl, C.; Perchthaler, M.; Varley, D.; Lochner, T.; Scheu, C.

2017-10-01

The work in hand presents an electron microscopy based in-depth study of micro- and nanoscale degradation processes that take place during the operation of high-temperature polymer-electrolyte-membrane fuel cells (HT-PEMFCs). Carbon supported Pt particles were used as cathodic catalyst material and the bimetallic, carbon supported Pt/Ru system was applied as anode. As membrane, cross-linked polybenzimidazole was used. Scanning electron microscopy analysis of cross-sections of as-prepared and long-term operated membrane-electrode-assemblies revealed insight into micrometer scale degradation processes: operation-caused catalyst redistribution and thinning of the membrane and electrodes. Transmission electron microscopy investigations were performed to unravel the nanometer scale phenomena: a band of Pt and Pt/Ru nanoparticles was detected in the membrane adjacent to the cathode catalyst layer. Quantification of the elemental composition of several individual nanoparticles and the overall band area revealed that they stem from both anode and cathode catalyst layers. The results presented do not demonstrate any catastrophic failure but rather intermediate states during fuel cell operation and indications to proceed with targeted HT-PEMFC optimization.

HSPES membrane electrode assembly

NASA Technical Reports Server (NTRS)

Kindler, Andrew (Inventor); Yen, Shiao-Ping (Inventor)

2000-01-01

An improved fuel cell electrode, as well as fuel cells and membrane electrode assemblies that include such an electrode, in which the electrode includes a backing layer having a sintered layer thereon, and a non-sintered free-catalyst layer. The invention also features a method of forming the electrode by sintering a backing material with a catalyst material and then applying a free-catalyst layer.

Probing platinum degradation in polymer electrolyte membrane fuel cells by synchrotron X-ray microscopy.

PubMed

Berejnov, Viatcheslav; Martin, Zulima; West, Marcia; Kundu, Sumit; Bessarabov, Dmitri; Stumper, Jürgen; Susac, Darija; Hitchcock, Adam P

2012-04-14

Synchrotron-based scanning transmission X-ray spectromicroscopy (STXM) was used to characterize the local chemical environment at and around the platinum particles in the membrane (PTIM) which form in operationally tested (end-of-life, EOL) catalyst coated membranes (CCMs) of polymer electrolyte membrane fuel cells (PEM-FC). The band of metallic Pt particles in operationally tested CCM membranes was imaged using transmission electron microscopy (TEM). The cathode catalyst layer in the beginning-of-life (BOL) CCMs was fabricated using commercially available catalysts created from Pt precursors with and without nitrogen containing ligands. The surface composition of these catalyst powders was measured by X-ray Photoelectron Spectroscopy (XPS). The local chemical environment of the PTIM in EOL CCMs was found to be directly related to the Pt precursor used in CCM fabrication. STXM chemical mapping at the N 1s edge revealed a characteristic spectrum at and around the dendritic Pt particles in CCMs fabricated with nitrogen containing Pt-precursors. This N 1s spectrum was identical to that of the cathode and different from the membrane. For CCM samples fabricated without nitrogen containing Pt-precursors the N 1s spectrum at the Pt particles was indistinguishable from that of the adjacent membrane. We interpret these observations to indicate that nitrogenous ligands in the nitrogen containing precursors, or decomposition product(s) from that source, are transported together with the dissolved Pt from the cathode into the membrane as a result of the catalyst degradation process. This places constraints on possible mechanisms for the PTIM band formation process.

"Catalysis in a tea bag": synthesis, catalytic performance and recycling of dendrimer-immobilised bis- and trisoxazoline copper catalysts.

PubMed

Gaab, Manuela; Bellemin-Laponnaz, Stéphane; Gade, Lutz H

2009-01-01

Bis- and trisoxazolines (BOX and trisox), containing a linker unit in the ligand backbone that allows their covalent attachment to carbosilane dendrimers, have been employed as polyfunctional ligands for recyclable Cu(II) Lewis acid catalysts that were immobilised in a membrane bag. The oxazolines contained an alkynyl unit attached to their backbone that was deprotonated with LDA or BuLi and then reacted with the chlorosilyl termini of zeroth-, first- and second-generation carbosilane dendrimers in the presence of TlPF(6). The functionalised dendritic systems were subsequently separated from excess ligand by way of dialysis. The general catalytic potential of these systems was assessed by studying two benchmark reactions, the alpha-hydrazination of a beta-keto ester as well as the Henry reaction of 2-nitrobenzaldehyde with nitromethane. For both reactions the bisoxazoline-based catalysts displayed superior selectivity and, in particular, catalyst activity. The latter was interpreted as being due to the hindered decoordination of the third oxazoline unit, the key step in the generation of the active catalyst, in the immobilised trisox-copper complexes. Solutions of the second-generation dendrimer catalysts were placed in membrane bags, fabricated from commercially available dialysis membranes, with the purpose of catalyst recycling based on dialysis. Overall, the supported BOX catalyst gave good and highly reproducible results throughout the study, whereas the performance of the trisox dendrimer system decreased monotonically. The reason for the different behaviour is the markedly lower activity of trisox-based catalysts relative to those based on the BOX ligand. This necessitated an increased reaction time for each cycle of the trisox derivatives, resulting in higher levels of catalyst leaching, which was attributed to a modification of the structure of the membrane by its exposure to the solvent trifluoroethanol at 40 degrees C.

Anion permselective membrane

NASA Technical Reports Server (NTRS)

Hodgdon, R. B.; Waite, W. A.

1982-01-01

The synthesis and fabrication of polymeric anion permselective membranes for redox systems are discussed. Variations of the prime candidate anion membrane formulation to achieve better resistance and/or lower permeability were explored. Processing parameters were evaluated to lower cost and fabricate larger sizes. The processing techniques to produce more membranes per batch were successfully integrated with the fabrication of larger membranes. Membranes of about 107 cm x 51 cm were made in excellent yield. Several measurements were made on the larger sample membranes. Among the data developed were water transport and transference numbers for these prime candidate membranes at 20 C. Other work done on this system included characterization of a number of specimens of candidate membranes which had been returned after service lives of up to sixteen months. Work with new polymer constituents, with new N.P.'s, catalysts and backing fabrics is discussed. Some work was also done to evaluate other proportions of the ingredients of the prime candidate system. The adoption of a flow selectivity test at elevated temperature was explored.

NASA redox storage system development project, calendar year 1982

NASA Technical Reports Server (NTRS)

1983-01-01

Development was continued for iron-chromium battery operation at 65 C. Membranes that were adequate at 25 C were shown to be unacceptable at 65 C with regard to selectivity. This led to the elevated-temperature, mixed-reactant mode of operation, in which each reactant solution, when discharged, contains both ferrous and chromic chlorides. This operating mode allows the use of very low-resistivity membranes, resulting in high energy efficiencies at current densities. It also allows the use of very simple techniques to correct for solvent or reactant transfer through cell membranes. Screening of candidate catalysts for the chromium electrode led to the development of a bismuth-lead candidate having several attractive characteristics.

Comparison of the performance between a spray gun and a spray boom in ornamentals.

PubMed

Foqué, D; Nuyttens, D

2011-01-01

Flemish greenhouse growers predominantly use handheld spray guns and spray lances for their crop protection purposes although these techniques are known for their heavy workload and their high operator exposure risks. Moreover, when these techniques are compared with spray boom equipment, they are often found to be less effective. On the other hand, handheld spraying techniques are less expensive and more flexible to use. Additionally, many Flemish growers are convinced that a high spray volume and spray pressure is needed to assure a good plant protection. The aim of this work was to evaluate and compare the spray deposition, penetration and uniformity between a manually pulled horizontal spray boom and a spray gun under controlled laboratory conditions. In total, six different spray application techniques were evaluated. In general, the total deposition results were comparable between the spray boom and the spray gun applications but the boom applications resulted in a more uniform spray distribution over the crop. On a plant level, the spray distribution was not uniform for the different techniques with highest deposits on the upper side of the top leaves. Using spray guns at a higher spray pressure did not improve spray penetration and deposition on the bottom side of the leaves. From the different nozzle types, the XR 80 03 gave the best results. Plant density clearly affected crop penetration and deposition on the bottom side of the leaves.

Impact of IrRu Oxygen Evolution Reaction Catalysts on Pt Nanostructured Thin Films under Start-Up/Shutdown Cycling

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cullen, David A; More, Karren Leslie; Atanasoska, Liliana

Electron microscopy and X-ray photoelectron spectroscopy (XPS) methods have been utilized to study the role of oxygen evolution reaction (OER) catalysts in mitigating degradation arising from start-up/shutdown events. Pt nanostructured thin films (NSTF) were coated with a Ru0.1Ir0.9 OER catalyst at loadings ranging from 1 to 10 g/cm2 and submitted to 5,000 potential cycles within a membrane electrode assembly. Analysis of the as-deposited catalyst showed that Ir and Ru coating is primarily metallic, and further evidence is provided to support the previously reported interaction between Ru and the perylene-red support. Aberration-corrected scanning transmission electron microscopy and energy dispersive X-ray spectroscopymore » were used to observe the impact of the OER catalysts on Pt dissolution and migration through the membrane. Elemental mapping showed a high percentage of the Ir catalyst was maintained on the NSTF whisker surfaces following testing. The presence of the OER catalysts greatly reduced the smoothing of the Pt NSTF whiskers, which has been correlated with Pt dissolution and losses in electrochemically active surface area. The dissolution of both Ir and Pt led to the formation of IrPt nanoparticle clusters in the membrane close to the cathode, as well as the formation of a Pt band deeper in the membrane.« less

Performance and durability of carbon black-supported Pd catalyst covered with silica layers in membrane-electrode assemblies of proton exchange membrane fuel cells

NASA Astrophysics Data System (ADS)

Fujii, Keitaro; Ito, Mizuki; Sato, Yasushi; Takenaka, Sakae; Kishida, Masahiro

2015-04-01

Pd metal particles supported on a high surface area carbon black (Pd/CB) were covered with silica layers to improve the durability under severe cathode condition of proton exchange membrane fuel cells (PEMFCs). The performance and the durability of the silica-coated Pd/CB (SiO2/Pd/CB) were investigated by rotating disk electrode (RDE) in aqueous HClO4 and single cell test of the membrane-electrode assemblies (MEAs). SiO2/Pd/CB showed excellent durability exceeding Pt/CB during potential cycle in single cell test as well as in RDE measurement while Pd/CB significantly degraded. Furthermore, the MEA using SiO2/Pd/CB as the cathode catalyst showed higher performance than that using Pd/CB even in the initial state. The catalytic activity of SiO2/Pd/CB was higher than that of Pd/CB, and the drop of the cell performances due to the inhibition of electron conduction, proton conduction, and oxygen diffusion by the silica layer was not significant. It has been shown that the silica-coating is a very practical technique that can stabilize metal species originally unstable in the cathode condition of PEMFCs without a decrease in the cell performance.

Preparation method of Ni@Pt/C nanocatalyst affects the performance of direct borohydride-hydrogen peroxide fuel cell: Improved power density and increased catalytic oxidation of borohydride.

PubMed

Hosseini, Mir Ghasem; Mahmoodi, Raana

2017-08-15

The Ni@Pt/C electrocatalysts were synthesized using two different methods: with sodium dodecyl sulfate (SDS) and without SDS. The metal loading in synthesized nanocatalysts was 20wt% and the molar ratio of Ni: Pt was 1:1. The structural characterizations of Ni@Pt/C electrocatalysts were investigated by field emission scanning electron microscopy (FE-SEM), energy-dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD), transmission electron microscopy (TEM) and high-resolution transmission electron microscopy (HR-TEM). The electrocatalytic activity of Ni@Pt/C electrocatalysts toward BH 4 - oxidation in alkaline medium was studied by means of cyclic voltammetry (CV), chronopotentiometry (CP), chronoamperometry (CA) and electrochemical impedance spectroscopy (EIS). The results showed that Ni@Pt/C electrocatalyst synthesized without SDS has superior catalytic activity toward borohydride oxidation (22016.92Ag Pt -1 ) in comparison with a catalyst prepared in the presence of SDS (17766.15Ag Pt -1 ) in NaBH 4 0.1M at 25°C. The Membrane Electrode Assembly (MEA) used in fuel cell set-up was fabricated with catalyst-coated membrane (CCM) technique. The effect of Ni@Pt/C catalysts prepared with two methods as anode catalyst on the performance of direct borohydride-hydrogen peroxide fuel cell was studied. The maximum power density was obtained using Ni@Pt/C catalyst synthesized without SDS at 60°C, 1M NaBH 4 and 2M H 2 O 2 (133.38mWcm -2 ). Copyright © 2017 Elsevier Inc. All rights reserved.

Degradation Study by Start-Up/Shut-Down Cycling of Superhydrophobic Electrosprayed Catalyst Layers Using a Localized Reference Electrode Technique.

PubMed

Ferreira-Aparicio, Paloma; Chaparro, Antonio M; Folgado, M Antonia; Conde, Julio J; Brightman, Edward; Hinds, Gareth

2017-03-29

Degradation of a polymer electrolyte membrane fuel cell (PEMFC) with electrosprayed cathode catalyst layers is investigated during cyclic start-up and shut-down events. The study is carried out within a single cell incorporating an array of reference electrodes that enables measurement of cell current as a function of local cathode potential (localized polarization curves). Accelerated degradation of the cell by start-up/shut-down cycling gives rise to inhomogeneous performance loss, which is more severe close to the gas outlet and occurs predominantly during start-up. The degradation consists primarily of loss of cathode catalyst activity and increase in cell internal resistance, which is attributed to carbon corrosion and Pt aggregation in both anode and cathode. Cells with an electrosprayed cathode catalyst layer show lower degradation rates during the first 100 cycles, compared with those of a conventional gas diffusion electrode. This difference in behavior is attributed to the high hydrophobicity of the electrosprayed catalyst layer microstructure, which retards the kinetics of corrosion of the carbon support. In the long term, however, the degradation rate is dominated by the Pt/C ratio in the cathode catalyst layer.

[Effects of exogenous spermidine on lipid peroxidation and membrane proton pump activity of cucumber seedling leaves under high temperature stress].

PubMed

Tian, Jing; Guo, Shi-Rong; Sun, Jin; Wang, Li-Ping; Yang, Yan-Juan; Li, Bin

2011-12-01

Taking a relatively heat-resistant cucumber (Cucumis sativus) cultivar 'Jinchun No. 4' as test material, a sand culture experiment was conducted in growth chamber to investigate the effects of foliar spraying spermidine (Spd) on the lipid peroxidation, membrane proton pump activity, and corresponding gene expression of cucumber seedling leaves under high temperature stress. Compared with the control, foliar spraying Spd increased the plant height, stem diameter, dry and fresh mass, and leaf area significantly, and inhibited the increase of leaf relative conductivity, malondialdehyde (MDA) content, and lipoxygenase (LOX) activity effectively. Foliar spraying Spd also helped to the increase of leaf plasma membrane- and tonoplast H(+)-ATPase activity, but no significant difference was observed in the gene expression levels. These results suggested that exogenous Spd could significantly decrease the leaf lipid peroxidation and increase the proton pump activity, and thus, stabilize the leaf membrane structure and function, alleviate the damage induced by high temperature stress, and enhance the heat tolerance of cucumber seedlings.

Immobilized TiO2 nanoparticles produced by flame spray for photocatalytic water remediation

NASA Astrophysics Data System (ADS)

Bettini, Luca Giacomo; Diamanti, Maria Vittoria; Sansotera, Maurizio; Pedeferri, Maria Pia; Navarrini, Walter; Milani, Paolo

2016-08-01

Anatase/rutile mixed-phase titanium dioxide (TiO2) photocatalysts in the form of nanostructured powders with different primary particle size, specific surface area, and rutile content were produced from the gas-phase by flame spray pyrolysis (FSP) starting from an organic solution containing titanium (IV) isopropoxide as Ti precursor. Flame spray-produced TiO2 powders were characterized by means of X-ray diffraction, Raman spectroscopy, and BET measurements. As-prepared powders were mainly composed of anatase crystallites with size ranging from 7 to 15 nm according to the synthesis conditions. TiO2 powders were embedded in a multilayered fluoropolymeric matrix to immobilize the nanoparticles into freestanding photocatalytic membranes. The photocatalytic activity of the TiO2-embedded membranes toward the abatement of hydrosoluble organic pollutants was evaluated employing the photodegradation of rhodamine B in aqueous solution as test reaction. The photoabatement rate of best performing membranes significantly overcomes that of membranes produced by the same method and incorporating commercial P25-TiO2.

Solvent-resistant nanofiltration for product purification and catalyst recovery in click chemistry reactions.

PubMed

Cano-Odena, Angels; Vandezande, Pieter; Fournier, David; Van Camp, Wim; Du Prez, Filip E; Vankelecom, Ivo F J

2010-01-18

The quickly developing field of "click" chemistry would undoubtedly benefit from the availability of an easy and efficient technology for product purification to reduce the potential health risks associated with the presence of copper in the final product. Therefore, solvent-resistant nanofiltration (SRNF) membranes have been developed to selectively separate "clicked" polymers from the copper catalyst and solvent. By using these solvent-stable cross-linked polyimide membranes in diafiltration, up to 98 % of the initially present copper could be removed through the membrane together with the DMF solvent, the polymer product being almost completely retained. This paper also presents the first SRNF application in which the catalyst permeates through the membrane and the reaction product is retained.

New insights into respirable protein powder preparation using a nano spray dryer.

PubMed

Bürki, K; Jeon, I; Arpagaus, C; Betz, G

2011-04-15

In this study the Nano Spray Dryer B-90 (BÜCHI Labortechnik AG, Flawil, Switzerland) was evaluated with regard to the drying of proteins and the preparation of respirable powders in the size range of 1-5 μm. β-galactosidase was chosen as a model protein and trehalose was added as a stabilizer. The influence of inlet temperature, hole size of the spray cap membrane and ethanol concentration in the spray solution was studied using a 3³ full factorial design. The investigated responses were enzyme activity, particle size, span, yield and shelf life. Furthermore, the particle morphology was examined. The inlet temperature as well as the interaction of inlet temperature and spray cap size significantly influenced the enzyme activity. Full activity was retained with the optimized process. The particle size was affected by the hole size of the spray cap membrane and the ethanol content. The smallest cap led to a monodisperse particle size distribution and the greatest yield of particles of respirable size. Higher product recovery was achieved with lower inlet temperatures, higher ethanol contents and smaller cap sizes. Particle morphology differed depending on the cap size. The protein exhibited higher storage stability when spray dried without ethanol and when a larger spray cap size was used. Copyright © 2011 Elsevier B.V. All rights reserved.

Characteristics and functionality of appetite-reducing thylakoid powders produced by three different drying processes.

PubMed

Östbring, Karolina; Sjöholm, Ingegerd; Sörenson, Henrietta; Ekholm, Andrej; Erlanson-Albertsson, Charlotte; Rayner, Marilyn

2018-03-01

Thylakoids, a chloroplast membrane extracted from green leaves, are a promising functional ingredient with appetite-reducing properties via their lipase-inhibiting effect. Thylakoids in powder form have been evaluated in animal and human models, but no comprehensive study has been conducted on powder characteristics. The aim was to investigate the effects of different isolation methods and drying techniques (drum-drying, spray-drying, freeze-drying) on thylakoids' physicochemical and functional properties. Freeze-drying yielded thylakoid powders with the highest lipase-inhibiting capacity. We hypothesize that the specific macromolecular structures involved in lipase inhibition were degraded to different degrees by exposure to heat during spray-drying and drum-drying. We identified lightness (Hunter's L-value), greenness (Hunter's a-value), chlorophyll content and emulsifying capacity to be correlated to lipase-inhibiting capacity. Thus, to optimize the thylakoids functional properties, the internal membrane structure indicated by retained green colour should be preserved. This opens possibilities to use chlorophyll content as a marker for thylakoid functionality in screening processes during process optimization. Thylakoids are heat sensitive, and a mild drying technique should be used in industrial production. Strong links between physicochemical parameters and lipase inhibition capacity were found that can be used to predict functionality. The approach from this study can be applied towards production of standardized high-quality functional food ingredients. © 2017 Society of Chemical Industry. © 2017 Society of Chemical Industry.

Synthesis of attrition-resistant heterogeneous catalysts using templated mesoporous silica

DOEpatents

Pham, Hien N.; Datye, Abhaya K.

2003-04-15

The present invention relates to catalysts in mesoporous structures. In a preferred embodiment, the invention comprises a method for encapsulating a dispersed insoluble compound in a mesoporous structure comprising combining a soluble oxide precursor, a solvent, and a surfactant to form a mixture; dispersing an insoluble compound in the mixture; spray-drying the mixture to produce dry powder; and calcining the powder to yield a porous structure comprising the dispersed insoluble compound.

A Membrane-Free Neutral pH Formate Fuel Cell Enabled by a Selective Nickel Sulfide Oxygen Reduction Catalyst.

PubMed

Yan, Bing; Concannon, Nolan M; Milshtein, Jarrod D; Brushett, Fikile R; Surendranath, Yogesh

2017-06-19

Polymer electrolyte membranes employed in contemporary fuel cells severely limit device design and restrict catalyst choice, but are essential for preventing short-circuiting reactions at unselective anode and cathode catalysts. Herein, we report that nickel sulfide Ni 3 S 2 is a highly selective catalyst for the oxygen reduction reaction in the presence of 1.0 m formate. We combine this selective cathode with a carbon-supported palladium (Pd/C) anode to establish a membrane-free, room-temperature formate fuel cell that operates under benign neutral pH conditions. Proof-of-concept cells display open circuit voltages of approximately 0.7 V and peak power values greater than 1 mW cm -2 , significantly outperforming the identical device employing an unselective platinum (Pt) cathode. The work establishes the power of selective catalysis to enable versatile membrane-free fuel cells. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nitrogen-doped three-dimensional graphene-supported platinum catalysts for polymer electrolyte membrane fuel cells application

NASA Astrophysics Data System (ADS)

Chu, Fuqiang; Li, Xingxing; Yuan, Wensen; Zhu, Huanhuan; Qin, Yong; Zhang, Shuai; Yuan, Ningyi; Lin, Bencai; Ding, Jianning

Catalysts are a key component of polymer electrolyte membrane fuel cells (PEMFCs). In this work, nitrogen-doped three-dimensional graphene-supported platinum (Pt-3DNG) catalysts are successfully prepared and characterized. SEM and TEM images show the Pt nanoparticles are uniformly dispersed in the sheets of nitrogen-doped 3DNG. Compared with that of the commercial Pt/C catalysts, Pt-3DNG show much better oxygen reduction reaction (ORR) activity and cycling stability, and the reduction in limit current density after 1000 cycles is only about 1.6% for the Pt-3DNG catalysts, whereas 7.2% for the commercial Pt/C catalysts. The single cell using Pt-3DNG catalysts in both the anode and the cathode show a higher peak power density (21.47mW cm-2) than that using commercial Pt/C catalysts (20.17mW cm-2) under the same conditions. These properties make this type of catalyst suitable for the application in PEMFCs.

Performance of polyethylene based radiation grafted anion exchange membrane with polystyrene-b-poly (ethylene/butylene)-b-polystyrene based ionomer using NiCo2O4 catalyst for water electrolysis

NASA Astrophysics Data System (ADS)

Gupta, Gaurav; Scott, Keith; Mamlouk, Mohamed

2018-01-01

A soluble anion exchange ionomer with high OH- ion conductivity comparable to that of H+ conductivity of Nafion is synthesised by chloromethylation of polystyrene-b-poly (ethylene/butylene)-b-polystyrene (SEBS) and used with NiCo2O4 electro-catalyst for water electrolysis. The ionomer has an ion exchange capacity of 1.9 mmol g-1 and ionic conductivity of 0.14 S cm-2 at 50 °C. The cell voltage at 20 °C at 100 mA cm-2 is 1.77 and 1.72 V in, 0.1 and 1.0 M NaOH, respectively, for an optimum loading of 10 mg cm-2 NiCo2O4. At 10 mg cm-2 NiCo2O4 electrolyser cell performance is at least equal to or superior to that of IrO2 at 2 mg cm-2 with excellent stability over 1 h. When the catalyst is sprayed on the GDL instead of CCM, the performance is further improved to 1.65 V at 100 mA cm-2 at 60 °C & 0.1 M KOH. The limited AEM electrolyser performance when operating with deionised water in comparison to PEM and alkaline electrolyser arises from the sluggish OER in the AEM environment equivalent to pH of 11.5 and the two orders of magnitude lower HER activity with respect to acid medium combined with the high Tafel slope of 120 mV dec-1.

A laser tomographic investigation of liquid fuel sprays

NASA Technical Reports Server (NTRS)

Yule, A. J.; Ahseng, C.; Felton, P.; Ungut, A.; Chigier, N. A.

1980-01-01

A light scattering technique is combined with a tomographic transformation to convert line of sight integrated data, measured in sprays, to measurements of droplet size and concentration in volume elements within the spray. The technique is developed and assessed by systematic experiments in axisymmetric sprays generated by twin-fluid atomisers. The good agreement found shows that, provided certain conditions are satisfied by the local spray structure, the technique provides information on spray structure, similar in detail and extent to that derived by photography, but with reduced experimental time. The technique is applied to an investigation of a kerosene spray vaporizing in a hot gas stream.

Stability of High-Performance Pt-Based Catalysts for Oxygen Reduction Reactions.

PubMed

Lin, Rui; Cai, Xin; Zeng, Hao; Yu, Zhuoping

2018-04-01

Due to their environmental sustainability and high efficiency, proton-exchange-membrane fuel cells (PEMFCs) are expected to be an essential type of energy source for electric vehicles, energy generation, and the space industry in the coming decades. Here, the recent developments regarding shape-controlled nanostructure catalysts are reviewed, with a focus on the stability of high-performance Pt-based catalysts and related mechanisms. The catalysts, which possess great activity, are still far from meeting the requirements of their applications, due to stability issues, especially in membrane electrode assemblies (MEAs). Thus, solutions toward the comprehensive performance of Pt-based catalysts are discussed here. The research trends and related theories that can promote the application of Pt-based catalysts are also provided. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Recent Advances in Pd-Based Membranes for Membrane Reactors.

PubMed

Arratibel Plazaola, Alba; Pacheco Tanaka, David Alfredo; Van Sint Annaland, Martin; Gallucci, Fausto

2017-01-01

Palladium-based membranes for hydrogen separation have been studied by several research groups during the last 40 years. Much effort has been dedicated to improving the hydrogen flux of these membranes employing different alloys, supports, deposition/production techniques, etc. High flux and cheap membranes, yet stable at different operating conditions are required for their exploitation at industrial scale. The integration of membranes in multifunctional reactors (membrane reactors) poses additional demands on the membranes as interactions at different levels between the catalyst and the membrane surface can occur. Particularly, when employing the membranes in fluidized bed reactors, the selective layer should be resistant to or protected against erosion. In this review we will also describe a novel kind of membranes, the pore-filled type membranes prepared by Pacheco Tanaka and coworkers that represent a possible solution to integrate thin selective membranes into membrane reactors while protecting the selective layer. This work is focused on recent advances on metallic supports, materials used as an intermetallic diffusion layer when metallic supports are used and the most recent advances on Pd-based composite membranes. Particular attention is paid to improvements on sulfur resistance of Pd based membranes, resistance to hydrogen embrittlement and stability at high temperature.

Membrane-Based Technologies in the Pharmaceutical Industry and Continuous Production of Polymer-Coated Crystals/Particles.

PubMed

Chen, Dengyue; Sirkar, Kamalesh K; Jin, Chi; Singh, Dhananjay; Pfeffer, Robert

2017-01-01

Membrane technologies are of increasing importance in a variety of separation and purification applications involving liquid phases and gaseous mixtures. Although the most widely used applications at this time are in water treatment including desalination, there are many applications in chemical, food, healthcare, paper and petrochemical industries. This brief review is concerned with existing and emerging applications of various membrane technologies in the pharmaceutical and biopharmaceutical industry. The goal of this review article is to identify important membrane processes and techniques which are being used or proposed to be used in the pharmaceutical and biopharmaceutical operations. How novel membrane processes can be useful for delivery of crystalline/particulate drugs is also of interest. Membrane separation technologies are extensively used in downstream processes for bio-pharmaceutical separation and purification operations via microfiltration, ultrafiltration and diafiltration. Also the new technique of membrane chromatography allows efficient purification of monoclonal antibodies. Membrane filtration techniques of reverse osmosis and nanofiltration are being combined with bioreactors and advanced oxidation processes to treat wastewaters from pharmaceutical plants. Nanofiltration with organic solvent-stable membranes can implement solvent exchange and catalyst recovery during organic solvent-based drug synthesis of pharmaceutical compounds/intermediates. Membranes in the form of hollow fibers can be conveniently used to implement crystallization of pharmaceutical compounds. The novel crystallization methods of solid hollow fiber cooling crystallizer (SHFCC) and porous hollow fiber anti-solvent crystallization (PHFAC) are being developed to provide efficient methods for continuous production of polymer-coated drug crystals in the area of drug delivery. This brief review provides a general introduction to various applications of membrane technologies in the pharmaceutical/biopharmaceutical industry with special emphasis on novel membrane techniques for pharmaceutical applications. The method of coating a drug particle with a polymer using the SHFCC method is stable and ready for scale-up for operation over an extended period. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

Realization of Both High-Performance and Enhanced Durability of Fuel Cells: Pt-Exoskeleton Structure Electrocatalysts.

PubMed

Kim, Ok-Hee; Cho, Yoon-Hwan; Jeon, Tae-Yeol; Kim, Jung Won; Cho, Yong-Hun; Sung, Yung-Eun

2015-07-01

Core-shell structure nanoparticles have been the subject of many studies over the past few years and continue to be studied as electrocatalysts for fuel cells. Therefore, many excellent core-shell catalysts have been fabricated, but few studies have reported the real application of these catalysts in a practical device actual application. In this paper, we demonstrate the use of platinum (Pt)-exoskeleton structure nanoparticles as cathode catalysts with high stability and remarkable Pt mass activity and report the outstanding performance of these materials when used in membrane-electrode assemblies (MEAs) within a polymer electrolyte membrane fuel cell. The stability and degradation characteristics of these materials were also investigated in single cells in an accelerated degradation test using load cycling, which is similar to the drive cycle of a polymer electrolyte membrane fuel cell used in vehicles. The MEAs with Pt-exoskeleton structure catalysts showed enhanced performance throughout the single cell test and exhibited improved degradation ability that differed from that of a commercial Pt/C catalyst.

A direct borohydride fuel cell with a polymer fiber membrane and non-noble metal catalysts.

PubMed

Yang, Xiaodong; Liu, Yongning; Li, Sai; Wei, Xiaozhu; Wang, Li; Chen, Yuanzhen

2012-01-01

Polymer electrolyte membranes (PEM) and Pt-based catalysts are two crucial components which determine the properties and price of fuel cells. Even though, PEM faces problem of fuel crossover in liquid fuel cells such as direct methanol fuel cell (DMFC) and direct borohydride fuel cell (DBFC), which lowers power output greatly. Here, we report a DBFC in which a polymer fiber membrane (PFM) was used, and metal oxides, such as LaNiO₃ and MnO₂, were used as cathode catalysts, meanwhile CoO was used as anode catalyst. Peak power density of 663 mW·cm⁻² has been achieved at 65°C, which increases by a factor of 1.7-3.7 compared with classic DBFCs. This fuel cell structure can also be extended to other liquid fuel cells, such as DMFC.

Preparation of mesoporous alumina particles by spray pyrolysis and application to double bond migration of 2-butene.

PubMed

Song, Ki Chang; Kim, Joo Hyun; Kim, Jin Han; Jung, Kyeong Youl; Park, Young-Kwon; Jeon, Jong-Ki

2011-07-01

The objective of the present study is to investigate the catalytic performance of mesoporous alumina that were prepared via spray pyrolysis for double bond migration from 2-butene to 1-butene. The mesoporous alumina particles were prepared via spray pyrolysis by changing the types of organic surfactants and Al precursors. The texture and acidic properties of mesoporous alumina were analyzed through N2 adsorption, SEM, ammonia-temperature programmed desorption, and FT-IR of adsorbed pyridine. The morphologies and texture properties of the mesoporous alumina were found to have been strongly influenced by the combination of the Al precursor and the structure-directing agents. The mesoporous alumina samples had two kinds of acidic sites: a Lewis acid site and a H-bonded weak acid site. 1-Butene was produced selectively through double bond migration of 2-butene over all of the mesoporous alumina catalysts. The catalyst prepared by using a chloride compound as an aluminium precursor and CTAC as a structure-directing agent showed the highest activity in the double bond migration of 2-butene, which was attributed to its large surface area and an overall high amount of acid sites.

A H2-evolving photocathode based on direct sensitization of MoS3 with an organic photovoltaic cell

PubMed Central

Bourgeteau, Tiphaine; Tondelier, Denis; Geffroy, Bernard; Brisse, Romain; Laberty-Robert, Christel; Campidelli, Stéphane; de Bettignies, Rémi; Artero, Vincent; Palacin, Serge; Jousselme, Bruno

2013-01-01

An organic solar cell based on a poly-3-hexylthiophene (P3HT): phenyl-C61-butyric acid (PCBM) bulk hetero-junction was directly coupled with molybdenum sulfide resulting in the design of a new type of photocathode for the production of hydrogen. Both the light-harvesting system and the catalyst were deposited by low-cost solution-processed methods, i.e. spin coating and spray coating respectively. Spray-coated MoS3 films are catalytically active in strongly acidic aqueous solutions with the best efficiencies for thicknesses of 40 to 90 nm. The photocathodes display photocurrents higher than reference samples, without catalyst or without coupling with a solar cell. Analysis by gas chromatography confirms the light-induced hydrogen evolution. The addition of titanium dioxide in the MoS3 film enhances electron transport and collection within thick films and therefore the performance of the photocathode. PMID:24404434

Improved aqueous scrubber for collection of soluble atmospheric trace gases

NASA Technical Reports Server (NTRS)

Cofer, W. R., III; Talbot, R. W.; Collins, V. G.

1985-01-01

A new concentration technique for the extraction and enrichment of water-soluble atmospheric trace gases has been developed. The gas scrubbing technique efficiently extracts soluble gases from a large volume flow rate of air sample into a small volume of refluxed trapping solution. The gas scrubber utilizes a small nebulizing nozzle that mixes the incoming air with an aqueous extracting solution to form an air/droplet mist. The mist provides excellent interfacial surface areas for mass transfer. The resulting mist sprays upward through the reaction chamber until it impinges upon a hydrophobic membrane that virtually blocks the passage of droplets but offers little resistance to the existing gas flow. Droplets containing the scrubbed gases coalesce on the membrane and drip back into the reservoir for further refluxing. After a suitable concentration period, the extracting solution containing the analyte can be withdrawn for analysis. The nebulization-reflex concentration technique is more efficient (maximum flow of gas through the minimum volume of extractant) than conventional bubbler/impinger gas extraction techniques and is offered as an alternative method.

Membrane-Filtered Olive Mill Wastewater: Quality Assessment of the Dried Phenolic-Rich Fraction.

PubMed

Sedej, Ivana; Milczarek, Rebecca; Wang, Selina C; Sheng, Runqi; de Jesús Avena-Bustillos, Roberto; Dao, Lan; Takeoka, Gary

2016-04-01

A current trend in olive mill wastewater (OMWW) management is to not only decrease environmental pollution but also to extract and utilize valuable by-products. Therefore, the objectives of this study were to explore different techniques for drying a phenolic-rich membrane filtration fraction of OMWW and compare the techniques in terms of the dried product quality and feasibility of the process. The OMWW from 2 (3-phase and 2-phase) California mills was subjected to a 2-step membrane filtration process using a novel vibratory system. The reverse osmosis retentate (RO-R) is a phenolic-rich coproduct stream, and the reverse osmosis permeate is a near-pure water stream that could be recycled into the milling process. Spray-, freeze-, and infrared-drying were applied to obtain solid material from the RO-R. Drying of the RO-R was made possible only with addition of 10% maltodextrin as a carrier. The total soluble phenolics in dried RO-R were in the range 0.15 to 0.58 mg gallic acid equivalents/g of dry weight for 2-phase RO-R, and 1.38 to 2.17 mg gallic acid equivalents/g of dry weight for the 3-phase RO-R. Spray-dried RO-R from 3-phase OMWW showed remarkable antioxidant activity. Protocatechuic acid, tyrosol, vanillic acid, and p-coumaric acid were quantified in all dried RO-R, whereas 3-hydroxytyrosol was found in 3-phase dried RO-R. This combination of separation and drying technologies helps to add value and shelf-stability to an olive oil by-product and increase environmental sustainability of its production. © 2016 Institute of Food Technologists®

Oxidative coupling of methane using inorganic membrane reactor

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ma, Y.H.; Moser, W.R.; Dixon, A.G.

1995-12-31

The goal of this research is to improve the oxidative coupling of methane in a catalytic inorganic membrane reactor. A specific target is to achieve conversion of methane to C{sub 2} hydrocarbons at very high selectivity and relatively higher yields than in fixed bed reactors by controlling the oxygen supply through the membrane. A membrane reactor has the advantage of precisely controlling the rate of delivery of oxygen to the catalyst. This facility permits balancing the rate of oxidation and reduction of the catalyst. In addition, membrane reactors minimize the concentration of gas phase oxygen thus reducing non selective gasmore » phase reactions, which are believed to be a main route for formation of CO{sub x} products. Such gas phase reactions are a cause for decreased selectivity in oxidative coupling of methane in conventional flow reactors. Membrane reactors could also produce higher product yields by providing better distribution of the reactant gases over the catalyst than the conventional plug flow reactors. Modeling work which aimed at predicting the observed experimental trends in porous membrane reactors was also undertaken in this research program.« less

Recent Advances in Catalyst Accelerated Stress Tests for Polymer Electrolyte Membrane Fuel Cells

DOE PAGES

Stariha, Sarah; Macauley, Natalia; Sneed, Brian T.; ...

2018-03-15

The U.S. Department of Energy (DOE) set the 2020 durability target for polymer electrolyte membrane fuel cell transportation applications at 5000 hours. Since it is impractical to test every fuel cell for this length of time, there is ever increasing interest in developing accelerated stress tests (ASTs) that can accurately simulate the material component degradation in the membrane electrode assembly (MEA) observed under automotive operating conditions, but over a much shorter time frame. In this study, a square-wave catalyst AST was examined that shows a 5X time acceleration factor over the triangle-wave catalyst AST and a 25X time acceleration factormore » over the modified wet drive-cycle catalyst durability protocol, significantly decreasing the testing time. These acceleration factors were correlated to the platinum (Pt) particle size increase and associated decrease in electrochemical surface area (ECSA). This square-wave AST has been adopted by the DOE as a standard protocol to evaluate catalyst durability. We also compare three catalyst-durability protocols using state-of-the-art platinum-cobalt catalysts supported on high surface area carbon (SOA Pt-Co/HSAC) in the cathode catalyst layer. The results for each of the three tests showed both catalyst particle size increase and transition metal leaching. Moreover the acceleration factors for the alloy catalysts were smaller due to Co leaching being the predominant mechanism of voltage decay in ~5 nm PtCo/C catalysts. Finally, an extremely harsh carbon corrosion AST was run using the same SOA Pt-Co/HSAC catalyst. This showed minimal change in particle size and a low percentage Co loss from the cathode catalyst particles, despite a significant loss in catalyst layer thickness and cell performance. The carbon corrosion rates during these various ASTs were directly measured by monitoring the CO 2 emission from the cathode, further confirming the ability of the square-wave AST to evaluate the electro-catalyst independently of the support.« less

Recent Advances in Catalyst Accelerated Stress Tests for Polymer Electrolyte Membrane Fuel Cells

DOE Office of Scientific and Technical Information (OSTI.GOV)

Stariha, Sarah; Macauley, Natalia; Sneed, Brian T.

The U.S. Department of Energy (DOE) set the 2020 durability target for polymer electrolyte membrane fuel cell transportation applications at 5000 hours. Since it is impractical to test every fuel cell for this length of time, there is ever increasing interest in developing accelerated stress tests (ASTs) that can accurately simulate the material component degradation in the membrane electrode assembly (MEA) observed under automotive operating conditions, but over a much shorter time frame. In this study, a square-wave catalyst AST was examined that shows a 5X time acceleration factor over the triangle-wave catalyst AST and a 25X time acceleration factormore » over the modified wet drive-cycle catalyst durability protocol, significantly decreasing the testing time. These acceleration factors were correlated to the platinum (Pt) particle size increase and associated decrease in electrochemical surface area (ECSA). This square-wave AST has been adopted by the DOE as a standard protocol to evaluate catalyst durability. We also compare three catalyst-durability protocols using state-of-the-art platinum-cobalt catalysts supported on high surface area carbon (SOA Pt-Co/HSAC) in the cathode catalyst layer. The results for each of the three tests showed both catalyst particle size increase and transition metal leaching. Moreover the acceleration factors for the alloy catalysts were smaller due to Co leaching being the predominant mechanism of voltage decay in ~5 nm PtCo/C catalysts. Finally, an extremely harsh carbon corrosion AST was run using the same SOA Pt-Co/HSAC catalyst. This showed minimal change in particle size and a low percentage Co loss from the cathode catalyst particles, despite a significant loss in catalyst layer thickness and cell performance. The carbon corrosion rates during these various ASTs were directly measured by monitoring the CO 2 emission from the cathode, further confirming the ability of the square-wave AST to evaluate the electro-catalyst independently of the support.« less

The Development of Novel, High-Flux, Heat Transfer Cells for Thermal Control in Microgravity

NASA Technical Reports Server (NTRS)

Smith, Marc K.; Glezer, Ari

1996-01-01

In order to meet the future needs of thermal management and control in space applications such as the Space Lab, new heat-transfer technology capable of much larger heat fluxes must be developed. To this end, we describe complementary numerical and experimental investigations into the fundamental fluid mechanics and heat-transfer processes involved in a radically new, self contained, heat transfer cell for microgravity applications. In contrast to conventional heat pipes, the heat transfer in this cell is based on a forced droplet evaporation process using a fine spray. The spray is produced by a novel fluidic technology recently developed at Georgia Tech. This technology is based on a vibration induced droplet atomization process. In this technique, a liquid droplet is placed on a flexible membrane and is vibrated normal to itself. When the proper drop size is attained, the droplet resonates with the surface motion of the membrane and almost immediately bursts into a shower of very fine secondary droplets. The small droplets travel to the opposite end of the cell where they impact a heated surface and are evaporated. The vapor returns to the cold end of the cell and condenses to form the large droplets that are fragmented to form the spray. Preliminary estimates show that a heat transfer cell based on this technology would have a heat-flux capacity that is an order of magnitude higher than those of current heat pipes designs used in microgravity applications.

Fabrication of three-dimensional buckypaper catalyst layer with Pt nanoparticles supported on polyelectrolyte functionalized carbon nanotubes for proton exchange membrane fuel cells

NASA Astrophysics Data System (ADS)

Zhu, Shiyao; Zheng, Junsheng; Huang, Jun; Dai, Ningning; Li, Ping; Zheng, Jim P.

2018-07-01

Polyelectrolyte poly(diallyldimethylammonium chloride) (PDDA) functionalized carbon nanotubes (CNTs) supported Pt electrocatalyst was synthesized as a substitute for commonly used Pt/C and Pt/CNTs (modified by harsh acid-oxidation treatment) catalysts. In addition, this catalyst was fabricated as the cathode catalyst layer (CL) with a unique double-layered structure for proton exchange membrane fuel cells (PEMFCs). Thermogravimetric analysis shows an enhanced thermal stability of Pt/PDDA-CNTs. The Pt/PDDA-CNTs catalyst with an average Pt particle size of ∼3.1 nm exhibits the best electrocatalytic activity and a significantly enhanced electrochemical stability. Scanning electron microscope, energy dispersive spectrometer and mercury intrusion porosimetry results demonstrate the gradient distribution of Pt content and pore size along the thickness of buckypaper catalyst layer (BPCL). The accelerated degradation test results of BPCLs indicate that this gradient structure can ensure a high Pt utilization in the BPCLs (up to 90%) and further improve the catalyst durability. In addition, the membrane electrode assembly (MEA) fabricated with cathode BPCL-PDDA shows the best single cell performance and long-term stability, and a reduction of Pt loading can be achieved. The feasibility of BPCL for improving the Pt utilization is also demonstrated by the cathode cyclic voltammetry in MEA.

A fluorescent imaging technique for quantifying spray deposits on plant leaves

USDA-ARS?s Scientific Manuscript database

Because of the unique characteristics of electrostatically-charged sprays, use of traditional methods to quantify deposition from these sprays has been challenging. A new fluorescent imaging technique was developed to quantify spray deposits from electrostatically-charged sprays on natural plant lea...

Analyzing the influence of high electrode potentials on intrinsic properties of catalyst coated membranes using impedance spectroscopy

NASA Astrophysics Data System (ADS)

Alink, Robert; Schüßler, Martina; Pospischil, Maximilian; Erath, Denis; Gerteisen, Dietmar

2016-09-01

Catalyst layers (CLs) with varying ionomer contents are produced using a stencil coating and screen printing technique. The optimum ionomer content of 31-34 wt% confirms the findings of other groups and performance is found to be independent of production technique. A new CL impedance transition line model is developed and fitted to in-situ data. The results indicate that the protonic contact resistance between CL and membrane is an important factor for the used transfer-decal process, especially for CLs with low ionomer loading. When subjected to potentials higher than 1.2 V, an increased performance is observed for low ionomer loading CLs. It is found that by applying the high potential to the electrode a significantly increased proton conductivity is counteracting and superimposing the loss of electrochemical surface area (ECSA) due to carbon corrosion. After aging, the performance of the 15 wt% CL is at the same level as the 31-34 wt% ionomer content CLs at the beginning of life, even though the ECSA is reduced due to carbon corrosion or platinum dissolution. The findings indicate that for the optimization of the ionomer loading, either the changing wetting properties or the redistribution of ionomer during lifetime have to be taken into account.

Synthesis of Copper-Based Nanostructured Catalysts on SiO2-Al2O3, SiO2-TiO2, and SiO2-ZrO2 Supports for NO Reduction.

PubMed

Namkhang, Pornpan; Kongkachuichay, Paisan

2015-07-01

The selective catalytic reduction of NO over a series of Cu-based catalysts supported on modified silica including SiO2-Al2O3, SiO2-TiO2, and SiO2-ZrO2 prepared via a sol-gel process and a flame spray pyrolysis (FSP) was studied. The prepared catalysts were characterized by means of TEM, XRD, XRF, TPR, and nitrogen physisorption measurement techniques, to determine particle diameter, morphology, crystallinity, phase composition, copper reducibility, surface area, and pore size of catalysts. The particles obtained from sol-gel method were almost spherical while the particles obtained from the FSP were clearly spherical and non-porous nanosized particles. The effects of Si:Al, Si:Ti, and Si:Zr molar ratio of precursor were identified as the domain for different crystalline phase of materials. It was clearly seen that a high SiO2 content inhibited the crystallization of materials. The BET surface area of catalysts obtained from sol-gel method was higher than that from the FSP and it shows that surface area increased with increasing SiO2 molar ratio due to high surface area from SiO2. The catalyst performances were tested for the selective catalytic reduction of NO with H2. It was found that the catalyst prepared over 7 wt% Cu on Si02-Al2O3 support was the most active compared with the others which converted NO as more than 70%. Moreover, the excess copper decreased the performance of NO reduction, due to the formation of CuO agglomeration covered on the porous silica as well as the alumina surface, preventing the direct contact of CO2 and AL2O3.

A direct borohydride fuel cell with a polymer fiber membrane and non-noble metal catalysts

PubMed Central

Yang, Xiaodong; Liu, Yongning; Li, Sai; Wei, Xiaozhu; Wang, Li; Chen, Yuanzhen

2012-01-01

Polymer electrolyte membranes (PEM) and Pt-based catalysts are two crucial components which determine the properties and price of fuel cells. Even though, PEM faces problem of fuel crossover in liquid fuel cells such as direct methanol fuel cell (DMFC) and direct borohydride fuel cell (DBFC), which lowers power output greatly. Here, we report a DBFC in which a polymer fiber membrane (PFM) was used, and metal oxides, such as LaNiO3 and MnO2, were used as cathode catalysts, meanwhile CoO was used as anode catalyst. Peak power density of 663 mW·cm−2 has been achieved at 65°C, which increases by a factor of 1.7–3.7 compared with classic DBFCs. This fuel cell structure can also be extended to other liquid fuel cells, such as DMFC. PMID:22880160

ATTRITION RESISTANT IRON-BASED FISCHER-TROPSCH CATALYSTS

DOE Office of Scientific and Technical Information (OSTI.GOV)

JAMES G. GOODWIN, JR.; JAMES J. SPIVEY; K. JOTHIMURUGESAN

1998-09-17

The Fischer-Tropsch (F-T) reaction provides a way of converting coal-derived synthesis gas (CO+H{sub 2}) to liquid fuels. Since the reaction is highly exothermic, one of the major problems in control of the reaction is heat removal. Recent work has shown that the use of slurry bubble column reactors (SBCRs) can largely solve this problem. Iron-based (Fe) catalysts are preferred catalysts for F-T when using low CO/H{sub 2} ratio synthesis gases derived from modern coal gasifiers. This is because in addition to reasonable F-T activity, the F-T catalysts also possess high water gas shift (WGS) activity. However, a serious problem withmore » the use of Fe catalysts in a SBCR is their tendency to undergo attrition. This can cause fouling/plugging of downstream filters and equipment, making the separation of catalyst from the oil/wax product very difficult if not impossible, and results in a steady loss of catalyst from the reactor. The objectives of this research are to develop a better understanding of the parameters affecting attrition resistance of Fe F-T catalysts suitable for use in SBCRs and to incorporate this understanding into the design of novel Fe catalysts having superior attrition resistance. Catalyst preparations will be based on the use of spray drying and will be scalable using commercially available equipment. The research will employ among other measurements, attrition testing and F-T synthesis, including long duration slurry reactor runs in order to ascertain the degree of success of the various preparations. The goal is to develop an Fe catalyst which can be used in a SBCR having only an internal filter for separation of the catalyst from the liquid product, without sacrificing F-T activity and selectivity. The effect of silica addition via coprecipitation and as a binder to a doubly promoted Fischer-Tropsch synthesis iron catalyst (100 Fe/5 Cu/4.2 K) was studied. The catalysts were prepared by coprecipitation, followed by binder addition and drying in a 1 m diameter, 2 m tall spray dryer. The binder silica content was varied from 0 to 20 wt %. A catalyst with 12 wt % binder silica was found to have the highest attrition resistance. F-T reaction studies over 100 hours in a fixed-bed reactor showed that this catalyst maintained around 95 % CO conversion with a methane selectivity of less than 7 wt % and a C{sub 5}{sup +} selectivity of greater than 73 wt %. The effect of adding precipitated silica from 0 to 20 parts by weight to this catalyst (containing 12 wt % binder silica) was also studied. Addition of precipitated silica was found to be detrimental to attrition resistance and resulted in increased methane and reduced wax formation.« less

Electrospun Nb-doped TiO2 nanofiber support for Pt nanoparticles with high electrocatalytic activity and durability

NASA Astrophysics Data System (ADS)

Kim, Minjoong; Kwon, Chorong; Eom, Kwangsup; Kim, Jihyun; Cho, Eunae

2017-03-01

This study explores a facile method to prepare an efficient and durable support for Pt catalyst of polymer electrolyte membrane fuel cell (PEMFC). As a candidate, Nb-doped TiO2 (Nb-TiO2) nanofibers are simply fabricated using an electrospinning technique, followed by a heat treatment. Doping Nb into the TiO2 nanofibers leads to a drastic increase in electrical conductivity with doping level of up to 25 at. % (Nb0.25Ti0.75O2). Pt nanoparticles are synthesized on the prepared 25 at. % Nb-doped TiO2-nanofibers (Pt/Nb-TiO2) as well as on a commercial powdered carbon black (Pt/C). The Pt/Nb-TiO2 nanofiber catalyst exhibits similar oxygen reaction reduction (ORR) activity to that of the Pt/C catalyst. However, during an accelerated stress test (AST), the Pt/Nb-TiO2 nanofiber catalyst retained more than 60% of the initial ORR activity while the Pt/C catalyst lost 65% of the initial activity. The excellent durability of the Pt/Nb-TiO2 nanofiber catalyst can be attributed to high corrosion resistance of TiO2 and strong interaction between Pt and TiO2.

Electrospun Nb-doped TiO2 nanofiber support for Pt nanoparticles with high electrocatalytic activity and durability.

PubMed

Kim, MinJoong; Kwon, ChoRong; Eom, KwangSup; Kim, JiHyun; Cho, EunAe

2017-03-14

This study explores a facile method to prepare an efficient and durable support for Pt catalyst of polymer electrolyte membrane fuel cell (PEMFC). As a candidate, Nb-doped TiO 2 (Nb-TiO 2 ) nanofibers are simply fabricated using an electrospinning technique, followed by a heat treatment. Doping Nb into the TiO 2 nanofibers leads to a drastic increase in electrical conductivity with doping level of up to 25 at. % (Nb 0.25 Ti 0.75 O 2 ). Pt nanoparticles are synthesized on the prepared 25 at. % Nb-doped TiO 2 -nanofibers (Pt/Nb-TiO 2 ) as well as on a commercial powdered carbon black (Pt/C). The Pt/Nb-TiO 2 nanofiber catalyst exhibits similar oxygen reaction reduction (ORR) activity to that of the Pt/C catalyst. However, during an accelerated stress test (AST), the Pt/Nb-TiO 2 nanofiber catalyst retained more than 60% of the initial ORR activity while the Pt/C catalyst lost 65% of the initial activity. The excellent durability of the Pt/Nb-TiO 2 nanofiber catalyst can be attributed to high corrosion resistance of TiO 2 and strong interaction between Pt and TiO 2 .

Electrospun Nb-doped TiO2 nanofiber support for Pt nanoparticles with high electrocatalytic activity and durability

PubMed Central

Kim, MinJoong; Kwon, ChoRong; Eom, KwangSup; Kim, JiHyun; Cho, EunAe

2017-01-01

This study explores a facile method to prepare an efficient and durable support for Pt catalyst of polymer electrolyte membrane fuel cell (PEMFC). As a candidate, Nb-doped TiO2 (Nb-TiO2) nanofibers are simply fabricated using an electrospinning technique, followed by a heat treatment. Doping Nb into the TiO2 nanofibers leads to a drastic increase in electrical conductivity with doping level of up to 25 at. % (Nb0.25Ti0.75O2). Pt nanoparticles are synthesized on the prepared 25 at. % Nb-doped TiO2-nanofibers (Pt/Nb-TiO2) as well as on a commercial powdered carbon black (Pt/C). The Pt/Nb-TiO2 nanofiber catalyst exhibits similar oxygen reaction reduction (ORR) activity to that of the Pt/C catalyst. However, during an accelerated stress test (AST), the Pt/Nb-TiO2 nanofiber catalyst retained more than 60% of the initial ORR activity while the Pt/C catalyst lost 65% of the initial activity. The excellent durability of the Pt/Nb-TiO2 nanofiber catalyst can be attributed to high corrosion resistance of TiO2 and strong interaction between Pt and TiO2. PMID:28290503

Graphene-Supported Platinum Catalyst-Based Membrane Electrode Assembly for PEM Fuel Cell

NASA Astrophysics Data System (ADS)

Devrim, Yilser; Albostan, Ayhan

2016-08-01

The aim of this study is the preparation and characterization of a graphene-supported platinum (Pt) catalyst for proton exchange membrane fuel cell (PEMFC) applications. The graphene-supported Pt catalysts were prepared by chemical reduction of graphene and chloroplatinic acid (H2PtCl6) in ethylene glycol. X-ray powder diffraction, thermogravimetric analysis (TGA) and scanning electron microscopy have been used to analyze structure and surface morphology of the graphene-supported catalyst. The TGA results showed that the Pt loading of the graphene-supported catalyst was 31%. The proof of the Pt particles on the support surfaces was also verified by energy-dispersive x-ray spectroscopy analysis. The commercial carbon-supported catalyst and prepared Pt/graphene catalysts were used as both anode and cathode electrodes for PEMFC at ambient pressure and 70°C. The maximum power density was obtained for the Pt/graphene-based membrane electrode assembly (MEA) with H2/O2 reactant gases as 0.925 W cm2. The maximum current density of the Pt/graphene-based MEA can reach 1.267 and 0.43 A/cm2 at 0.6 V with H2/O2 and H2/air, respectively. The MEA prepared by the Pt/graphene catalyst shows good stability in long-term PEMFC durability tests. The PEMFC cell voltage was maintained at 0.6 V without apparent voltage drop when operated at 0.43 A/cm2 constant current density and 70°C for 400 h. As a result, PEMFC performance was found to be superlative for the graphene-supported Pt catalyst compared with the Pt/C commercial catalyst. The results indicate the graphene-supported Pt catalyst could be utilized as the electrocatalyst for PEMFC applications.

Catalytic Partial Oxidation Reforming of JP8 AND S8

DTIC Science & Technology

2007-06-01

separated from the gas mixtures. The membrane used is normally palladium . This membrane allows the hydrogen created to be used as fuel in the fuel cell...for a hydrocarbon such as propane, a catalyst with rhodium (Rh) supported on alumina has shown promising results. Pt and Ni catalysts have been

Recovery of homogeneous polyoxometallate catalysts from aqueous and organic media by a mesoporous ceramic membrane without loss of catalytic activity.

PubMed

Roy Chowdhury, Sankhanilay; Witte, Peter T; Blank, Dave H A; Alsters, Paul L; Ten Elshof, Johan E

2006-04-03

The recovery of homogeneous polyoxometallate (POM) oxidation catalysts from aqueous and non-aqueous media by a nanofiltration process using mesoporous gamma-alumina membranes is reported. The recovery of Q(12)[WZn(3)(ZnW(9)O(34))(2)] (Q=[MeN(n-C(8)H(17))(3)](+)) from toluene-based media was quantitative within experimental error, while up to 97 % of Na(12)[WZn(3)(ZnW(9)O(34))(2)] could be recovered from water. The toluene-soluble POM catalyst was used repeatedly in the conversion of cyclooctene to cyclooctene oxide and separated from the product mixture after each reaction. The catalytic activity increased steadily with the number of times that the catalyst had been recycled, which was attributed to partial removal of the excess QCl that is known to have a negative influence on the catalytic activity. Differences in the permeability of the membrane for different liquid media can be attributed to viscosity differences and/or capillary condensation effects. The influence of membrane pore radius on permeability and recovery is discussed.

Use of Iba Techniques to Characterize High Velocity Thermal Spray Coatings

NASA Astrophysics Data System (ADS)

Trompetter, W.; Markwitz, A.; Hyland, M.

Spray coatings are being used in an increasingly wide range of industries to improve the abrasive, erosive and sliding wear of machine components. Over the past decade industries have moved to the application of supersonic high velocity thermal spray techniques. These coating techniques produce superior coating quality in comparison to other traditional techniques such as plasma spraying. To date the knowledge of the bonding processes and the structure of the particles within thermal spray coatings is very subjective. The aim of this research is to improve our understanding of these materials through the use of IBA techniques in conjunction with other materials analysis techniques. Samples were prepared by spraying a widely used commercial NiCr powder onto substrates using a HVAF (high velocity air fuel) thermal spraying technique. Detailed analysis of the composition and structure of the power particles revealed two distinct types of particles. The majority was NiCr particles with a significant minority of particles composing of SiO2/CrO3. When the particles were investigated both as raw powder and in the sprayed coating, it was surprising to find that the composition of the coating meterial remained unchanged during the coating process despite the high velocity application.

Supported inorganic membranes

DOEpatents

Sehgal, Rakesh; Brinker, Charles Jeffrey

1998-01-01

Supported inorganic membranes capable of molecular sieving, and methods for their production, are provided. The subject membranes exhibit high flux and high selectivity. The subject membranes are substantially defect free and less than about 100 nm thick. The pores of the subject membranes have an average critical pore radius of less than about 5 .ANG., and have a narrow pore size distribution. The subject membranes are prepared by coating a porous substrate with a polymeric sol, preferably under conditions of low relative pressure of the liquid constituents of the sol. The coated substrate is dried and calcined to produce the subject supported membrane. Also provided are methods of derivatizing the surface of supported inorganic membranes with metal alkoxides. The subject membranes find use in a variety of applications, such as the separation of constituents of gaseous streams, as catalysts and catalyst supports, and the like.

Membrane-electrode structures for molecular catalysts for use in fuel cells and other electrochemical devices

DOEpatents

Kerr, John B.; Zhu, Xiaobing; Hwang, Gi Suk; Martin, Zulima; He, Qinggang; Driscoll, Peter; Weber, Adam; Clark, Kyle

2016-09-27

Water soluble catalysts, (M)meso-tetra(N-Methyl-4-Pyridyl)Porphinepentachloride (M=Fe, Co, Mn & Cu), have been incorporated into the polymer binder of oxygen reduction cathodes in membrane electrode assemblies used in PEM fuel cells and found to support encouragingly high current densities. The voltages achieved are low compared to commercial platinum catalysts but entirely consistent with the behavior observed in electroanalytical measurements of the homogeneous catalysts. A model of the dynamics of the electrode action has been developed and validated and this allows the MEA electrodes to be optimized for any chemistry that has been demonstrated in solution. It has been shown that improvements to the performance will come from modifications to the structure of the catalyst combined with optimization of the electrode structure and a well-founded pathway to practical non-platinum group metal catalysts exists.

Electrochemical device for converting carbon dioxide to a reaction product

DOE Office of Scientific and Technical Information (OSTI.GOV)

Masel, Richard I.; Chen, Qingmei; Liu, Zengcai

An electrochemical device converts carbon dioxide to a reaction product. The device includes an anode and a cathode, each comprising a quantity of catalyst. The anode and cathode each has reactant introduced thereto. A polymer electrolyte membrane is interposed between the anode and the cathode. At least a portion of the cathode catalyst is directly exposed to gaseous carbon dioxide during electrolysis. The average current density at the membrane is at least 20 mA/cm.sup.2, measured as the area of the cathode gas diffusion layer that is covered by catalyst, and CO selectivity is at least 50% at a cell potentialmore » of 3.0 V. In some embodiments, the polymer electrolyte membrane comprises a polymer in which a constituent monomer is (p-vinylbenzyl)-R, where R is selected from the group consisting of imidazoliums, pyridiniums and phosphoniums. In some embodiments, the polymer electrolyte membrane is a Helper Membrane comprising a polymer containing an imidazolium ligand, a pyridinium ligand, or a phosphonium ligand.« less

Amorphous nickel boride membrane on a platinum-nickel alloy surface for enhanced oxygen reduction reaction.

PubMed

He, Daping; Zhang, Libo; He, Dongsheng; Zhou, Gang; Lin, Yue; Deng, Zhaoxiang; Hong, Xun; Wu, Yuen; Chen, Chen; Li, Yadong

2016-08-09

The low activity of the oxygen reduction reaction in polymer electrolyte membrane fuel cells is a major barrier for electrocatalysis, and hence needs to be optimized. Tuning the surface electronic structure of platinum-based bimetallic alloys, a promising oxygen reduction reaction catalyst, plays a key role in controlling its interaction with reactants, and thus affects the efficiency. Here we report that a dealloying process can be utilized to experimentally fabricate the interface between dealloyed platinum-nickel alloy and amorphous nickel boride membrane. The coating membrane works as an electron acceptor to tune the surface electronic structure of the platinum-nickel catalyst, and this composite catalyst composed of crystalline platinum-nickel covered by amorphous nickel boride achieves a 27-times enhancement in mass activity relative to commercial platinum/carbon at 0.9 V for the oxygen reduction reaction performance. Moreover, this interactional effect between a crystalline surface and amorphous membrane can be readily generalized to facilitate the 3-times higher catalytic activity of commercial platinum/carbon.

Mordenite/Nafion and analcime/Nafion composite membranes prepared by spray method for improved direct methanol fuel cell performance

NASA Astrophysics Data System (ADS)

Prapainainar, Paweena; Du, Zehui; Kongkachuichay, Paisan; Holmes, Stuart M.; Prapainainar, Chaiwat

2017-11-01

The aim of this work was to improve proton exchange membranes (PEMs) used in direct methanol fuel cells (DMFCs). A membrane with a high proton conductivity and low methanol permeability was required. Zeolite filler in Nafion (NF matrix) composite membranes were prepared using two types of zeolite, mordenite (MOR) and analcime (ANA). Spray method was used to prepare the composite membranes, and properties of the membranes were investigated: mechanical properties, solubility, water and methanol uptake, ion-exchange capacity (IEC), proton conductivity, methanol permeability, and DMFC performance. It was found that MOR filler showed higher performance than ANA. The MOR/Nafion composite membrane gave better properties than ANA/Nafion composite membrane, including a higher proton conductivity and a methanol permeability that was 2-3 times lower. The highest DMFC performance (10.75 mW cm-2) was obtained at 70 °C and with 2 M methanol, with a value 1.5 times higher than that of ANA/Nafion composite membrane and two times higher than that of commercial Nafion 117 (NF 117).

Critical advancements in achieving high power and stable nonprecious metal catalyst–based MEAs for real-world proton exchange membrane fuel cell applications

PubMed Central

Zhou, Yingjie; Bai, Kyoung

2018-01-01

Despite great progress in the development of nonprecious metal catalysts (NPMCs) over the past several decades, the performance and stability of these promising catalysts have not yet achieved commercial readiness for proton exchange membrane fuel cells (PEMFCs). Through rational design of the cathode catalyst layer (CCL), we demonstrate the highest reported performance for an NPMC-based membrane electrode assembly (MEA), achieving a peak power of 570 mW/cm2 under air. This record performance is achieved using a precommercial catalyst for which nearly all pores are <3 nm in diameter, challenging previous beliefs regarding the need for larger catalyst pores to achieve high current densities. This advance is achieved at industrially relevant scales (50 cm2 MEA) using a precommercial NPMC. In situ electrochemical analysis of the CCLs is also used to help gain insight into the degradation mechanism observed during galvanostatic testing. Overall, the performance of this NPMC-based MEA has achieved commercial readiness and will be introduced into an NPMC-based product for portable power applications. PMID:29582018

Space and Industrial Brine Drying Technologies

NASA Technical Reports Server (NTRS)

Jones, Harry W.; Wisniewski, Richard S.; Flynn, Michael; Shaw, Hali

2014-01-01

This survey describes brine drying technologies that have been developed for use in space and industry. NASA has long considered developing a brine drying system for the International Space Station (ISS). Possible processes include conduction drying in many forms, spray drying, distillation, freezing and freeze drying, membrane filtration, and electrical processes. Commercial processes use similar technologies. Some proposed space systems combine several approaches. The current most promising candidates for use on the ISS use either conduction drying with membrane filtration or spray drying.

Electrochemical performance and durability of carbon supported Pt catalyst in contact with aqueous and polymeric proton conductors.

PubMed

Andersen, Shuang Ma; Skou, Eivind

2014-10-08

Significant differences in catalyst performance and durability are often observed between the use of a liquid electrolyte (e.g., sulfuric acid), and a solid polymer electrolyte (e.g., Nafion). To understand this phenomenon, we studied the electrochemical behavior of a commercially available carbon supported platinum catalyst in four different electrode structures: catalyst powder (CP), catalyst ionomer electrode (CIE), half membrane electrode assembly (HMEA), and full membrane electrode assembly (FMEA) in both ex situ and in situ experiments under a simulated start/stop cycle. We found that the catalyst performance and stability are very much influenced by the presence of the Nafion ionomers. The proton conducting phase provided by the ionomer and the self-assembled electrode structure render the catalysts a higher utilization and better stability. This is probably due to an enhanced dispersion, an improved proton-catalyst interface, the restriction of catalyst particle aggregation, and the improved stability of the ionomer phase especially after the lamination. Therefore, an innovative electrode HMEA design for ex-situ catalyst characterization is proposed. The electrode structure is identical to the one used in a real fuel cell, where the protons transport takes place solely through solid state proton conducting phase.

New materials for polymer electrolyte membrane fuel cell current collectors

NASA Astrophysics Data System (ADS)

Hentall, Philip L.; Lakeman, J. Barry; Mepsted, Gary O.; Adcock, Paul L.; Moore, Jon M.

Polymer Electrolyte Membrane Fuel cells for automotive applications need to have high power density, and be inexpensive and robust to compete effectively with the internal combustion engine. Development of membranes and new electrodes and catalysts have increased power significantly, but further improvements may be achieved by the use of new materials and construction techniques in the manufacture of the bipolar plates. To show this, a variety of materials have been fabricated into flow field plates, both metallic and graphitic, and single fuel cell tests were conducted to determine the performance of each material. Maximum power was obtained with materials which had lowest contact resistance and good electrical conductivity. The performance of the best material was characterised as a function of cell compression and flow field geometry.

Fabrication and Wettability Study of WO3 Coated Photocatalytic Membrane for Oil-Water Separation: A Comparative Study with ZnO Coated Membrane.

PubMed

Gondal, Mohammed A; Sadullah, Muhammad S; Qahtan, Talal F; Dastageer, Mohamed A; Baig, Umair; McKinley, Gareth H

2017-05-10

Superhydrophilic and underwater superoleophobic surfaces were fabricated by facile spray coating of nanostructured WO 3 on stainless steel meshes and compared its performance in oil-water separation with ZnO coated meshes. The gravity driven oil-water separation system was designed using these surfaces as the separation media and it was noticed that WO 3 coated stainless steel mesh showed high separation efficiency (99%), with pore size as high as 150 µm, whereas ZnO coated surfaces failed in the process of oil-water separation when the pore exceeded 50 µm size. Since, nanostructured WO 3 is a well known catalyst, the simultaneous photocatalytic degradation of organic pollutants present in the separated water from the oil water separation process were tested using WO 3 coated surfaces under UV radiation and the efficiency of this degradation was found to be quite significant. These results assure that with little improvisation on the oil water separation system, these surfaces can be made multifunctional to work simultaneously for oil-water separation and demineralization of organic pollutants from the separated water. Fabrication of the separating surface, their morphological characteristics, wettability, oil water separation efficiency and photo-catalytic degradation efficiency are enunciated.

Pt-Pd bimetallic nanoparticles on MWCNTs: catalyst for hydrogen peroxide electrosynthesis

NASA Astrophysics Data System (ADS)

Félix-Navarro, R. M.; Beltrán-Gastélum, M.; Salazar-Gastélum, M. I.; Silva-Carrillo, C.; Reynoso-Soto, E. A.; Pérez-Sicairos, S.; Lin, S. W.; Paraguay-Delgado, F.; Alonso-Núñez, G.

2013-08-01

Bimetallic nanoparticles of Pt-Pd were deposited by the microemulsion method on a multiwall carbon nanotube (MWCNTs) to obtain a Pt-Pd/MWCNTs for electrocatalytic reduction of O2 to H2O2. The activity and selectivity of the catalyst was determined qualitatively by the rotating disk electrode method in acidic medium. The catalyst was spray-coated onto a reticulated vitreous carbon substrate and quantitatively was tested in bulk electrolysis for 20 min under potentiostatic conditions (0.5 V vs Ag/AgCl) in a 0.5 M H2SO4 electrolyte using dissolved O2. The bulk electrolysis experiments show that the Pt-Pd/MWCNTs catalyst is more efficient for H2O2 electrogeneration than a MWCNTs catalyst. Nitrobenzene degradation by electrogenerated H2O2 alone and Electro-Fenton process were also tested. Our results show that both processes decompose nitrobenzene, but the Electro-Fenton process does it more efficiently. The prepared nanoparticulated catalyst shows a great potential in environmental applications.

High Performance Fe- and N- Doped Carbon Catalyst with Graphene Structure for Oxygen Reduction

NASA Astrophysics Data System (ADS)

Peng, Hongliang; Mo, Zaiyong; Liao, Shijun; Liang, Huagen; Yang, Lijun; Luo, Fan; Song, Huiyu; Zhong, Yiliang; Zhang, Bingqing

2013-05-01

Proton exchange membrane fuel cells are promising candidates for a clean and efficient energy conversion in the future, the development of carbon based inexpensive non-precious metal ORR catalyst has becoming one of the most attractive topics in fuel cell field. Herein we report a Fe- and N- doped carbon catalyst Fe-PANI/C-Mela with graphene structure and the surface area up to 702 m2 g-1. In 0.1 M HClO4 electrolyte, the ORR onset potential for the catalyst is high up to 0.98 V, and the half-wave potential is only 60 mV less than that of the Pt/C catalyst (Loadings: 51 μg Pt cm-2). The catalyst shows high stability after 10,000 cyclic voltammetry cycles. A membrane electrode assembly made with the catalyst as a cathode is tested in a H2-air single cell, the maximum power density reached ~0.33 W cm2 at 0.47 V.

High Performance Platinum Group Metal Free Membrane Electrode Assemblies through Control of Interfacial Processes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ayers, Katherine; Capuano, Christopher; Atanassov, Plamen

The quantitative goal of this project was to produce a high-performance anion exchange membrane water electrolyzer (AEM-WE) completely free of platinum group metals (PGMs), which could operate for at least 500 hours with less than 50 microV/hour degradation, at 500 mA/cm 2. To achieve this goal, work focused on the optimization of electrocatalyst conductivity, with dispersion and utilization in the membrane electrode assembly (MEA) improved through refinement of deposition techniques. Critical factors were also explored with significant work undertaken by Northeastern University to further understand catalyst-membrane-ionomer interfaces and how they differ from liquid electrolyte. Water management and optimal cell operationalmore » parameters were established through the design, fabrication, and test of a new test station at Proton specific for AEM evaluation. Additionally, AEM material stability and robustness at high potentials and gas evolution conditions were advanced at Penn State.« less

Breakthrough and future: nanoscale controls of compositions, morphologies, and mesochannel orientations toward advanced mesoporous materials.

PubMed

Yamauchi, Yusuke; Suzuki, Norihiro; Radhakrishnan, Logudurai; Wang, Liang

2009-01-01

Currently, ordered mesoporous materials prepared through the self-assembly of surfactants have attracted growing interests owing to their special properties, including uniform mesopores and a high specific surface area. Here we focus on fine controls of compositions, morphologies, mesochannel orientations which are important factors for design of mesoporous materials with new functionalities. This Review describes our recent progress toward advanced mesoporous materials. Mesoporous materials now include a variety of inorganic-based materials, for example, transition-metal oxides, carbons, inorganic-organic hybrid materials, polymers, and even metals. Mesoporous metals with metallic frameworks can be produced by using surfactant-based synthesis with electrochemical methods. Owing to their metallic frameworks, mesoporous metals with high electroconductivity and high surface areas hold promise for a wide range of potential applications, such as electronic devices, magnetic recording media, and metal catalysts. Fabrication of mesoporous materials with controllable morphologies is also one of the main subjects in this rapidly developing research field. Mesoporous materials in the form of films, spheres, fibers, and tubes have been obtained by various synthetic processes such as evaporation-mediated direct templating (EDIT), spray-dried techniques, and collaboration with hard-templates such as porous anodic alumina and polymer membranes. Furthermore, we have developed several approaches for orientation controls of 1D mesochannels. The macroscopic-scale controls of mesochannels are important for innovative applications such as molecular-scale devices and electrodes with enhanced diffusions of guest species. Copyright 2009 The Japan Chemical Journal Forum and Wiley Periodicals, Inc.

Recycling of used perfluorosulfonic acid membranes

DOEpatents

Grot, Stephen [Middletown, DE; Grot, Walther [Chadds Ford, PA

2007-08-14

A method for recovering and recycling catalyst coated fuel cell membranes includes dissolving the used membranes in water and solvent, heating the dissolved membranes under pressure and separating the components. Active membranes are produced from the recycled materials.

Heterodoped nanotubes: theory, synthesis, and characterization of phosphorus-nitrogen doped multiwalled carbon nanotubes.

PubMed

Cruz-Silva, Eduardo; Cullen, David A; Gu, Lin; Romo-Herrera, Jose Manuel; Muñoz-Sandoval, Emilio; López-Urías, Florentino; Sumpter, Bobby G; Meunier, Vincent; Charlier, Jean-Christophe; Smith, David J; Terrones, Humberto; Terrones, Mauricio

2008-03-01

Arrays of multiwalled carbon nanotubes doped with phosphorus (P) and nitrogen (N) are synthesized using a solution of ferrocene, triphenyl-phosphine, and benzylamine in conjunction with spray pyrolysis. We demonstrate that iron phosphide (Fe(3)P) nanoparticles act as catalysts during nanotube growth, leading to the formation of novel PN-doped multiwalled carbon nanotubes. The samples were examined by high resolution electron microscopy and microanalysis techniques, and their chemical stability was explored by means of thermogravimetric analysis in the presence of oxygen. The PN-doped structures reveal important morphology and chemical changes when compared to N-doped nanotubes. These types of heterodoped nanotubes are predicted to offer many new opportunities in the fabrication of fast-response chemical sensors.

Electrocatalysts by atomic layer deposition for fuel cell applications

DOE PAGES

Cheng, Niancai; Shao, Yuyan; Liu, Jun; ...

2016-01-22

Here, fuel cells are a promising technology solution for reliable and clean energy because they offer high energy conversion efficiency and low emission of pollutants. However, high cost and insufficient durability are considerable challenges for widespread adoption of polymer electrolyte membrane fuel cells (PEMFCs) in practical applications. Current PEMFCs catalysts have been identified as major contributors to both the high cost and limited durability. Atomic layer deposition (ALD) is emerging as a powerful technique for solving these problems due to its exclusive advantages over other methods. In this review, we summarize recent developments of ALD in PEMFCs with a focusmore » on design of materials for improved catalyst activity and durability. New research directions and future trends have also been discussed.« less

Novel thin/tunable gas diffusion electrodes with ultra-low catalyst loading for hydrogen evolution reactions in proton exchange membrane electrolyzer cells

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kang, Zhenye; Yang, Gaoqiang; Mo, Jingke

2018-05-01

Proton exchange membrane electrolyzer cells (PEMECs) have received great attention for hydrogen/oxygen production due to their high efficiencies even at low-temperature operation. Because of the high cost of noble platinum-group metal (PGM) catalysts (Ir, Ru, Pt, etc.) that are widely used in water splitting, a PEMEC with low catalyst loadings and high catalyst utilizations is strongly desired for its wide commercialization. In this study, the ultrafast and multiscale hydrogen evolution reaction (HER) phenomena in an operating PEMEC is in-situ observed for the first time. The visualization results reveal that the HER and hydrogen bubble nucleation mainly occur on catalyst layersmore » at the rim of the pores of the thin/tunable liquid/gas diffusion layers (TT-LGDLs). This indicates that the catalyst material of the conventional catalyst-coated membrane (CCM) that is located in the middle area of the LGDL pore is underutilized/inactive. Based on this discovery, a novel thin and tunable gas diffusion electrode (GDE) with a Pt catalyst thickness of 15 nm and a total thickness of about 25 um has been proposed and developed by taking advantage of advanced micro/nano manufacturing. The novel thin GDEs are comprehensively characterized both ex-situ and in-situ, and exhibit excellent PEMEC performance. More importantly, they achieve catalyst mass activity of up to 58 times higher than conventional CCM at 1.6 V under the operating conditions of 80 degrees C and 1 atm. This study demonstrates a promising concept for PEMEC electrode development, and provides a direction of future catalyst designs and fabrications for electrochemical devices.« less

Highly Durable Supportless Pt Hollow Spheres Designed for Enhanced Oxygen Transport in Cathode Catalyst Layers of Proton Exchange Membrane Fuel Cells.

PubMed

Dogan, Didem C; Cho, Seonghun; Hwang, Sun-Mi; Kim, Young-Min; Guim, Hwanuk; Yang, Tae-Hyun; Park, Seok-Hee; Park, Gu-Gon; Yim, Sung-Dae

2016-10-10

Supportless Pt catalysts have several advantages over conventional carbon-supported Pt catalysts in that they are not susceptible to carbon corrosion. However, the need for high Pt loadings in membrane electrode assemblies (MEAs) to achieve state-of-the-art fuel cell performance has limited their application in proton exchange membrane fuel cells. Herein, we report a new approach to the design of a supportless Pt catalyst in terms of catalyst layer architecture, which is crucial for fuel cell performance as it affects water management and oxygen transport in the catalyst layers. Large Pt hollow spheres (PtHSs) 100 nm in size were designed and prepared using a carbon template method. Despite their large size, the unique structure of the PtHSs, which are composed of a thin-layered shell of Pt nanoparticles (ca. 7 nm thick), exhibited a high surface area comparable to that of commercial Pt black (PtB). The PtHS structure also exhibited twice the durability of PtB after 2000 potential cycles (0-1.3 V, 50 mV/s). A MEA fabricated with PtHSs showed significant improvement in fuel cell performance compared to PtB-based MEAs at high current densities (>800 mA/cm 2 ). This was mainly due to the 2.7 times lower mass transport resistance in the PtHS-based catalyst layers compared to that in PtB, owing to the formation of macropores between the PtHSs and high porosity (90%) in the PtHS catalyst layers. The present study demonstrates a successful example of catalyst design in terms of catalyst layer architecture, which may be applied to a real fuel cell system.

Novel thin/tunable gas diffusion electrodes with ultra-low catalyst loading for hydrogen evolution reactions in proton exchange membrane electrolyzer cells

DOE PAGES

Kang, Zhenye; Yang, Gaoqiang; Mo, Jingke; ...

2018-03-09

Proton exchange membrane electrolyzer cells (PEMECs) have received great attention for hydrogen/oxygen production due to their high efficiencies even at low-temperature operation. Because of the high cost of noble platinum-group metal (PGM) catalysts (Ir, Ru, Pt, etc.) that are widely used in water splitting, a PEMEC with low catalyst loadings and high catalyst utilizations is strongly desired for its wide commercialization. In this study, the ultrafast and multiscale hydrogen evolution reaction (HER) phenomena in an operating PEMEC is in-situ observed for the first time. The visualization results reveal that the HER and hydrogen bubble nucleation mainly occur on catalyst layersmore » at the rim of the pores of the thin/tunable liquid/gas diffusion layers (TT-LGDLs). This indicates that the catalyst material of the conventional catalyst-coated membrane (CCM) that is located in the middle area of the LGDL pore is underutilized/inactive. Based on this discovery, a novel thin and tunable gas diffusion electrode (GDE) with a Pt catalyst thickness of 15 nm and a total thickness of about 25 um has been proposed and developed by taking advantage of advanced micro/nano manufacturing. The novel thin GDEs are comprehensively characterized both ex-situ and in-situ, and exhibit excellent PEMEC performance. More importantly, they achieve catalyst mass activity of up to 58 times higher than conventional CCM at 1.6 V under the operating conditions of 80 degrees C and 1 atm. This study demonstrates a promising concept for PEMEC electrode development, and provides a direction of future catalyst designs and fabrications for electrochemical devices.« less

Novel thin/tunable gas diffusion electrodes with ultra-low catalyst loading for hydrogen evolution reactions in proton exchange membrane electrolyzer cells

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kang, Zhenye; Yang, Gaoqiang; Mo, Jingke

Proton exchange membrane electrolyzer cells (PEMECs) have received great attention for hydrogen/oxygen production due to their high efficiencies even at low-temperature operation. Because of the high cost of noble platinum-group metal (PGM) catalysts (Ir, Ru, Pt, etc.) that are widely used in water splitting, a PEMEC with low catalyst loadings and high catalyst utilizations is strongly desired for its wide commercialization. In this study, the ultrafast and multiscale hydrogen evolution reaction (HER) phenomena in an operating PEMEC is in-situ observed for the first time. The visualization results reveal that the HER and hydrogen bubble nucleation mainly occur on catalyst layersmore » at the rim of the pores of the thin/tunable liquid/gas diffusion layers (TT-LGDLs). This indicates that the catalyst material of the conventional catalyst-coated membrane (CCM) that is located in the middle area of the LGDL pore is underutilized/inactive. Based on this discovery, a novel thin and tunable gas diffusion electrode (GDE) with a Pt catalyst thickness of 15 nm and a total thickness of about 25 um has been proposed and developed by taking advantage of advanced micro/nano manufacturing. The novel thin GDEs are comprehensively characterized both ex-situ and in-situ, and exhibit excellent PEMEC performance. More importantly, they achieve catalyst mass activity of up to 58 times higher than conventional CCM at 1.6 V under the operating conditions of 80 degrees C and 1 atm. This study demonstrates a promising concept for PEMEC electrode development, and provides a direction of future catalyst designs and fabrications for electrochemical devices.« less

Functionalized polymer nanofibre membranes for protection from chemical warfare stimulants

NASA Astrophysics Data System (ADS)

Ramaseshan, Ramakrishnan; Sundarrajan, Subramanian; Liu, Yingjun; Barhate, R. S.; Lala, Neeta L.; Ramakrishna, S.

2006-06-01

A catalyst for the detoxification of nerve agents is synthesized from β-cyclodextrin (β-CD) and o-iodosobenzoic acid (IBA). Functionalized polymer nanofibre membranes from PVC polymer are fabricated with β-CD, IBA, a blend of β-CD+IBA, and the synthesized catalyst. These functionalized nanofibres are then tested for the decontamination of paraoxon, a nerve agent stimulant, and it is observed that the stimulant gets hydrolysed. The kinetics of hydrolysis is investigated using UV spectroscopy. The rates of hydrolysis for different organophosphate hydrolyzing agents are compared. The reactivity and amount of adsorption of these catalysts are of higher capacity than the conventionally used activated charcoal. A new design for protective wear is proposed based on the functionalized nanofibre membrane.

Nitrogen-Coordinated Single Cobalt Atom Catalysts for Oxygen Reduction in Proton Exchange Membrane Fuel Cells

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Xiao Xia; Cullen, David A.; Pan, Yung-Tin

Due to the Fenton reaction, the presence of Fe and peroxide in electrodes generates free radicals causing serious degradation of the organic ionomer and the membrane. Pt-free and Fe-free cathode catalysts therefore are urgently needed for durable and inexpensive proton exchange membrane fuel cells (PEMFCs). In this paper, a high-performance nitrogen-coordinated single Co atom catalyst is derived from Co-doped metal-organic frameworks (MOFs) through a one-step thermal activation. Aberration-corrected electron microscopy combined with X-ray absorption spectroscopy virtually verifies the CoN 4 coordination at an atomic level in the catalysts. Through investigating effects of Co doping contents and thermal activation temperature, anmore » atomically Co site dispersed catalyst with optimal chemical and structural properties has achieved respectable activity and stability for the oxygen reduction reaction (ORR) in challenging acidic media (e.g., half-wave potential of 0.80 V vs reversible hydrogen electrode (RHE). The performance is comparable to Fe-based catalysts and 60 mV lower than Pt/C -60 μg Pt cm -2). Fuel cell tests confirm that catalyst activity and stability can translate to high-performance cathodes in PEMFCs. Finally, the remarkably enhanced ORR performance is attributed to the presence of well-dispersed CoN 4 active sites embedded in 3D porous MOF-derived carbon particles, omitting any inactive Co aggregates.« less

Nitrogen-Coordinated Single Cobalt Atom Catalysts for Oxygen Reduction in Proton Exchange Membrane Fuel Cells

DOE PAGES

Wang, Xiao Xia; Cullen, David A.; Pan, Yung-Tin; ...

2018-01-24

Due to the Fenton reaction, the presence of Fe and peroxide in electrodes generates free radicals causing serious degradation of the organic ionomer and the membrane. Pt-free and Fe-free cathode catalysts therefore are urgently needed for durable and inexpensive proton exchange membrane fuel cells (PEMFCs). In this paper, a high-performance nitrogen-coordinated single Co atom catalyst is derived from Co-doped metal-organic frameworks (MOFs) through a one-step thermal activation. Aberration-corrected electron microscopy combined with X-ray absorption spectroscopy virtually verifies the CoN 4 coordination at an atomic level in the catalysts. Through investigating effects of Co doping contents and thermal activation temperature, anmore » atomically Co site dispersed catalyst with optimal chemical and structural properties has achieved respectable activity and stability for the oxygen reduction reaction (ORR) in challenging acidic media (e.g., half-wave potential of 0.80 V vs reversible hydrogen electrode (RHE). The performance is comparable to Fe-based catalysts and 60 mV lower than Pt/C -60 μg Pt cm -2). Fuel cell tests confirm that catalyst activity and stability can translate to high-performance cathodes in PEMFCs. Finally, the remarkably enhanced ORR performance is attributed to the presence of well-dispersed CoN 4 active sites embedded in 3D porous MOF-derived carbon particles, omitting any inactive Co aggregates.« less

Nitrogen-Coordinated Single Cobalt Atom Catalysts for Oxygen Reduction in Proton Exchange Membrane Fuel Cells.

PubMed

Wang, Xiao Xia; Cullen, David A; Pan, Yung-Tin; Hwang, Sooyeon; Wang, Maoyu; Feng, Zhenxing; Wang, Jingyun; Engelhard, Mark H; Zhang, Hanguang; He, Yanghua; Shao, Yuyan; Su, Dong; More, Karren L; Spendelow, Jacob S; Wu, Gang

2018-03-01

Due to the Fenton reaction, the presence of Fe and peroxide in electrodes generates free radicals causing serious degradation of the organic ionomer and the membrane. Pt-free and Fe-free cathode catalysts therefore are urgently needed for durable and inexpensive proton exchange membrane fuel cells (PEMFCs). Herein, a high-performance nitrogen-coordinated single Co atom catalyst is derived from Co-doped metal-organic frameworks (MOFs) through a one-step thermal activation. Aberration-corrected electron microscopy combined with X-ray absorption spectroscopy virtually verifies the CoN 4 coordination at an atomic level in the catalysts. Through investigating effects of Co doping contents and thermal activation temperature, an atomically Co site dispersed catalyst with optimal chemical and structural properties has achieved respectable activity and stability for the oxygen reduction reaction (ORR) in challenging acidic media (e.g., half-wave potential of 0.80 V vs reversible hydrogen electrode (RHE). The performance is comparable to Fe-based catalysts and 60 mV lower than Pt/C -60 μg Pt cm -2 ). Fuel cell tests confirm that catalyst activity and stability can translate to high-performance cathodes in PEMFCs. The remarkably enhanced ORR performance is attributed to the presence of well-dispersed CoN 4 active sites embedded in 3D porous MOF-derived carbon particles, omitting any inactive Co aggregates. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

In situ observations of water production and distribution in an operating H2/O2 PEM fuel cell assembly using 1H NMR microscopy.

PubMed

Feindel, Kirk W; LaRocque, Logan P-A; Starke, Dieter; Bergens, Steven H; Wasylishen, Roderick E

2004-09-22

Proton NMR imaging was used to investigate in situ the distribution of water in a polymer electrolyte membrane fuel cell operating on H2 and O2. In a single experiment, water was monitored in the gas flow channels, the membrane electrode assembly, and in the membrane surrounding the catalysts. Radial gradient diffusion removes water from the catalysts into the surrounding membrane. This research demonstrates the strength of 1H NMR microscopy as an aid for designing fuel cells to optimize water management.

Continuous growth of single-wall carbon nanotubes using chemical vapor deposition

DOEpatents

Grigorian, Leonid [Raymond, OH; Hornyak, Louis [Evergreen, CO; Dillon, Anne C [Boulder, CO; Heben, Michael J [Denver, CO

2008-10-07

The invention relates to a chemical vapor deposition process for the continuous growth of a carbon single-wall nanotube where a carbon-containing gas composition is contacted with a porous membrane and decomposed in the presence of a catalyst to grow single-wall carbon nanotube material. A pressure differential exists across the porous membrane such that the pressure on one side of the membrane is less than that on the other side of the membrane. The single-wall carbon nanotube growth may occur predominately on the low-pressure side of the membrane or, in a different embodiment of the invention, may occur predominately in between the catalyst and the membrane. The invention also relates to an apparatus used with the carbon vapor deposition process.

Continuous growth of single-wall carbon nanotubes using chemical vapor deposition

DOEpatents

Grigorian, Leonid; Hornyak, Louis; Dillon, Anne C; Heben, Michael J

2014-09-23

The invention relates to a chemical vapor deposition process for the continuous growth of a carbon single-wall nanotube where a carbon-containing gas composition is contacted with a porous membrane and decomposed in the presence of a catalyst to grow single-wall carbon nanotube material. A pressure differential exists across the porous membrane such that the pressure on one side of the membrane is less than that on the other side of the membrane. The single-wall carbon nanotube growth may occur predominately on the low-pressure side of the membrane or, in a different embodiment of the invention, may occur predominately in between the catalyst and the membrane. The invention also relates to an apparatus used with the carbon vapor deposition process.

Chemical microreactor and method thereof

DOEpatents

Morse, Jeffrey D.; Jankowski, Alan

2005-11-01

A chemical microreactor suitable for generation of hydrogen fuel from liquid sources such as ammonia, methanol, and butane through steam reforming processes when mixed with an appropriate amount of water contains capillary microchannels with integrated resistive heaters to facilitate the occurrence of catalytic steam reforming reactions. One such microreactor employs a packed catalyst capillary microchannel and at least one porous membrane. Another employs a porous membrane with a large surface area or a porous membrane support structure containing a plurality of porous membranes having a large surface area in the aggregate, i.e., greater than about 1 m.sup.2 /cm.sup.3. The packed catalyst capillary microchannels, porous membranes and porous membrane support structures may be formed by a variety of methods.

Influence of the membrane ion exchange capacity on the catalyst layer of proton exchange membrane fuel cell

NASA Astrophysics Data System (ADS)

Navessin, Titichai

2005-07-01

This work investigated the effect of ion exchange capacity (IEC) of polymer electrolyte membranes (PEM) on the PEM fuel cell cathode catalyst layer. A series of radiation grafted ethylene tetrafluoroethylene-g-polystyrene sulfonic acid (ETFE-g-PSSA) membranes was used to provide a systematic variation of IEC. A method to fabricate gas diffusion electrodes (GDEs) was adapted and custom-made GDEs with known compositions were prepared. Oxygen electrochemistry, mass transport properties, water absorption behaviour and proton conductivity were studied in relation to the IEC. Electrochemical characterization including cyclic voltammetry, electrochemical impedance spectroscopy and linear sweep voltammetry were employed. The agglomerate model for cathodes was adapted and used to extract mass transport parameters from experimental results. Prior to investigation in fuel cell systems, studies were performed in a half-fuel cell, which simplified complicating parameters associated with fuel cell operation. It was found that membranes with higher IEC resulted in a higher active surface area of electrode. In contrast, they exhibited lower oxygen reduction performance. The extracted effective diffusion coefficient of oxygen and O2 solubility in the catalyst layer was used to estimate the extent of flooding, which revealed that ˜67--70% of void space was filled with water. The membrane's IEC regulates the extent of flooding of the cathode, which in turn affects its electrochemical characteristics. The investigation under operating fuel cell conditions revealed an increase in fuel cell performance with increasing IEC---a contradicting trend to that found for the half-fuel cell. This is explained by the interplay of electroosmotic flux and hydraulic counterflux in the membrane which affects water management in the membrane electrode assembly (MEA). The influence was most significant in the cathode catalyst layer, where it affects mass transport and electrochemical characteristics. It was found that the higher IEC facilitated better water management in MEAs. Comparing results obtained with half fuel cell and fuel cell systems revealed insights into the state of hydration and effective use of Pt in the catalyst layer. The two types of measurements provide a convenient approach to study the interplay of different mechanisms of water flux in the membrane.

PdRu/C catalysts for ethanol oxidation in anion-exchange membrane direct ethanol fuel cells

NASA Astrophysics Data System (ADS)

Ma, Liang; He, Hui; Hsu, Andrew; Chen, Rongrong

2013-11-01

Carbon supported PdRu catalysts with various Pd:Ru atomic ratios were synthesized by impregnation method, and characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), electrochemical half-cell tests, and the anion-exchange membrane direct ethanol fuel cell (AEM-DEFC) tests. XRD results suggest that the PdRu metal exists on carbon support in an alloy form. TEM study shows that the bimetallic PdRu/C catalysts have slightly smaller average particle size than the single metal Pd/C catalyst. Lower onset potential and peak potential and much higher steady state current for ethanol oxidation in alkaline media were observed on the bimetallic catalysts (PdxRuy/C) than on the Pd/C, while the activity for ethanol oxidation on the pure Ru/C was not noticeable. By using Pd/C anode catalysts and MnO2 cathode catalysts, AEM-DEFCs free from the expensive Pt catalyst were assembled. The AEM DEFC using the bimetallic Pd3Ru/C anode catalyst showed a peak power density as high as 176 mW cm-2 at 80 °C, about 1.8 times higher than that using the single metal Pd/C catalyst. The role of Ru for enhancing the EOR activity of Pd/C catalysts is discussed.

Oxygen activation at the plasma membrane: relation between superoxide and hydroxyl radical production by isolated membranes.

PubMed

Heyno, Eiri; Mary, Véronique; Schopfer, Peter; Krieger-Liszkay, Anja

2011-07-01

Production of reactive oxygen species (hydroxyl radicals, superoxide radicals and hydrogen peroxide) was studied using EPR spin-trapping techniques and specific dyes in isolated plasma membranes from the growing and the non-growing zones of hypocotyls and roots of etiolated soybean seedlings as well as coleoptiles and roots of etiolated maize seedlings. NAD(P)H mediated the production of superoxide in all plasma membrane samples. Hydroxyl radicals were only produced by the membranes of the hypocotyl growing zone when a Fenton catalyst (FeEDTA) was present. By contrast, in membranes from other parts of the seedlings a low rate of spontaneous hydroxyl radical formation was observed due to the presence of small amounts of tightly bound peroxidase. It is concluded that apoplastic hydroxyl radical generation depends fully, or for the most part, on peroxidase localized in the cell wall. In soybean plasma membranes from the growing zone of the hypocotyl pharmacological tests showed that the superoxide production could potentially be attributed to the action of at least two enzymes, an NADPH oxidase and, in the presence of menadione, a quinone reductase.

Solar radiation synthesis of functional carbonaceous materials using Al2O3/TiO2-Cu-HA doped catalyst

NASA Astrophysics Data System (ADS)

Stanciu, Elena Manuela; Pascu, Alexandru; Roată, Ionut Claudiu; Croitoru, Cătălin; Tierean, Mircea; Rosca, Julia Mirza; Hulka, Iosif

2018-04-01

Single carbon nanotubes were synthesized through a physical vapor deposition method, using concentrated solar radiation as means of vaporization and promoting the formation of carbonaceous plasma plume. A novel catalyst, containing multiple hybrid ceramic/metal phases has been obtained through flame spraying. In conjunction with this catalyst, good quality nanomaterials, such as long single-walled nanotubes and nanoparticles have been obtained and characterized by both morphological (SEM, TEM) as well as structural means on analysis (XRD, FTIR). A mild oxidation of the carbonaceous phase has been reported, which could prove useful in applications in conjunction with metals or hydrophilic polymers as potential matrices for nanocomposites obtaining.

Developing testing methods for characterizing emissions and sources of exposures from polyurehane products

EPA Science Inventory

The relationship between onsite manufacture of spray polyurethane foam insulation (SPFI) and potential exposures to diisocyanate compounds, amine catalysts, flame retardants, and blowing agents, as well as aldehydes and other volatile or semivolatile organic compounds that may be...

Methods of conditioning direct methanol fuel cells

DOEpatents

Rice, Cynthia; Ren, Xiaoming; Gottesfeld, Shimshon

2005-11-08

Methods for conditioning the membrane electrode assembly of a direct methanol fuel cell ("DMFC") are disclosed. In a first method, an electrical current of polarity opposite to that used in a functioning direct methanol fuel cell is passed through the anode surface of the membrane electrode assembly. In a second method, methanol is supplied to an anode surface of the membrane electrode assembly, allowed to cross over the polymer electrolyte membrane of the membrane electrode assembly to a cathode surface of the membrane electrode assembly, and an electrical current of polarity opposite to that in a functioning direct methanol fuel cell is drawn through the membrane electrode assembly, wherein methanol is oxidized at the cathode surface of the membrane electrode assembly while the catalyst on the anode surface is reduced. Surface oxides on the direct methanol fuel cell anode catalyst of the membrane electrode assembly are thereby reduced.

Method of making MEA for PEM/SPE fuel cell

DOEpatents

Hulett, Jay S.

2000-01-01

A method of making a membrane-electrode-assembly (MEA) for a PEM/SPE fuel cell comprising applying a slurry of electrode-forming material directly onto a membrane-electrolyte film. The slurry comprises a liquid vehicle carrying catalyst particles and a binder for the catalyst particles. The membrane-electrolyte is preswollen by contact with the vehicle before the electrode-forming slurry is applied to the membrane-electrolyte. The swollen membrane-electrolyte is constrained against shrinking in the "x" and "y" directions during drying. Following assembly of the fuel cell, the MEA is rehydrated inside the fuel cell such that it swells in the "z" direction for enhanced electrical contact with contiguous electrically conductive components of the fuel cell.

Pd-Ag Membrane Coupled to a Two-Zone Fluidized Bed Reactor (TZFBR) for Propane Dehydrogenation on a Pt-Sn/MgAl2O4 Catalyst

PubMed Central

Medrano, José-Antonio; Julián, Ignacio; Herguido, Javier; Menéndez, Miguel

2013-01-01

Several reactor configurations have been tested for catalytic propane dehydrogenation employing Pt-Sn/MgAl2O4 as a catalyst. Pd-Ag alloy membranes coupled to the multifunctional Two-Zone Fluidized Bed Reactor (TZFBR) provide an improvement in propane conversion by hydrogen removal from the reaction bed through the inorganic membrane in addition to in situ catalyst regeneration. Twofold process intensification is thereby achieved when compared to the use of traditional fluidized bed reactors (FBR), where coke formation and thermodynamic equilibrium represent important process limitations. Experiments were carried out at 500–575 °C and with catalyst mass to molar flow of fed propane ratios between 15.1 and 35.2 g min mmol−1, employing three different reactor configurations: FBR, TZFBR and TZFBR + Membrane (TZFBR + MB). The results in the FBR showed catalyst deactivation, which was faster at high temperatures. In contrast, by employing the TZFBR with the optimum regenerative agent flow (diluted oxygen), the process activity was sustained throughout the time on stream. The TZFBR + MB showed promising results in catalytic propane dehydrogenation, displacing the reaction towards higher propylene production and giving the best results among the different reactor configurations studied. Furthermore, the results obtained in this study were better than those reported on conventional reactors. PMID:24958620

Combination of Trichoderma harzianum endochitinase and a membrane-affecting fungicide on control of Alternaria leaf spot in transgenic broccoli plants.

PubMed

Mora, A; Earle, E D

2001-04-01

Progeny from transgenic broccoli (cv. Green Comet) expressing a Trichoderma harzianum endochitinase gene were used to assess the interaction between endochitinase and the fungicide Bayleton in the control of Alternaria brassicicola. In vitro assays have shown synergistic effects of endochitinase and fungicides on fungal pathogens. Our study examined the in planta effects of endochitinase and Bayleton, individually and in combination. Two month old transgenic and non-transgenic plants were sprayed with ED50 levels of Bayleton and/or inoculated with an A. brassicicola spore suspension. Disease levels in non-sprayed transgenic plants were not statistically different from sprayed transgenic plants nor from sprayed non-transgenic controls. Thus endochitinase-transgenic plants alone provided a significant reduction of disease severity, comparable to the protection by fungicide on non-transgenic plants. Comparison of the expected additive and observed effects revealed no synergism between endochitinase and Bayleton (at ED50 level), and usually less than an additive effect. Some transgenic lines sprayed with fungicide at doses higher than ED50 showed resistance similar to the non-sprayed transgenic lines, again suggesting no synergistic effect. Lack of synergism may be due to incomplete digestion of the cell wall by endochitinase, so that the effect of Bayleton at the cell membrane is not enhanced.

DEVELOPMENT OF ATTRITION RESISTANT IRON-BASED FISCHER-TROPSCH CATALYSTS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Adeyinka A. Adeyiga

2001-09-01

The Fischer-Tropsch (F-T) reaction provides a way of converting coal-derived synthesis gas (CO+H{sub 2}) to liquid fuels. Since the reaction is highly exothermic, one of the major problems in control of the reaction is heat removal. Recent work has shown that the use of slurry bubble column reactors (SBCRs) can largely solve this problem. The use of iron-based catalysts is attractive not only due to their low cost and ready availability, but also due to their high water-gas shift activity which makes it possible to use these catalysts with low H{sub 2}/CO ratios. However, a serious problem with use ofmore » Fe catalysts in a SBCR is their tendency to undergo attrition. This can cause fouling/plugging of downstream filters and equipment, makes the separation of catalyst from the oil/wax product very difficult if not impossible, and results in a steady loss of catalyst from the reactor. Recently, fundamental understanding of physical attrition is being addressed by incorporating suitable binders into the catalyst recipe. This has resulted in the preparation of a spray dried Fe-based catalyst having aps of 70 mm with high attrition resistance. This Fe-based attrition resistant, active and selective catalyst gave 95% CO conversion through 125 hours of testing in a fixed-bed at 270 C, 1.48 MPa, H{sub 2}/CO=0.67 and 2.0 NL/g-cat/h with C{sub 5}{sup +} selectivity of >78% and methane selectivity of <5%. However, further development of the catalyst is needed to address the chemical attrition due to phase changes that any Fe-catalyst goes through potentially causing internal stresses within the particle and resulting in weakening, spalling or cracking. The objective of this research is to develop robust iron-based Fischer-Tropsch catalysts that have suitable activity, selectivity and stability to be used in the slurry bubble column reactor. Specifically we aim to develop to: (i) improve the performance and preparation procedure of the high activity, high attrition resistant, high alpha iron-based catalysts synthesized at Hampton University, (ii) seek improvements in the catalyst performance through variations in process conditions, pretreatment procedures and/or modifications in catalyst preparation steps and (iii) investigate the performance in a slurry reactor. The effort during the reporting period has been devoted to attrition study of the iron-based catalysts. Precipitated silica appeared to decrease attrition resistance of spray-dried iron FT catalysts. It was found that the catalyst with precipitated silica content at around 12wt% showed the lowest attrition resistance. The results of net change in volume moment and catalyst morphology showed supporting evidences to the attrition results. Catalysts with low attrition resistance generated more fines loss, had higher net change in volume moment and showed more breakage of particles. BET surface area and pore volume of this catalyst series fluctuated; therefore no conclusion can be drawn from the data obtained. However, catalyst with no precipitated silica showed the lowest in BET surface area and pore volume, as expected. Addition of precipitated silica to the catalysts had no effect to the phase changes of iron that could have significant influence to catalyst attrition. The presence of precipitated silica is needed for enhancing catalyst surface area; however, the amount of silica added should be compromising with attrition resistance of catalysts.« less

Enhanced Performance of non-PGM Catalysts in Air Operated PEM-Fuel Cells

DOE PAGES

Barkholtz, Heather M.; Chong, Lina; Kaiser, Zachary Brian; ...

2016-10-13

Here a non-platinum group metal (non-PGM) oxygen reduction catalyst was prepared from “support-free” zeolitic imidazolate framework (ZIF) precursor and tested in the proton exchange membrane fuel cell with air as the cathode feed. The iron nitrogen and carbon composite (FeeNeC) based catalyst has high specific surface area decorated uniformly with active sites, which redefines the triple phase boundary (TPB) and requires re-optimization of the cathodic membrane electrode fabrication to ensure efficient mass and charge transports to the catalyst surface. This study reports an effort in optimizing catalytic ink formulation for the membrane electrode preparation and its impact to the fuelmore » cell performance under air. Through optimization, the fuel cell areal current density as high as 115.2 mA/cm 2 at 0.8 V or 147.6 mA/cm 2 at 0.8 V iR-free has been achieved under one bar air. We also investigated impacts on fuel cell internal impedance and the water formation.« less

The reasons for the high power density of fuel cells fabricated with directly deposited membranes

NASA Astrophysics Data System (ADS)

Vierrath, Severin; Breitwieser, Matthias; Klingele, Matthias; Britton, Benjamin; Holdcroft, Steven; Zengerle, Roland; Thiele, Simon

2016-09-01

In a previous study, we reported that polymer electrolyte fuel cells prepared by direct membrane deposition (DMD) produced power densities in excess of 4 W/cm2. In this study, the underlying origins that give rise to these high power densities are investigated and reported. The membranes of high power, DMD-fabricated fuel cells are relatively thin (12 μm) compared to typical benchmark, commercially available membranes. Electrochemical impedance spectroscopy, at high current densities (2.2 A/cm2) reveals that mass transport resistance was half that of reference, catalyst-coated-membranes (CCM). This is attributed to an improved oxygen supply in the cathode catalyst layer by way of a reduced propensity of flooding, and which is facilitated by an enhancement in the back diffusion of water from cathode to anode through the thin directly deposited membrane. DMD-fabricated membrane-electrode-assemblies possess 50% reduction in ionic resistance (15 mΩcm2) compared to conventional CCMs, with contributions of 9 mΩcm2 for the membrane resistance and 6 mΩcm2 for the contact resistance of the membrane and catalyst layer ionomer. The improved mass transport is responsible for 90% of the increase in power density of the DMD fuel cell, while the reduced ionic resistance accounts for a 10% of the improvement.

Development of low-loading, carbon monoxide tolerant PEM fuel cell electrodes

NASA Astrophysics Data System (ADS)

Haug, Andrew Thomas

This work discusses the problems of, and potential solutions to, high catalyst cost of and carbon monoxide (CO) poisoning of the proton-exchange membrane fuel cell (PEMFC). As this is a comprehensive work, background on fuel cells and specifically PEMFCs is first presented. A discussion of the current status of PEMFCs is presented showing ongoing work for stationary, transportation, portable and military applications. This leads into two of the more significant problems preventing widespread commercialization of PEMFC technology: poisoning of the catalyst by CO and the cost of the catalyst. A thorough examination of CO poisoning of the PEMFC anode is presented from how CO comes to be present in the feed stream of the PEMFC anode to how it then poisons the PEMFC anode. The first work presented here describes the development of a novel CO tolerant anode (the Ruthenium filter). It shows that by placing a layer of carbon-supported Ruthenium catalyst between the Pt catalyst and the anode flow field to form a filter, tolerance to CO will be increased relative to a Pt:Ru alloy when oxygen is added to the anode fuel stream. Secondly, after an introduction to catalyst preparation techniques used today and a brief discussion of catalyst-cost in PEMFCs, it is shown how sputter-deposition technology may be used to create more kinetically active PEMFC catalyst electrodes versus standard ink-based techniques. The technologies of the Ru filter and sputter-deposition are then combined to create a low-loading, CO tolerant anode for the PEMFC. In the final work, the effect of the airbleed on CO oxidation is then modeled. In the concluding chapter, it is shown how the work presented can lead the PEMFC closer to large-scale commercialization. The Appendix A provides a detailed method by which PEMFC MEAs were manufactured using catalyst inks. This method served as the basis for all original works presented. Appendix B--F provide further background and information on the mathematical model developed, including a printout of the Fortran code used to generate the model results.

Fluxing template-assisted synthesis of sponge-like Fe2O3 microspheres toward efficient catalysis for CO oxidation

NASA Astrophysics Data System (ADS)

Li, Wenge; Hu, Yanjie; Jiang, Hao; Jiang, Yi; Wang, Yang; Huang, Su; Biswas, Pratim; Li, Chunzhong

2018-06-01

Constructing a porous architecture is a considerable strategy to enhance the catalytic activity of metal oxides catalysts for CO oxidation. In this work, we have developed porous sponge-like Fe2O3 microspheres by employing a facile aerosol spray pyrolysis. The NaNO3 salt in the spray solution plays a crucial role as a fluxing sacrifice template in the formation of the sponge-like structure, in which a high surface area of 216.2 m2 g-1 and an average pore size of 4 nm are obtained. This novel Fe2O3 catalyst exhibits an improved catalytic activity compared to usual iron oxides catalysts. Nearly 50% CO conversion at a relatively low temperature of 200 °C and 100% CO conversion at 300 °C at a space velocity of 60 000 ml h-1 g-1 are achieved. Furthermore, it displays an outstanding catalytic stability without distinct decay for 1000 min in a continuous stream at 300 °C. In addition to the effect of plentiful adsorption sites for the gas reactant, the promoted catalytic performance is also attributed to the function of abundant OH groups rooted in the large surface of the sponge-like structure, which induces faster reaction rate of CO oxidation via a bicarbonate route.

Center for the Polyurethanes Industry summary of unpublished industrial hygiene studies related to the evaluation of emissions of spray polyurethane foam insulation.

PubMed

Wood, Richard D

2017-09-01

Spray polyurethane foam (SPF) insulation is used as thermal insulation for residential and commercial buildings. It has many advantages over other forms insulation; however, concerns have been raised related to chemical emissions during and after application. The American Chemistry Council's (ACC's) Center for the Polyurethanes Industry (CPI) has gathered previously unpublished industrial hygiene air sampling studies submitted by member companies that were completed during an eight-year period from 2007-2014. These studies address emissions from medium density closed cell and low density open cell formulations. This article summarizes the results of personal and area air samples collected during application and post application of SPF to interior building surfaces in both laboratory and field environments. Chemicals of interest included: Volatile Organic Compounds (VOCs), methylene diphenyl diisocyanate (MDI), flame retardants, amine catalysts, blowing agents, and aldehydes. Overall, the results indicate that SPF applicators and workers in close proximity to the application are potentially exposed to MDI in excess of recommended and governmental occupational exposure limits and should use personal protective equipment (PPE) consisting of air supplied respirators and full-body protective clothing to reduce exposure. Catalyst emissions can be reduced by using reactive catalysts in SPF formulations, and mechanical ventilation is important in controlling emissions during and after application.

Improved Cathode Structure for a Direct Methanol Fuel Cell

NASA Technical Reports Server (NTRS)

Valdez, Thomas; Narayanan, Sekharipuram

2005-01-01

An improved cathode structure on a membrane/electrode assembly has been developed for a direct methanol fuel cell, in a continuing effort to realize practical power systems containing such fuel cells. This cathode structure is intended particularly to afford better cell performance at a low airflow rate. A membrane/electrode assembly of the type for which the improved cathode structure was developed (see Figure 1) is fabricated in a process that includes brush painting and spray coating of catalyst layers onto a polymer-electrolyte membrane and onto gas-diffusion backings that also act as current collectors. The aforementioned layers are then dried and hot-pressed together. When completed, the membrane/electrode assembly contains (1) an anode containing a fine metal black of Pt/Ru alloy, (2) a membrane made of Nafion 117 or equivalent (a perfluorosulfonic acid-based hydrophilic, proton-conducting ion-exchange polymer), (3) a cathode structure (in the present case, the improved cathode structure described below), and (4) the electrically conductive gas-diffusion backing layers, which are made of Toray 060(TradeMark)(or equivalent) carbon paper containing between 5 and 6 weight percent of poly(tetrafluoroethylene). The need for an improved cathode structure arises for the following reasons: In the design and operation of a fuel-cell power system, the airflow rate is a critical parameter that determines the overall efficiency, cell voltage, and power density. It is desirable to operate at a low airflow rate in order to obtain thermal and water balance and to minimize the size and mass of the system. The performances of membrane/electrode assemblies of prior design are limited at low airflow rates. Methanol crossover increases the required airflow rate. Hence, one way to reduce the required airflow rate is to reduce the effect of methanol crossover. Improvement of the cathode structure - in particular, addition of hydrophobic particles to the cathode - has been demonstrated to mitigate the effects of crossover and decrease the airflow required.

Method for forming a chemical microreactor

DOEpatents

Morse, Jeffrey D [Martinez, CA; Jankowski, Alan [Livermore, CA

2009-05-19

Disclosed is a chemical microreactor that provides a means to generate hydrogen fuel from liquid sources such as ammonia, methanol, and butane through steam reforming processes when mixed with an appropriate amount of water. The microreactor contains capillary microchannels with integrated resistive heaters to facilitate the occurrence of catalytic steam reforming reactions. Two distinct embodiment styles are discussed. One embodiment style employs a packed catalyst capillary microchannel and at least one porous membrane. Another embodiment style employs a porous membrane with a large surface area or a porous membrane support structure containing a plurality of porous membranes having a large surface area in the aggregate, i.e., greater than about 1 m.sup.2/cm.sup.3. Various methods to form packed catalyst capillary microchannels, porous membranes and porous membrane support structures are also disclosed.

Effect of Particle Size and Operating Conditions on Pt 3Co PEMFC Cathode Catalyst Durability

DOE PAGES

Gummalla, Mallika; Ball, Sarah; Condit, David; ...

2015-05-29

The initial performance and decay trends of polymer electrolyte membrane fuel cells (PEMFC) cathodes with Pt 3Co catalysts of three mean particle sizes (4.9 nm, 8.1 nm, and 14.8 nm) with identical Pt loadings are compared. Even though the cathode based on 4.9 nm catalyst exhibited the highest initial electrochemical surface area (ECA) and mass activity, the cathode based on 8.1 nm catalyst showed better initial performance at high currents. Owing to the low mass activity of the large particles, the initial performance of the 14.8 nm Pt3Co-based electrode was the lowest. The performance decay rate of the electrodes withmore » the smallest Pt 3Co particle size was the highest and that of the largest Pt 3Co particle size was lowest. Interestingly, with increasing number of decay cycles (0.6 to 1.0 V, 50 mV/s), the relative improvement in performance of the cathode based on 8.1 nm Pt 3Co over the 4.9 nm Pt 3Co increased, owing to better stability of the 8.1 nm catalyst. The electron microprobe analysis (EMPA) of the decayed membrane-electrode assembly (MEA) showed that the amount of Co in the membrane was lower for the larger particles, and the platinum loss into the membrane also decreased with increasing particle size. This suggests that the higher initial performance at high currents with 8.1 nm Pt 3Co could be due to lower contamination of the ionomer in the electrode. Furthermore, lower loss of Co from the catalyst with increased particle size could be one of the factors contributing to the stability of ECA and mass activity of electrodes with larger cathode catalyst particles. To delineate the impact of particle size and alloy effects, these results are compared with prior work from our research group on size effects of pure platinum catalysts. The impact of PEMFC operating conditions, including upper potential, relative humidity, and temperature on the alloy catalyst decay trends, along with the EMPA analysis of the decayed MEAs, are reported.« less

Oxygen permeation through Nafion 117 membrane and its impact on efficiency of polymer membrane ethanol fuel cell

NASA Astrophysics Data System (ADS)

Jablonski, Andrzej; Kulesza, Pawel J.; Lewera, Adam

2011-05-01

We investigate oxygen permeation through Nafion 117 membrane in a direct ethanol fuel cell and elucidate how it affects the fuel cell efficiency. An obvious symptom of oxygen permeation is the presence of significant amounts of acetaldehyde and acetic acid in the mixture leaving anode when no current was drawn from the fuel cell (i.e. under the open circuit conditions). This parasitic process severely lowers efficiency of the fuel cell because ethanol is found to be directly oxidized on the surface of catalyst by oxygen coming through membrane from cathode in the absence of electric current flowing in the external circuit. Three commonly used carbon-supported anode catalysts are investigated, Pt, Pt/Ru and Pt/Sn. Products of ethanol oxidation are determined qualitatively and quantitatively at open circuit as a function of temperature and pressure, and we aim at determining whether the oxygen permeation or the catalyst's activity limits the parasitic ethanol oxidation. Our results strongly imply the need to develop more selective membranes that would be less oxygen permeable.

Sunlight-Driven Hydrogen Formation by Membrane-Supported Photoelectrochemical Water Splitting

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lewis, Nathan S.

2014-03-26

This report describes the significant advances in the development of the polymer-supported photoelectrochemical water-splitting system that was proposed under DOE grant number DE-FG02-05ER15754. We developed Si microwire-array photoelectrodes, demonstrated control over the material and light-absorption properties of the microwire-array photoelectrodes, developed inexpensive processes for synthesizing the arrays, and doped the arrays p-type for use as photocathodes. We also developed techniques for depositing metal-nanoparticle catalysts of the hydrogen-evolution reaction (HER) on the wire arrays, investigated the stability and catalytic performance of the nanoparticles, and demonstrated that Ni-Mo alloys are promising earth-abundant catalysts of the HER. We also developed methods that allowmore » reuse of the single-crystalline Si substrates used for microwire growth and methods of embedding the microwire photocathodes in plastic to enable large-scale processing and deployment of the technology. Furthermore we developed techniques for controlling the structure of WO3 films, and demonstrated that structural control can improve the quantum yield of photoanodes. Thus, by the conclusion of this project, we demonstrated significant advances in the development of all components of a sunlight-driven membrane-supported photoelectrochemical water-splitting system. This final report provides descriptions of some of the scientific accomplishments that were achieved under the support of this project and also provides references to the peer-reviewed publications that resulted from this effort.« less

Development of materials for mini DMFC working at room temperature for portable applications

NASA Astrophysics Data System (ADS)

Coutanceau, C.; Koffi, R. K.; Léger, J.-M.; Marestin, K.; Mercier, R.; Nayoze, C.; Capron, P.

Methanol permeability measurements and direct methanol fuel cell tests were performed at room temperature with different commercially available or recast Nafion ® membranes and sulfonated polyimide (SPI) membranes. Power densities as high as 20 mW cm -2 could be obtained with Nafion ® 115. However, in order to meet the technological requirements for portable applications, thinner membranes have to be considered. As the MeOH crossover increases greatly (from (7 to 20) × 10 -8 mol s -1 cm -2) while Nafion ® membranes thickness decreases, non-perfluorinated polymers having high IEC are promising candidates for DMFC working at room temperature. The development catalysts tolerant to methanol is also relevant for this application. In spite of the low permeability to MeOH of SPI membranes, the obtained electrical performance with E-TEK electrodes based MEAs was lower than that obtained with Nafion ® membranes. No significant increase of performances was neither evidenced by using homemade PtCr(7:3)/C and PtRu(4:1)/C catalysts instead of E-TEK electrodes with recast Nafion ® based MEAs. However, MEAs composed with thin SPI membranes (50 μm) and homemade PtCr/C catalysts gave very promising results (18 mW cm -2). Based on experimental observations, a speculative explanation of this result is given.

Effects of nozzle type and spray angle on spray deposition in ivy pot plants.

PubMed

Foqué, Dieter; Nuyttens, David

2011-02-01

Fewer plant protection products are now authorised for use in ornamental growings. Frequent spraying with the same product or a suboptimal technique can lead to resistance in pests and diseases. Better application techniques could improve the sustainable use of the plant protection products still available. Spray boom systems--instead of the still predominantly used spray guns--might improve crop protection management in greenhouses considerably. The effect of nozzle type, spray pressure and spray angle on spray deposition and coverage in ivy pot plants was studied, with a focus on crop penetration and spraying the bottom side of the leaves in this dense crop. The experiments showed a significant and important effect of collector position on deposition and coverage in the plant. Although spray deposition and coverage on the bottom side of the leaves are generally low, they could be improved 3.0-4.9-fold using the appropriate application technique. When using a spray boom in a dense crop, the nozzle choice, spray pressure and spray angle should be well considered. The hollow-cone, the air-inclusion flat-fan and the standard flat-fan nozzle with an inclined spray angle performed best because of the effect of swirling droplets, droplets with a high momentum and droplet direction respectively. Copyright © 2010 Society of Chemical Industry.

Enhancing oxygen transport through Mixed-Ionic-and-Electronic-Conducting ceramic membranes

NASA Astrophysics Data System (ADS)

Yu, Anthony S.

Ceramic membranes based on Mixed-Ionic-and-Electronic-Conducting (MIEC) oxides are capable of separating oxygen from air in the presence of an oxygen partial-pressure gradient. These MIEC membranes show great promise for oxygen consuming industrial processes, such as the production of syngas from steam reforming of natural gas (SRM), as well as for electricity generation in Solid Oxide Fuel Cells (SOFC). For both applications, the overall performance is dictated by the rate of oxygen transport across the membrane. Oxygen transport across MIEC membranes is composed of a bulk oxygen-ion diffusion process and surface processes, such as surface reactions and adsorption/desorption of gaseous reactants/products. The main goal of this thesis was to determine which process is rate-limiting in order to significantly enhance the overall rate of oxygen transport in MIEC membrane systems. The rate-limiting step was determined by evaluating the total resistance to oxygen transfer, Rtot. Rtot is the sum of a bulk diffusion resistance in the membrane itself, Rb, and interfacial loss components, Rs. Rb is a function of the membrane's ionic conductivity and thickness, while Rs arises primarily from slow surface-exchange kinetics that cause the P(O2) at the surfaces of the membrane to differ from the P(O 2) in the adjacent gas phases. Rtot can be calculated from the Nernst potential across the membrane and the measured oxygen flux. The rate-limiting process can be determined by evaluating the relative contributions of the various losses, Rs and Rb, to Rtot. Using this method, this thesis demonstrates that for most membrane systems, Rs is the dominating factor. In the development of membrane systems with high oxygen transport rates, thin membranes with high ionic conductivities are required to achieve fast bulk oxygen-ion diffusion. However, as membrane thickness is decreased, surface reaction kinetics become more important in determining the overall transport rate. The two approaches to increase surface reaction kinetics and decrease Rs that were examined in this thesis involved modifying the surface microstructure, as well as adding both metallic (e.g. Pt) and oxide (e.g. CeO2, La0.8Sr0.2FeO3) catalysts to both membrane surfaces. These two approaches were investigated for single-phase MIEC membrane reactors (La0.9Ca0.1FeO3-delta ), as well as composite membrane reactors composed of an electronic conductor (La0.8Sr-0.2CrO3-delta) and an ionic conductor (YSZ). The use of catalysts and microstructure modifications to decrease interfacial losses is equally important for SOFCs. In this thesis, the electrochemical activity and microstructure of metallic catalysts formed by "ex-solving" metals from an oxide lattice, and oxide catalysts deposited by Atomic Layer Deposition (ALD) were investigated. It is shown that these methods for depositing catalysts resulted in very different effects on electrode performance when compared to the same catalysts deposited by wet impregnation. For example, when transition metals, such as Ni and Co, were "ex-solved" from a La0.8Sr0.2CrO3-delta anode lattice, these "ex-solved" metal particles not only exhibited great catalytic activity, they were also less prone to coking compared to their wet impregnated counterparts. On the cathode side, thin layers of various oxides (e.g. Al 2O3, CeOx, SrO) that were deposited using ALD also exhibited drastically different electrochemical activity compared to their wet impregnated counterparts. It was determined that differences in electrochemical activity could be attributed to a difference in the oxide morphology, showing that a catalyst's microstructure and morphology are very important in dictating its overall activity in SOFC electrodes.

Mathematical modeling of methyl ester concentration distribution in a continuous membrane tubular reactor and comparison with conventional tubular reactor

NASA Astrophysics Data System (ADS)

Talaghat, M. R.; Jokar, S. M.; Modarres, E.

2017-10-01

The reduction of fossil fuel resources and environmental issues made researchers find alternative fuels include biodiesels. One of the most widely used methods for production of biodiesel on a commercial scale is transesterification method. In this work, the biodiesel production by a transesterification method was modeled. Sodium hydroxide was considered as a catalyst to produce biodiesel from canola oil and methanol in a continuous tubular ceramic membranes reactor. As the Biodiesel production reaction from triglycerides is an equilibrium reaction, the reaction rate constants depend on temperature and related linearly to catalyst concentration. By using the mass balance for a membrane tubular reactor and considering the variation of raw materials and products concentration with time, the set of governing equations were solved by numerical methods. The results clearly show the superiority of membrane reactor than conventional tubular reactors. Afterward, the influences of molar ratio of alcohol to oil, weight percentage of the catalyst, and residence time on the performance of biodiesel production reactor were investigated.

DE-FG02-08ER64658 (OASIS) - Final Technical Report

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sharman, Jonathan

Project OASIS (Operation of Advanced Structures, Interfaces and Sub-components for MEAs) was a 12 month project that ran from 1st September 2008 to 31st August 2009, and was managed by the Department of Energy Office of Science, Chicago Office, as Award No DE-FG02-08ER64658, with Johnson Matthey Fuel Cells Inc. as the sole contractor. The project was completed on schedule, with technical successes (details below) and payment of the full grant award made by DOE. The aim of the project was the development of membrane electrode assemblies (MEAs) for H2/air polymer electrolyte membrane (PEM) fuel cells that would give higher performancemore » under hot/dry and dry operating conditions, ideally with no loss of performance under wet conditions. Reducing or eliminating the need for humidifying the incoming gases will allow significant system cost and size reduction for many fuel cell applications including automotive, stationary and back-up power, and portable systems. Portable systems are also of particular interest in military markets. In previous work Johnson Matthey Fuel Cells had developed very stable, corrosion-resistant catalysts suitable for resisting degradation by carbon corrosion in particular. These materials were applied within the OASIS project as they are considered necessary for systems such as automotive where multiple start-stop events are experienced. These catalysts were contrasted with more conventional materials in the design of catalyst layers and novel microporous layers (MPLs) and gas diffusion layer (GDL) combinations were also explored. Early on in the work it was shown how much more aggressive high temperature operation is than dry operation. At the same humidity, tests at 110?C caused much more dehydration than tests at 80?C and the high temperature condition was much more revealing of improvements made to MEA design. Alloy catalysts were introduced and compared with Pt catalysts with a range of particle sizes. It was apparent that the larger particle sizes of the alloy catalysts led to a reduction in performance that offset much of their kinetic advantage. The Pt-only materials clearly showed that small particles are beneficial to good performance under hot/dry conditions, because of their higher surface area, although they are known to be less stable to cyclic operation. An ex-situ water vapour sorption technique was developed that showed a very clear correlation with in-cell performance: catalyst powders that absorbed more water gave better performance in-cell. It was shown that alloy catalysts could give a 25 mV advantage over Pt-only at 1 Acm-2. GDL design was also shown to influence performance and more permeable GDLs on the anode allowed better membrane hydration and therefore conductivity. A very impermeable GDL on the cathode caused cathode flooding even under dry conditions, but a novel cathode MPL incorporating ionomer and operating at 110?C, 33/17% RH showed a 150 mV gain at 800 mAcm-2 over the conventional MPL. This project has increased the understanding of the factors that influence performance loss under dry conditions, including the development of an insightful ex-situ characterisation technique (Dynamic Vapour Sorption). All the approaches investigated can be readily implemented in state-of the-art MEAs, although optimisation would be needed to integrate the new designs with existing MEA types and to tune to the exact range of operating conditions. The work is thus expected to benefit the public by feeding through more condition-tolerant production MEAs to a range of applications and thereby accelerate the commercialisation of fuel cell technology. In summary, a number of specific catalyst, catalyst layer, MPL and GDL improvements were made during this project. Often the best designs under dry conditions translated to some performance loss under wet conditions, but compromise situations were also found where dry performance was improved with no loss of wet performance.« less

Novel synthesis of highly durable and active Pt catalyst encapsulated in nitrogen containing carbon for polymer electrolyte membrane fuel cell

NASA Astrophysics Data System (ADS)

Lee, Hyunjoon; Sung, Yung-Eun; Choi, Insoo; Lim, Taeho; Kwon, Oh Joong

2017-09-01

Novel synthesis of a Pt catalyst encapsulated in a N-containing carbon layer for use in a polymer electrolyte membrane fuel cell is described in this study. A Pt-aniline complex, formed by mixing Pt precursor and aniline monomer, was used as the source of Pt, C, and N. Heat treatment of the Pt-aniline complex with carbon black yielded 5 nm Pt nanoparticles encapsulated by a N-containing carbon layer originating from aniline carbonization. The synthesized Pt catalyst exhibited higher mass specific activity to oxygen reduction reaction than that shown by conventional Pt/C catalyst because pyridinic N with graphitic carbon in the carbon layer provided active sites for oxygen reduction reaction in addition to those provided by Pt. In single cell testing, initial performance of the synthesized catalyst was limited because the thick catalyst layer increased resistance related to mass transfer. However, it was observed that the carbon layer successfully prevented Pt nanoparticles from growing via agglomeration and Ostwald ripening under fuel cell operation, thereby improving durability. Furthermore, a mass specific performance of the synthesized catalyst higher than that of a conventional Pt/C catalyst was achieved by modifying the synthesized catalyst's layer thickness.

Fuel cell anode configuration for CO tolerance

DOEpatents

Uribe, Francisco A.; Zawodzinski, Thomas A.

2004-11-16

A polymer electrolyte fuel cell (PEFC) is designed to operate on a reformate fuel stream containing oxygen and diluted hydrogen fuel with CO impurities. A polymer electrolyte membrane has an electrocatalytic surface formed from an electrocatalyst mixed with the polymer and bonded on an anode side of the membrane. An anode backing is formed of a porous electrically conductive material and has a first surface abutting the electrocatalytic surface and a second surface facing away from the membrane. The second surface has an oxidation catalyst layer effective to catalyze the oxidation of CO by oxygen present in the fuel stream where at least the layer of oxidation catalyst is formed of a non-precious metal oxidation catalyst selected from the group consisting of Cu, Fe, Co, Tb, W, Mo, Sn, and oxides thereof, and other metals having at least two low oxidation states.

Comparison of attrition test methods: ASTM standard fluidized bed vs jet cup

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhao, R.; Goodwin, J.G. Jr.; Jothimurugesan, K.

2000-05-01

Attrition resistance is one of the key design parameters for catalysts used in fluidized-bed and slurry phase types of reactors. The ASTM fluidized-bed test has been one of the most commonly used attrition resistance evaluation methods; however, it requires the use of 50 g samples--a large amount for catalyst development studies. Recently a test using the jet cup requiring only 5 g samples has been proposed. In the present study, two series of spray-dried iron catalysts were evaluated using both the ASTM fluidized-bed test and a test based on the jet cup to determine this comparability. It is shown thatmore » the two tests give comparable results. This paper, by reporting a comparison of the jet-cup test with the ASTM standard, provides a basis for utilizing the more efficient jet cup with confidence in catalyst attrition studies.« less

Pt-Ni/WC Alloy Nanorods Arrays as ORR Catalyst for PEM Fuel Cells

DOE Office of Scientific and Technical Information (OSTI.GOV)

Begum, Mahbuba; Yurukcu, Mesut; Yurtsever, Fatma

Polymer electrolyte membrane fuel cells (PEMFCs) among the other types of fuel cell technology are attractive power sources, especially for electric vehicle applications. While significant progress and plausible prospects of PEMFCs have been achieved, there are still some challenges related to the performance, durability, and cost that need to be overcome to make them economically viable for widespread commercialization. Our strategy is to develop thin films of high-active and stable catalyst coated on vertically aligned nanorod arrays of conductive and stable support. In this work, we fabricated tungsten carbide (WC) nanorods as support and coated them with a platinum-nickel (Pt-Ni)more » alloy shell denoted as Pt-Ni/WC catalysts. The Pt- Ni/WC nanorods were deposited on glassy carbon disks as well as on silicon substrates for evaluation of their electrocatalytic oxygen reduction reaction (ORR) activity and physical properties. Cyclic voltammetry experiments using rotating disk electrode were performed in perchloric acid (0.1 M HClO4) electrolyte at room temperature to characterize the ORR activity and stability of Pt-Ni/WC nanorods catalysts. Scanning electron microscopy and X-ray diffraction techniques were utilized to study the morphology and crystallographic properties, respectively.« less

Alkaline direct alcohol fuel cells using an anion exchange membrane

NASA Astrophysics Data System (ADS)

Matsuoka, Koji; Iriyama, Yasutoshi; Abe, Takeshi; Matsuoka, Masao; Ogumi, Zempachi

Alkaline direct alcohol fuel cells using an OH-form anion exchange membrane and polyhydric alcohols were studied. A high open circuit voltage of ca. 800 mV was obtained for a cell using Pt-Ru/C (anode) and Pt/C (cathode) at 323 K, which was about 100-200 mV higher than that for a DMFC using Nafion ®. The maximum power densities were in the order of ethylene glycol > glycerol > methanol > erythritol > xylitol. Silver catalysts were used as a cathode catalyst to fabricate alkaline fuel cells, since silver catalyst is almost inactive in the oxidation of polyhydric alcohols. Alkaline direct ethylene glycol fuel cells using silver as a cathode catalyst gave excellent performance because higher concentrations of fuel could be supplied to the anode.

Catalytic reforming of methane to syngas in an oxygen-permeative membrane reactor

NASA Astrophysics Data System (ADS)

Urano, Takeshi; Kubo, Keiko; Saito, Tomoyuki; Hitomi, Atsushi

2011-05-01

For fuel cell applications, partial oxidative reforming of methane to syngas, hydrogen and carbon monoxide, was performed via a dense oxygen-permeative ceramic membrane composed by both ionic and electronic conductive materials. The modification of Ni-based catalyst by noble metals was investigated to increase oxygen permeation flux and decrease carbon deposition during reforming reaction. The role of each component in catalyst was also discussed.

Immobilized biocatalytic process development and potential application in membrane separation: a review.

PubMed

Chakraborty, Sudip; Rusli, Handajaya; Nath, Arijit; Sikder, Jaya; Bhattacharjee, Chiranjib; Curcio, Stefano; Drioli, Enrico

2016-01-01

Biocatalytic membrane reactors have been widely used in different industries including food, fine chemicals, biological, biomedical, pharmaceuticals, environmental treatment and so on. This article gives an overview of the different immobilized enzymatic processes and their advantages over the conventional chemical catalysts. The application of a membrane bioreactor (MBR) reduces the energy consumption, and system size, in line with process intensification. The performances of MBR are considerably influenced by substrate concentration, immobilized matrix material, types of immobilization and the type of reactor. Advantages of a membrane associated bioreactor over a free-enzyme biochemical reaction, and a packed bed reactor are, large surface area of immobilization matrix, reuse of enzymes, better product recovery along with heterogeneous reactions, and continuous operation of the reactor. The present research work highlights immobilization techniques, reactor setup, enzyme stability under immobilized conditions, the hydrodynamics of MBR, and its application, particularly, in the field of sugar, starch, drinks, milk, pharmaceutical industries and energy generation.

Nanoscale current imaging of the conducting channels in proton exchange membrane fuel cells.

PubMed

Bussian, David A; O'Dea, James R; Metiu, Horia; Buratto, Steven K

2007-02-01

The electrochemically active area of a proton exchange membrane fuel cell (PEMFC) is investigated using conductive probe atomic force microscopy (CP-AFM). A platinum-coated AFM tip is used as a nanoscale cathode in an operating PEMFC. We present results that show highly inhomogeneous distributions of conductive surface domains at several length scales. At length scales on the order of the aqueous domains of the membrane, approximately 50 nm, we observe single channel electrochemistry. I-V curves for single conducting channels are obtained, which yield insight into the nature of conductive regions across the PEM. In addition, we demonstrate a new characterization technique, phase current correlation microscopy, which gives a direct measure of the electrochemical activity for each aqueous domain. This shows that a large number ( approximately 60%) of the aqueous domains present at the surface of an operating Nafion membrane are inactive. We attribute this to a combination of limited aqueous domain connectivity and catalyst accessibility.

Oxygen-consuming chlor alkali cell configured to minimize peroxide formation

DOEpatents

Chlistunoff, Jerzy B [Los Alamos, NM; Lipp, Ludwig [Brookfield, CT; Gottesfeld, Shimshon [Niskayuna, NY

2006-08-01

Oxygen-consuming zero gap chlor-alkali cell was configured to minimize peroxide formation. The cell included an ion-exchange membrane that divided the cell into an anode chamber including an anode and a cathode chamber including an oxygen gas diffusion cathode. The cathode included a single-piece of electrically conducting graphitized carbon cloth. Catalyst and polytetrafluoroethylene were attached to only one side of the cloth. When the cathode was positioned against the cation exchange membrane with the catalyst side away from the membrane, electrolysis of sodium chloride to chlorine and caustic (sodium hydroxide) proceeded with minimal peroxide formation.

Quaternized poly(styrene ethylene butylene poly styrene)/multiwalled carbon nanotube composites for alkaline fuel cell applications.

PubMed

Vinodh, Rajangam; Sangeetha, Dharmalingam

2013-08-01

The present study is aimed at synthesizing a novel anion exchange composite membrane from quaternized polystyrene-block-poly(ethylene-ran-butylene)-block-polystyrene [QPSEBS] and functionalized multi walled carbon nanotubes (f-MWCNT) by solution casting method. The characteristic properties of the QPSEBS/f-MWCNT composite membranes were investigated using Fourier transform infrared (FTIR), UV-Visible spectroscopy, thermo-gravimetric analysis (TGA), scanning electron microscopy (SEM), X-ray diffraction (XRD) studies and Raman spectroscopy. The water uptake, ion exchange capacity, ionic conductivity, methanol permeability and selectivity ratio of the membranes were also studied. The prepared composite membranes were tested in an in-house fabricated alkaline membrane fuel cell (AMFC) set up using Pt/C as the common anode catalyst and three different cathode catalysts namely Pt/C, Pd-Ni/C and Ag/C. Among all the three cathode catalysts, Pt/C for QPSEBS/5% f-MWCNT is found to show the maximum power density and open circuit voltage (OCV) of 187 mW cm(-2) and 0.73 V respectively. For direct methanol alkaline membrane fuel cells (DMAMFC), the OCV of QPSEBS/5% f-MWCNT is found to be 0.76 V and the maximum power density of 59.5 mW cm(-2) is achieved at a current density of 175 mA cm(-2).

Ultrasonic technique for measuring porosity of plasma-sprayed alumina coatings

NASA Astrophysics Data System (ADS)

Parthasarathi, S.; Tittmann, B. R.; Onesto, E. J.

1997-12-01

Porosity is an important factor in plasma-sprayed coatings, especially ceramic coatings. Excessive poros-ity can adversely affect the performance of the coated component in various ways. An ultrasonic nonde-structive measurement technique has been developed to measure porosity in plasma-sprayed alumina coatings. The technique is generic and can be extended to other ceramic coating systems. To test the tech-nique, freestanding alumina coatings with varying levels of porosity were fabricated via plasma spray. Samples with varying porosity, obtained through innovative fabrication techniques, were used to gener-ate a calibration curve. The ultrasonic velocity in the low-frequency range was found to be dependent on the density of freestanding coatings (measured via Archimedian techniques). This dependence is the basis of the development of a technique to measure the density of coatings.

Electrospraying and ultraviolet light curing of nanometer-thin polydimethylsiloxane membranes for low-voltage dielectric elastomer transducers

NASA Astrophysics Data System (ADS)

Osmani, Bekim; Töpper, Tino; Siketanc, Matej; Kovacs, Gabor M.; Müller, Bert

2017-04-01

Dielectric elastomer transducers (DETs) have attracted interest as actuators, sensors, and even as self-sensing actuators for applications in medicine, soft robotics, and microfluidics. To reach strains of more than 10 %, they currently require operating voltages of several hundred volts. In medical applications for artificial muscles, however, their operation is limited to a very few tens of volts, which implies high permittivity materials and thin-film structures. Such micro- or nanostructures can be prepared using electro-spraying, a cost-effective technique that allows upscaling using multiple nozzles for the fabrication of silicone films down to nanometer thickness. Deposition rates of several micrometers per hour have already been reached. It has been recently demonstrated that such membranes can be fabricated by electro-spraying and subsequent ultraviolet light irradiation. Herein, we introduce a relatively fast deposition of a dimethyl silicone copolymer fluid that contains mercaptopropyl side chains in addition to the methyl groups. Its elastic modulus was tuned with the irradiation dose of the 200 W Hg-Xe lamp. We also investigated the formation of elastomer films, using polymer concentrations in ethyl acetate of 1, 2, 5 and 10 vol%. After curing, the surface roughness was measured by means of atomic force microscopy. This instrument also enabled us to determine the average elastic modulus out of, for example, 400 nanoindentation measurements, using a spherical tip with a radius of 500 nm. The elastomer films were cured for a period of less than one minute, a speed that makes it feasible to combine electro-spraying and in situ curing in a single process step for fabricating low-voltage, multilayer DETs.

Investigation of the Interaction between Nafion Ionomer and Surface Functionalized Carbon Black Using Both Ultrasmall Angle X-ray Scattering and Cryo-TEM

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang, Fan; Xin, Le; Uzunoglu, Aytekin

In making a catalyst ink, the interaction between Nafion ionomer and catalyst support are the key factors that directly affect both ionic conductivity and electronic conductivity of the catalyst layer in a membrane electrode assembly (MEA). One of the major aims of this investigation is to understand the behavior of the catalyst support, Vulcan XC-72 (XC-72) aggregates, in the existence of the Nafion ionomer in a catalyst ink to fill the knowledge gap of the interaction of these components. The dispersion of catalyst ink not only depends on the solvent, but also depends on the interaction of Nafion and carbonmore » particles in the ink. The interaction of Nafion ionomer particles and XC-72 catalyst aggregates in liquid media was studied using ultra small angle x-ray scattering (USAXS) and cryogenic TEM techniques. Carbon black XC-72) and functionalized carbon black systems were introduced to study the interaction behaviors. A multiple curve fitting was used to extract the particle size and size distribution from scattering data. The results suggest that the particle size and size distribution of each system changed significantly in Nafion + XC-72 system, Nafion + NH2-XC72 system, and Nafion + SO3H-XC-72 system, which indicates that an interaction among these components (i.e. ionomer particles and XC-72 aggregates) exists. The cryogenic TEM, which allows for the observation the size of particles in a liquid, was used to validate the scattering results and shows excellent agreement.« less

NiMn layered double hydroxide nanosheets/NiCo2O4 nanowires with surface rich high valence state metal oxide as an efficient electrocatalyst for oxygen evolution reaction

NASA Astrophysics Data System (ADS)

Yang, Liting; Chen, Lin; Yang, Dawen; Yu, Xu; Xue, Huaiguo; Feng, Ligang

2018-07-01

High valence transition metal oxide is significant for anode catalyst of proton membrane water electrolysis technique. Herein, we demonstrate NiMn layered double hydroxide nanosheets/NiCo2O4 nanowires hierarchical nanocomposite catalyst with surface rich high valence metal oxide as an efficient catalyst for oxygen evolution reaction. A low overpotential of 310 mV is needed to drive a 10 mA cm-2 with a Tafel slope of 99 mV dec-1, and a remarkable stability during 8 h is demonstrated in a chronoamperometry test. Theoretical calculation displays the change in the rate-determining step on the nanocomposite electrode in comparison to NiCo2O4 nanowires alone. It is found high valence Ni and Mn oxide in the catalyst system can efficiently facilitate the charge transport across the electrode/electrolyte interface. The enhanced electrical conductivity, more accessible active sites and synergistic effects between NiMn layered double hydroxide nanosheets and NiCo2O4 nanowires can account for the excellent oxygen evolution reaction. The catalytic performance is comparable to most of the best non-noble catalysts and IrO2 noble catalyst, indicating the promising applications in water-splitting technology. It is an important step in the development of hierarchical nanocomposites by surface valence state tuning as an alternative to noble metals for oxygen evolution reaction.

Solar fuel generator

DOEpatents

Lewis, Nathan S.; West, William C.

2017-01-17

The disclosure provides conductive membranes for water splitting and solar fuel generation. The membranes comprise an embedded semiconductive/photoactive material and an oxygen or hydrogen evolution catalyst. Also provided are chassis and cassettes containing the membranes for use in fuel generation.

Solar Fuel Generator

NASA Technical Reports Server (NTRS)

West, William C. (Inventor); Lewis, Nathan S. (Inventor)

2017-01-01

The disclosure provides conductive membranes for water splitting and solar fuel generation. The membranes comprise an embedded semiconductive/photoactive material and an oxygen or hydrogen evolution catalyst. Also provided are chassis and cassettes containing the membranes for use in fuel generation.

Performance of polymer nano composite membrane electrode assembly using Alginate as a dopant in polymer electrolyte membrane fuel cell

NASA Astrophysics Data System (ADS)

Mulijani, S.

2017-01-01

Polymer membrane and composite polymer for membrane electrode assembly (MEAs) are synthesized and studied for usage in direct methanol fuel cell (DMFC). In this study, we prepared 3 type of MEAs, polystyrene (PS), sulfonated polystyrene (SPS) and composite polymer SPS-alginat membrane via catalyst hot pressed method. The performance and properties of prepared MEAs were evaluated and analyzed by impedance spectrometry and scanning electron microscopy (SEM). The result showed that, water up take of MEA composite polymer SPS-alginate was obtained higher than that in SPS and PS. The proton conductivity of MEA-SPS-alginate was also higher than that PS and PSS. SEM characterization revealed that the intimate contact between the carbon catalyst layers (CL) and the membranes, and the uniformly porous structure correlate positively with the MEAs prepared by hot pressed method, exhibiting high performances for DMFC.

Catalytic, Conductive Bipolar Membrane Interfaces through Layer-by-Layer Deposition for the Design of Membrane-Integrated Artificial Photosynthesis Systems.

PubMed

McDonald, Michael B; Freund, Michael S; Hammond, Paula T

2017-11-23

In the presence of an electric field, bipolar membranes (BPMs) are capable of initiating water disassociation (WD) within the interfacial region, which can make water splitting for renewable energy in the presence of a pH gradient possible. In addition to WD catalytic efficiency, there is also the need for electronic conductivity in this region for membrane-integrated artificial photosynthesis (AP) systems. Graphene oxide (GO) was shown to catalyze WD and to be controllably reduced, which resulted in electronic conductivity. Layer-by-layer (LbL) film deposition was employed to improve GO film uniformity in the interfacial region to enhance WD catalysis and, through the addition of a conducting polymer in the process, add electronic conductivity in a hybrid film. Three different deposition methods were tested to optimize conducting polymer synthesis with the oxidant in a metastable solution and to yield the best film properties. It was found that an approach that included substrate dipping in a solution containing the expected final monomer/oxidant ratio provided the most predictable film growth and smoothest films (by UV/Vis spectroscopy and atomic force microscopy/scanning electron microscopy, respectively), whereas dipping in excess oxidant or co-spraying the oxidant and monomer produced heterogeneous films. Optimized films were found to be electronically conductive and produced a membrane ohmic drop that was acceptable for AP applications. Films were integrated into the interfacial region of BPMs and revealed superior WD efficiency (≥1.4 V at 10 mA cm -2 ) for thinner films (<10 bilayers≈100 nm) than for either the pure GO catalyst or conducting polymer individually, which indicated that there was a synergistic effect between these materials in the structure configured by the LbL method. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Laser absorption-scattering technique applied to asymmetric evaporating fuel sprays for simultaneous measurement of vapor/liquid mass distributions

NASA Astrophysics Data System (ADS)

Gao, J.; Nishida, K.

2010-10-01

This paper describes an Ultraviolet-Visible Laser Absorption-Scattering (UV-Vis LAS) imaging technique applied to asymmetric fuel sprays. Continuing from the previous studies, the detailed measurement principle was derived. It is demonstrated that, by means of this technique, cumulative masses and mass distributions of vapor/liquid phases can be quantitatively measured no matter what shape the spray is. A systematic uncertainty analysis was performed, and the measurement accuracy was also verified through a series of experiments on the completely vaporized fuel spray. The results show that the Molar Absorption Coefficient (MAC) of the test fuel, which is typically pressure and temperature dependent, is the major error source. The measurement error in the vapor determination has been shown to be approximately 18% under the assumption of constant MAC of the test fuel. Two application examples of the extended LAS technique were presented for exploring the dynamics and physical insight of the evaporating fuel sprays: diesel sprays injected by group-hole nozzles and gasoline sprays impinging on an inclined wall.

Degradation of organic dyes using spray deposited nanocrystalline stratified WO3/TiO2 photoelectrodes under sunlight illumination

NASA Astrophysics Data System (ADS)

Hunge, Y. M.; Yadav, A. A.; Mahadik, M. A.; Bulakhe, R. N.; Shim, J. J.; Mathe, V. L.; Bhosale, C. H.

2018-02-01

The need to utilize TiO2 based metal oxide hetero nanostructures for the degradation of environmental pollutants like Rhodamine B and reactive red 152 from the wastewater using stratified WO3/TiO2 catalyst under sunlight illumination. WO3, TiO2 and stratified WO3/TiO2 catalysts were prepared by a spray pyrolysis method. It was found that the stratified WO3/TiO2 heterostructure has high crystallinity, no mixed phase formation occurs, strong optical absorption in the visible region of the solar spectrum, and large surface area. The photocatalytic activity was tested for degradation of Rhodamine B (Rh B) and reactive red 152 in an aqueous medium. TiO2 layer in stratified WO3/TiO2 catalyst helps to extend its absorption spectrum in the solar light region. Rh B and Reactive red 152is eliminated up to 98 and 94% within the 30 and 40 min respectively at optimum experimental condition by stratified WO3/TiO2. Moreover, stratified WO3/TiO2 photoelectrode has good stability and reusability than individual TiO2 and WO3 thin film in the degradation of Rh B and reactive red 152. The photoelectrocatalytic experimental results indicate that stratified WO3/TiO2 photoelectrode is a promising material for dye removal.

Catalyst containing oxygen transport membrane

DOEpatents

Christie, Gervase Maxwell; Wilson, Jamie Robyn; van Hassel, Bart Antonie

2012-12-04

A composite oxygen transport membrane having a dense layer, a porous support layer and an intermediate porous layer located between the dense layer and the porous support layer. Both the dense layer and the intermediate porous layer are formed from an ionic conductive material to conduct oxygen ions and an electrically conductive material to conduct electrons. The porous support layer has a high permeability, high porosity, and a high average pore diameter and the intermediate porous layer has a lower permeability and lower pore diameter than the porous support layer. Catalyst particles selected to promote oxidation of a combustible substance are located in the intermediate porous layer and in the porous support adjacent to the intermediate porous layer. The catalyst particles can be formed by wicking a solution of catalyst precursors through the porous support toward the intermediate porous layer.

Effect of spray application technique on spray deposition in greenhouse strawberries and tomatoes.

PubMed

Braekman, Pascal; Foque, Dieter; Messens, Winy; Van Labeke, Marie-Christine; Pieters, Jan G; Nuyttens, David

2010-02-01

Increasingly, Flemish greenhouse growers are using spray booms instead of spray guns to apply plant protection products. Although the advantages of spray booms are well known, growers still have many questions concerning nozzle choice and settings. Spray deposition using a vertical spray boom in tomatoes and strawberries was compared with reference spray equipment. Five different settings of nozzle type, size and pressure were tested with the spray boom. In general, the standard vertical spray boom performed better than the reference spray equipment in strawberries (spray gun) and in tomatoes (air-assisted sprayer). Nozzle type and settings significantly affected spray deposition and crop penetration. Highest overall deposits in strawberries were achieved using air-inclusion or extended-range nozzles. In tomatoes, the extended-range nozzles and the twin air-inclusion nozzles performed best. Using smaller-size extended-range nozzles above the recommended pressure range resulted in lower deposits, especially inside the crop canopy. The use of a vertical spray boom is a promising technique for applying plant protection products in a safe and efficient way in tomatoes and strawberries, and nozzle choice and setting should be carefully considered.

Graphitized Carbon: A Promising Stable Cathode Catalyst Support Material for Long Term PEMFC Applications.

PubMed

Mohanta, Paritosh Kumar; Regnet, Fabian; Jörissen, Ludwig

2018-05-28

Stability of cathode catalyst support material is one of the big challenges of polymer electrolyte membrane fuel cells (PEMFC) for long term applications. Traditional carbon black (CB) supports are not stable enough to prevent oxidation to CO₂ under fuel cell operating conditions. The feasibility of a graphitized carbon (GC) as a cathode catalyst support for low temperature PEMFC is investigated herein. GC and CB supported Pt electrocatalysts were prepared via an already developed polyol process. The physical characterization of the prepared catalysts was performed using transmission electron microscope (TEM), X-ray Powder Diffraction (XRD) and inductively coupled plasma optical emission spectrometry (ICP-OES) analysis, and their electrochemical characterizations were conducted via cyclic voltammetry(CV), rotating disk electrode (RDE) and potential cycling, and eventually, the catalysts were processed using membrane electrode assemblies (MEA) for single cell performance tests. Electrochemical impedance spectroscopy (EIS) and scanning electrochemical microscopy (SEM) have been used as MEA diagonostic tools. GC showed superior stability over CB in acid electrolyte under potential conditions. Single cell MEA performance of the GC-supported catalyst is comparable with the CB-supported catalyst. A correlation of MEA performance of the supported catalysts of different Brunauer⁻Emmett⁻Teller (BET) surface areas with the ionomer content was also established. GC was identified as a promising candidate for catalyst support in terms of both of the stability and the performance of fuel cell.

Insights into Spray Development from Metered-Dose Inhalers Through Quantitative X-ray Radiography

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mason-Smith, Nicholas; Duke, Daniel J.; Kastengren, Alan L.

Typical methods to study pMDI sprays employ particle sizing or visible light diagnostics, which suffer in regions of high spray density. X-ray techniques can be applied to pharmaceutical sprays to obtain information unattainable by conventional particle sizing and light-based techniques. We present a technique for obtaining quantitative measurements of spray density in pMDI sprays. A monochromatic focused X-ray beam was used to perform quantitative radiography measurements in the near-nozzle region and plume of HFA-propelled sprays. Measurements were obtained with a temporal resolution of 0.184 ms and spatial resolution of 5 mu m. Steady flow conditions were reached after around 30more » ms for the formulations examined with the spray device used. Spray evolution was affected by the inclusion of ethanol in the formulation and unaffected by the inclusion of 0.1% drug by weight. Estimation of the nozzle exit density showed that vapour is likely to dominate the flow leaving the inhaler nozzle during steady flow. Quantitative measurements in pMDI sprays allow the determination of nozzle exit conditions that are difficult to obtain experimentally by other means. Measurements of these nozzle exit conditions can improve understanding of the atomization mechanisms responsible for pMDI spray droplet and particle formation.« less

Discovery of true electrochemical reactions for ultrahigh catalyst mass activity in water splitting

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mo, Jingke; Kang, Zhenye; Retterer, Scott T.

Better understanding of true electrochemical reaction behaviors in electrochemical energy devices has long been desired. It has been assumed so far that the reactions occur across the entire catalyst layer (CL), which is designed and fabricated uniformly with catalysts, conductors of protons and electrons, and pathways for reactants and products. By introducing a state-of-the-art characterization system, a thin, highly tunable liquid/gas diffusion layer (LGDL), and an innovative design of electrochemical proton exchange membrane electrolyzer cells (PEMECs), the electrochemical reactions on both microspatial and microtemporal scales are revealed for the first time. Surprisingly, reactions occur only on the CL adjacent tomore » good electrical conductors. On the basis of these findings, new CL fabrications on the novel LGDLs exhibit more than 50 times higher mass activity than conventional catalyst-coated membranes in PEMECs. In conclusion, this discovery presents an opportunity to enhance the multiphase interfacial effects, maximizing the use of the catalysts and significantly reducing the cost of these devices.« less

Discovery of true electrochemical reactions for ultrahigh catalyst mass activity in water splitting

PubMed Central

Mo, Jingke; Kang, Zhenye; Retterer, Scott T.; Cullen, David A.; Toops, Todd J.; Green, Johney B.; Mench, Matthew M.; Zhang, Feng-Yuan

2016-01-01

Better understanding of true electrochemical reaction behaviors in electrochemical energy devices has long been desired. It has been assumed so far that the reactions occur across the entire catalyst layer (CL), which is designed and fabricated uniformly with catalysts, conductors of protons and electrons, and pathways for reactants and products. By introducing a state-of-the-art characterization system, a thin, highly tunable liquid/gas diffusion layer (LGDL), and an innovative design of electrochemical proton exchange membrane electrolyzer cells (PEMECs), the electrochemical reactions on both microspatial and microtemporal scales are revealed for the first time. Surprisingly, reactions occur only on the CL adjacent to good electrical conductors. On the basis of these findings, new CL fabrications on the novel LGDLs exhibit more than 50 times higher mass activity than conventional catalyst-coated membranes in PEMECs. This discovery presents an opportunity to enhance the multiphase interfacial effects, maximizing the use of the catalysts and significantly reducing the cost of these devices. PMID:28138516

Discovery of true electrochemical reactions for ultrahigh catalyst mass activity in water splitting

DOE PAGES

Mo, Jingke; Kang, Zhenye; Retterer, Scott T.; ...

2016-11-18

Better understanding of true electrochemical reaction behaviors in electrochemical energy devices has long been desired. It has been assumed so far that the reactions occur across the entire catalyst layer (CL), which is designed and fabricated uniformly with catalysts, conductors of protons and electrons, and pathways for reactants and products. By introducing a state-of-the-art characterization system, a thin, highly tunable liquid/gas diffusion layer (LGDL), and an innovative design of electrochemical proton exchange membrane electrolyzer cells (PEMECs), the electrochemical reactions on both microspatial and microtemporal scales are revealed for the first time. Surprisingly, reactions occur only on the CL adjacent tomore » good electrical conductors. On the basis of these findings, new CL fabrications on the novel LGDLs exhibit more than 50 times higher mass activity than conventional catalyst-coated membranes in PEMECs. In conclusion, this discovery presents an opportunity to enhance the multiphase interfacial effects, maximizing the use of the catalysts and significantly reducing the cost of these devices.« less

A Planar-Fluorescence Imaging Technique for Studying Droplet-Turbulence Interactions in Vaporizing Sprays

NASA Technical Reports Server (NTRS)

Santavicca, Dom A.; Coy, E.

1990-01-01

Droplet turbulence interactions directly affect the vaporization and dispersion of droplets in liquid sprays and therefore play a major role in fuel oxidizer mixing in liquid fueled combustion systems. Proper characterization of droplet turbulence interactions in vaporizing sprays require measurement of droplet size velocity and size temperature correlations. A planar, fluorescence imaging technique is described which is being developed for simultaneously measuring the size, velocity, and temperature of individual droplets in vaporizing sprays. Preliminary droplet size velocity correlation measurements made with this technique are presented. These measurements are also compared to and show very good agreement with measurements made in the same spray using a phase Doppler particle analyzer.

A Review of Recent Developments in X-Ray Diagnostics for Turbulent and Optically Dense Rocket Sprays

NASA Technical Reports Server (NTRS)

Radke, Christopher; Halls, Benjamin; Kastengren, Alan; Meyer, Terrence

2017-01-01

Highly efficient mixing and atomization of fuel and oxidizers is an important factor in many propulsion and power generating applications. To better quantify breakup and mixing in atomizing sprays, several diagnostic techniques have been developed to collect droplet information and spray statistics. Several optical based techniques, such as Ballistic Imaging and SLIPI have previously demonstrated qualitative measurements in optically dense sprays, however these techniques have produced limited quantitative information in the near injector region. To complement to these advances, a recent wave of developments utilizing synchrotron based x-rays have been successful been implemented facilitating the collection of quantitative measurements in optically dense sprays.

[Study on spray-drier preparation technology of weitai granules using orthogonal experiments].

PubMed

Qu, Cai-Hong; Yang, Li; Chen, Zhi-Liang

2006-04-01

To screen preparation technique in order to raise the end-product and economical efficiency of spray-drier preparation technology of weitai granules. Newly Fluid-bed-spray-drier-granulation technique was adoped and taken extracting technique, temperature of exit and entry and the matching of accessories as inspecting factors, two levels of each factors, end-product and the water content of semi-finished weitai granules as inspecting marker, the best preparation technique of weitai granules was screened by orthogonal desing. Among the 3 factors, the matching of accessories was most notalbe (P < 0.01), next was the temperature of exit and entry (P < 0.05). However, the extracting technique was of little importance (P > 0.05). The optimum spray-drier granulation technique of weitai granules is A3B1C3.

Formation of Platinum Catalyst on Carbon Black Using an In-Liquid Plasma Method for Fuel Cells.

PubMed

Show, Yoshiyuki; Ueno, Yutaro

2017-01-31

Platinum (Pt) catalyst was formed on the surface of carbon black using an in-liquid plasma method. The formed Pt catalyst showed the average particle size of 4.1 nm. This Pt catalyst was applied to a polymer electrolyte membrane fuel cell (PEMFC). The PEMFC showed an open voltage of 0.85 V and a maximum output power density of 216 mW/cm2.

Formation of Platinum Catalyst on Carbon Black Using an In-Liquid Plasma Method for Fuel Cells

PubMed Central

Show, Yoshiyuki; Ueno, Yutaro

2017-01-01

Platinum (Pt) catalyst was formed on the surface of carbon black using an in-liquid plasma method. The formed Pt catalyst showed the average particle size of 4.1 nm. This Pt catalyst was applied to a polymer electrolyte membrane fuel cell (PEMFC). The PEMFC showed an open voltage of 0.85 V and a maximum output power density of 216 mW/cm2. PMID:28336864

Chemical compositions, methods of making the chemical compositions, and structures made from the chemical compositions

DOEpatents

Yang, Lei; Cheng, Zhe; Liu, Ze; Liu, Meilin

2015-01-13

Embodiments of the present disclosure include chemical compositions, structures, anodes, cathodes, electrolytes for solid oxide fuel cells, solid oxide fuel cells, fuel cells, fuel cell membranes, separation membranes, catalytic membranes, sensors, coatings for electrolytes, electrodes, membranes, and catalysts, and the like, are disclosed.

An application of digital image processing techniques to the characterization of liquid petroleum gas (LPG) spray

NASA Astrophysics Data System (ADS)

Qi, Y. L.; Xu, B. Y.; Cai, S. L.

2006-12-01

To control fuel injection, optimize combustion and reduce emissions for LPG (liquefied petroleum gas) engines, it is necessary and important to understand the characteristics of LPG sprays. The present work investigates the geometry of LPG sprays, including spray tip penetration, spray angle, projected spray area and spray volume, by using schlieren photography and digital image processing techniques. Two types of single nozzle injectors were studied, with the same nozzle diameter, but one with and one without a double-hole flow-split head. A code developed to analyse the results directly from the digitized images is shown to be more accurate and efficient than manual measurement and analysis. Test results show that a higher injection pressure produces a longer spray tip penetration, a larger projected spray area and spray volume, but a smaller spray cone angle. The injector with the double-hole split-head nozzle produces better atomization and shorter tip penetration at medium and late injection times, but longer tip penetration in the early stage.

Catalytic nanoporous membranes

DOEpatents

Pellin, Michael J [Naperville, IL; Hryn, John N [Naperville, IL; Elam, Jeffrey W [Elmhurst, IL

2009-12-01

A nanoporous catalytic membrane which displays several unique features including pores which can go through the entire thickness of the membrane. The membrane has a higher catalytic and product selectivity than conventional catalysts. Anodic aluminum oxide (AAO) membranes serve as the catalyst substrate. This substrate is then subjected to Atomic Layer Deposition (ALD), which allows the controlled narrowing of the pores from 40 nm to 10 nm in the substrate by deposition of a preparatory material. Subsequent deposition of a catalytic layer on the inner surfaces of the pores reduces pore sizes to less than 10 nm and allows for a higher degree of reaction selectivity. The small pore sizes allow control over which molecules enter the pores, and the flow-through feature can allow for partial oxidation of reactant species as opposed to complete oxidation. A nanoporous separation membrane, produced by ALD is also provided for use in gaseous and liquid separations. The membrane has a high flow rate of material with 100% selectivity.

Growth of vertically aligned carbon nanotubes on silicon and quartz substrate by spray pyrolysis of a natural precursor: Turpentine oil

NASA Astrophysics Data System (ADS)

Afre, Rakesh A.; Soga, T.; Jimbo, T.; Kumar, Mukul; Ando, Y.; Sharon, M.

2005-10-01

Vertically aligned carbon nanotubes (VACNTs) were grown by spray pyrolysis of turpentine oil and ferrocene mixture at 700 °C. Using this simple method, we report the successful growth of vertically aligned nanotubes of 300 μm length and diameter in the range of 50-100 nm on Si(1 0 0) substrate. The ferrocene act as an in situ Fe catalyst precursor and forming the nanosize iron particles for formation of VACNTs on Si and quartz substrates. Morphological differences between aligned carbon nanotubes grown on different substrates are studied and discussed by SEM, TEM and Raman spectroscopy characterizations.

High Performance Fuel Cell and Electrolyzer Membrane Electrode Assemblies (MEAs) for Space Energy Storage Systems

NASA Technical Reports Server (NTRS)

Valdez, Thomas I.; Billings, Keith J.; Kisor, Adam; Bennett, William R.; Jakupca, Ian J.; Burke, Kenneth; Hoberecht, Mark A.

2012-01-01

Regenerative fuel cells provide a pathway to energy storage system development that are game changers for NASA missions. The fuel cell/ electrolysis MEA performance requirements 0.92 V/ 1.44 V at 200 mA/cm2 can be met. Fuel Cell MEAs have been incorporated into advanced NFT stacks. Electrolyzer stack development in progress. Fuel Cell MEA performance is a strong function of membrane selection, membrane selection will be driven by durability requirements. Electrolyzer MEA performance is catalysts driven, catalyst selection will be driven by durability requirements. Round Trip Efficiency, based on a cell performance, is approximately 65%.

Ceramic oxygen transport membrane array reactor and reforming method

DOEpatents

Kelly, Sean M.; Christie, Gervase Maxwell; Rosen, Lee J.; Robinson, Charles; Wilson, Jamie R.; Gonzalez, Javier E.; Doraswami, Uttam R.

2016-09-27

A commercially viable modular ceramic oxygen transport membrane reforming reactor for producing a synthesis gas that improves the thermal coupling of reactively-driven oxygen transport membrane tubes and catalyst reforming tubes required to efficiently and effectively produce synthesis gas.

Comparision on dynamic behavior of diesel spray and rapeseed oil spray in diesel engine

NASA Astrophysics Data System (ADS)

Sapit, Azwan; Azahari Razali, Mohd; Faisal Hushim, Mohd; Jaat, Norrizam; Nizam Mohammad, Akmal; Khalid, Amir

2017-04-01

Fuel-air mixing is important process in diesel combustion. It significantly affects the combustion and emission of diesel engine. Biomass fuel has high viscosity and high distillation temperature and may negatively affect the fuel-air mixing process. Thus, study on the spray development and atomization of this type of fuel is important. This study investigates the atomization characteristics and droplet dynamic behaviors of diesel engine spray fuelled by rapeseed oil (RO) and comparison to diesel fuel (GO). Optical observation of RO spray was carried out using shadowgraph photography technique. Single nano-spark photography technique was used to study the characteristics of the spray while dual nano-spark shadowgraph technique was used to study the spray droplet behavior. Using in-house image processing algorithm, the images were processed and the boundary condition of each spray was also studied. The results show that RO has very poor atomization due to the high viscosity nature of the fuel when compared to GO. This is in agreement with the results from spray droplet dynamic behavior studies that shows due to the high viscosity, the RO spray droplets are large in size and travel downward, with very little influence of entrainment effect due to its large kinematic energy.

Steam reforming of commercial ultra-low sulphur diesel

NASA Astrophysics Data System (ADS)

Boon, Jurriaan; van Dijk, Eric; de Munck, Sander; van den Brink, Ruud

Two main routes for small-scale diesel steam reforming exist: low-temperature pre-reforming followed by well-established methane steam reforming on the one hand and direct steam reforming on the other hand. Tests with commercial catalysts and commercially obtained diesel fuels are presented for both processes. The fuels contained up to 6.5 ppmw sulphur and up to 4.5 vol.% of biomass-derived fatty acid methyl ester (FAME). Pre-reforming sulphur-free diesel at around 475 °C has been tested with a commercial nickel catalyst for 118 h without observing catalyst deactivation, at steam-to-carbon ratios as low as 2.6. Direct steam reforming at temperatures up to 800 °C has been tested with a commercial precious metal catalyst for a total of 1190 h with two catalyst batches at steam-to-carbon ratios as low as 2.5. Deactivation was neither observed with lower steam-to-carbon ratios nor for increasing sulphur concentration. The importance of good fuel evaporation and mixing for correct testing of catalysts is illustrated. Diesel containing biodiesel components resulted in poor spray quality, hence poor mixing and evaporation upstream, eventually causing decreasing catalyst performance. The feasibility of direct high temperature steam reforming of commercial low-sulphur diesel has been demonstrated.

A novel membrane-less direct alcohol fuel cell

NASA Astrophysics Data System (ADS)

Yi, Qingfeng; Chen, Qinghua; Yang, Zheng

2015-12-01

Membrane-less fuel cell possesses such advantages as simplified design and lower cost. In this paper, a membrane-less direct alcohol fuel cell is constructed by using multi-walled carbon nanotubes (MWCNT) supported Pd and ternary PdSnNi composites as the anode catalysts and Fe/C-PANI composite, produced by direct pyrolysis of Fe-doped polyaniline precursor, as the oxygen reduction reaction (ORR) catalyst. The alcohols investigated in the present study are methanol, ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol and sec-butanol. The cathode catalyst Fe/C-PANI is electrochemically inactive to oxidation of the alcohols. The performance of the cell with various alcohols in 1 mol L-1 NaOH solution on either Pd/MWCNT or PdSnNi/MWCNT catalyst has been evaluated. In any case, the performance of the cell using the anode catalyst PdSnNi/MWCNT is considerably better than Pd/MWCNT. For the PdSnNi/MWCNT, the maximum power densities of the cell using methanol (0.5 mol L-1), ethanol (0.5 mol L-1), n-propanol (0.5 mol L-1), iso-propanol (0.5 mol L-1), n-butanol (0.2 mol L-1), iso-butanol (0.2 mol L-1) and sec-butanol (0.2 mol L-1) are 0.34, 1.03, 1.07, 0.44, 0.50, 0.31 and 0.15 mW cm-2, respectively.

Catalyst containing oxygen transport membrane

DOEpatents

Lane, Jonathan A.; Wilson, Jamie R.; Christie, Gervase Maxwell; Petigny, Nathalie; Sarantopoulos, Christos

2017-02-07

A composite oxygen transport membrane having a dense layer, a porous support layer and an intermediate porous layer located between the dense layer and the porous support layer. Both the dense layer and the intermediate porous layer are formed from an ionic conductive material to conduct oxygen ions and an electrically conductive material to conduct electrons. The porous support layer has a high permeability, high porosity, and a microstructure exhibiting substantially uniform pore size distribution as a result of using PMMA pore forming materials or a bi-modal particle size distribution of the porous support layer materials. Catalyst particles selected to promote oxidation of a combustible substance are located in the intermediate porous layer and in the porous support adjacent to the intermediate porous layer. The catalyst particles can be formed by wicking a solution of catalyst precursors through the porous support toward the intermediate porous layer.

Plasma Spraying of Ceramics with Particular Difficulties in Processing

NASA Astrophysics Data System (ADS)

Mauer, G.; Schlegel, N.; Guignard, A.; Jarligo, M. O.; Rezanka, S.; Hospach, A.; Vaßen, R.

2015-01-01

Emerging new applications and growing demands of plasma-sprayed coatings initiate the development of new materials. Regarding ceramics, often complex compositions are employed to achieve advanced material properties, e.g., high thermal stability, low thermal conductivity, high electronic and ionic conductivity as well as specific thermo-mechanical properties and microstructures. Such materials however, often involve particular difficulties in processing by plasma spraying. The inhomogeneous dissociation and evaporation behavior of individual constituents can lead to changes of the chemical composition and the formation of secondary phases in the deposited coatings. Hence, undesired effects on the coating characteristics are encountered. In this work, examples of such challenging materials are investigated, namely pyrochlores applied for thermal barrier coatings as well as perovskites for gas separation membranes. In particular, new plasma spray processes like suspension plasma spraying and plasma spray-physical vapor deposition are considered. In some cases, plasma diagnostics are applied to analyze the processing conditions.

Simple fabrication of 12 μm thin nanocomposite fuel cell membranes by direct electrospinning and printing

NASA Astrophysics Data System (ADS)

Breitwieser, Matthias; Klose, Carolin; Klingele, Matthias; Hartmann, Armin; Erben, Johannes; Cho, Hyeongrae; Kerres, Jochen; Zengerle, Roland; Thiele, Simon

2017-01-01

Direct membrane deposition (DMD) was recently introduced as a novel polymer electrolyte membrane fabrication method. Here, this approach is extended to fabricate 12 μm thin nanocomposite fuel cell membranes. Poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) nanofibers are directly electrospun onto gas diffusion electrodes. By inkjet-printing Nafion ionomer dispersion into the pore space of PVDF-HFP nanofiber mats, composite membranes of 12 μm thickness were fabricated. At 120 °C and 35% relative humidity, stoichiometric 1.5/2.5 H2/air flow and atmospheric pressure, the power density of the DMD fuel cell (0.19 W cm-2), was about 1.7 times higher than that of the reference fuel cell (0.11 W cm-2) with Nafion HP membrane and identical catalyst. A lower ionic resistance and, especially at 120 °C, a reduced charge transfer resistance is found compared to the Nafion HP membrane. A 100 h accelerated stress test revealed a voltage decay of below 0.8 mV h-1, which is in the range of literature values for significantly thicker reinforced membranes. Finally, this novel fabrication approach enables new degrees of freedom in the design of complex composite membranes. The presented combination of scalable deposition techniques has the potential to simplify and thus reduce cost of composite membrane fabrication at a larger scale.

Design Optimization of Liquid Fueled High Velocity Oxy- Fuel Thermal Spraying Technique for Durable Coating for Fossil Power Systems

DOE Office of Scientific and Technical Information (OSTI.GOV)

Choudhuri, Ahsan; Love, Norman

High-velocity oxy–fuel (HVOF) thermal spraying was developed in 1930 and has been commercially available for twenty-five years. HVOF thermal spraying has several benefits over the more conventional plasma spray technique including a faster deposition rate which leads to quicker turn-around, with more durable coatings and higher bond strength, hardness and wear resistance due to a homogeneous distribution of the sprayed particles. HVOF thermal spraying is frequently used in engineering to deposit cermets, metallic alloys, composites and polymers, to enhance product life and performance. HVOF thermal spraying system is a highly promising technique for applying durable coatings on structural materials formore » corrosive and high temperature environments in advanced ultra-supercritical coal- fired (AUSC) boilers, steam turbines and gas turbines. HVOF thermal spraying is the preferred method for producing coatings with low porosity and high adhesion. HVOF thermal spray process has been shown to be one of the most efficient techniques to deposit high performance coatings at moderate cost. Variables affecting the deposit formation and coating properties include hardware characteristics such as nozzle geometry and spraying distance and process parameters such as equivalence ratio, gas flow density, and powder feedstock. In the spray process, the powder particles experience very high speeds combined with fast heating to the powder material melting point or above. This high temperature causes evaporation of the powder, dissolution, and phase transformations. Due to the complex nature of the HVOF technique, the control and optimization of the process is difficult. In general, good coating quality with suitable properties and required performance for specific applications is the goal in producing thermal spray coatings. In order to reach this goal, a deeper understanding of the spray process as a whole is needed. Although many researchers studied commercial HVOF thermal spray systems, there exists a lack of fundamental understanding of the effect of hardware characteristics and operating parameters on HVOF thermally sprayed coatings. Motivated by these issues, this study is devoted to investigate the effect of hardware characteristics (e.g. spraying distance) and operating parameters (e.g. combustion chamber pressure, equivalence ratio, and total gas flow rate) on HVOF sprayed coatings using Inconel 718 alloy. The current study provides extensive understanding of several key operating and process parameters to optimize the next generation of HVOF thermally sprayed coatings for high temperature and harsh environment applications. A facility was developed to support this endeavor in a safe and efficient way, including a HVOF thermal spray system with a Data Acquisition and Remote Controls system (DARCS). The coatings microstructure and morphology were examined using X-Ray Diffraction (XRD), Scanning Electron Microscope (SEM) and Nanoindentation.« less

Halloysite-derived nitrogen doped carbon electrocatalysts for anion exchange membrane fuel cells

NASA Astrophysics Data System (ADS)

Lu, Yaxiang; Wang, Lianqin; Preuß, Kathrin; Qiao, Mo; Titirici, Maria-Magdalena; Varcoe, John; Cai, Qiong

2017-12-01

Developing the low-cost, highly active carbonaceous materials for oxygen reduction reaction (ORR) catalysts has been a high-priority research direction for durable fuel cells. In this paper, two novel N-doped carbonaceous materials with flaky and rod-like morphology using the natural halloysite as template are obtained from urea nitrogen source as well as glucose (denoted as GU) and furfural (denoted as FU) carbon precursors, respectively, which can be directly applied as metal-free electrocatalysts for ORR in alkaline electrolyte. Importantly, compared with a benchmark Pt/C (20wt%) catalyst, the as-prepared carbon catalysts demonstrate higher retention in diffusion limiting current density (after 3000 cycles) and enhanced methanol tolerances with only 50-60mV negative shift in half-wave potentials. In addition, electrocatalytic activity, durability and methanol tolerant capability of the two N-doped carbon catalysts are systematically evaluated, and the underneath reasons of the outperformance of rod-like catalysts over the flaky are revealed. At last, the produced carbonaceous catalysts are also used as cathodes in the single cell H2/O2 anion exchange membrane fuel cell (AEMFC), in which the rod-like FU delivers a peak power density as high as 703 mW cm-2 (vs. 1106 mW cm-2 with a Pt/C benchmark cathode catalyst).

Hierarchical nanostructured hollow spherical carbon with mesoporous shell as a unique cathode catalyst support in proton exchange membrane fuel cell.

PubMed

Fang, Baizeng; Kim, Jung Ho; Kim, Minsik; Kim, Minwoo; Yu, Jong-Sung

2009-03-07

Hierarchical nanostructured spherical carbon with hollow macroporous core in combination with mesoporous shell has been explored to support Pt cathode catalyst with high metal loading in proton exchange membrane fuel cell (PEMFC). The hollow core-mesoporous shell carbon (HCMSC) has unique structural characteristics such as large specific surface area and mesoporous volume, ensuring uniform dispersion of the supported high loading (60 wt%) Pt nanoparticles with small particle size, and well-developed three-dimensionally interconnected hierarchical porosity network, facilitating fast mass transport. The HCMSC-supported Pt(60 wt%) cathode catalyst has demonstrated markedly enhanced catalytic activity toward oxygen reduction and greatly improved PEMFC polarization performance compared with carbon black Vulcan XC-72 (VC)-supported ones. Furthermore, the HCMSC-supported Pt(40 wt%) or Pt(60 wt%) outperforms the HCMSC-supported Pt(20 wt%) even at a low catalyst loading of 0.2 mg Pt cm(-2) in the cathode, which is completely different from the VC-supported Pt catalysts. The capability of supporting high loading Pt is supposed to accelerate the commercialization of PEMFC due to the anticipated significant reduction in the amount of catalyst support required, diffusion layer thickness and fabricating cost of the supported Pt catalyst electrode.

Highly Selective TiN-Supported Highly Dispersed Pt Catalyst: Ultra Active toward Hydrogen Oxidation and Inactive toward Oxygen Reduction.

PubMed

Luo, Junming; Tang, Haibo; Tian, Xinlong; Hou, Sanying; Li, Xiuhua; Du, Li; Liao, Shijun

2018-01-31

The severe dissolution of the cathode catalyst, caused by an undesired oxygen reduction reaction at the anode during startup and shutdown, is a fatal challenge to practical applications of polymer electrolyte membrane fuel cells. To address this important issue, according to the distinct structure-sensitivity between the σ-type bond in H 2 and the π-type bond in O 2 , we design a HD-Pt/TiN material by highly dispersing Pt on the TiN surface to inhibit the unwanted oxygen reduction reaction. The highly dispersed Pt/TiN catalyst exhibits excellent selectivity toward hydrogen oxidation and oxygen reduction reactions. With a Pt loading of 0.88 wt %, our catalyst shows excellent hydrogen oxidation reaction activity, close to that of commercial 20 wt % Pt/C catalyst, and much lower oxygen reduction reaction activity than the commercial 20 wt % Pt/C catalyst. The lack of well-ordered Pt facets is responsible for the excellent selectivity of the HD-Pt/TiN materials toward hydrogen oxidation and oxygen reduction reactions. Our work provides a new and cost-effective solution to design selective catalysts toward hydrogen oxidation and oxygen reduction reactions, making the strategy of using oxygen-tolerant anode catalyst to improve the stability of polymer electrolyte membrane fuel cells during startup and shutdown more affordable and practical.

Novel Techniques for Quantification of Correlation Between Primary Liquid Jet Breakup and Downstream Spray Characteristics

DTIC Science & Technology

2016-05-08

unlimited. 5 1. Introduction Several liquid -fuelled combustion systems, such as liquid propellant rocket engines and gas turbines...AFRL-AFOSR-JP-TR-2016-0084 Novel techniques for quantification of correlation between primary liquid jet breakup and downstream spray characteristics...to 17 Apr 2016 4.  TITLE AND SUBTITLE Novel techniques for quantification of correlation between primary liquid jet breakup and downstream spray

Novel Techniques for Quantification of Correlation Between Primary Liquid Jet Breakup and Downstream Spray Characteristics

DTIC Science & Technology

2016-10-05

unlimited. 5 1. Introduction Several liquid -fuelled combustion systems, such as liquid propellant rocket engines and gas turbines...AFRL-AFOSR-JP-TR-2016-0084 Novel techniques for quantification of correlation between primary liquid jet breakup and downstream spray characteristics...to 17 Apr 2016 4.  TITLE AND SUBTITLE Novel techniques for quantification of correlation between primary liquid jet breakup and downstream spray

Fabrication of polymer electrolyte membrane fuel cell MEAs utilizing inkjet print technology

NASA Astrophysics Data System (ADS)

Towne, Silas; Viswanathan, Vish; Holbery, James; Rieke, Peter

Utilizing drop-on-demand technology, we have successfully fabricated hydrogen-air polymer electrolyte membrane fuel cells (PEMFC), demonstrated some of the processing advantages of this technology and have demonstrated that the performance is comparable to conventionally fabricated membrane electrode assemblies (MEAs). Commercial desktop inkjet printers were used to deposit the active catalyst electrode layer directly from print cartridges onto Nafion ® polymer membranes in the hydrogen form. The layers were well-adhered and withstood simple tape peel, bending and abrasion tests and did so without any post-deposition hot press step. The elimination of this processing step suggests that inkjet-based fabrication or similar processing technologies may provide a route to less expensive large-scale fabrication of PEMFCs. When tested in our experimental apparatus, open circuit voltages up to 0.87 V and power densities of up to 155 mW cm -2 were obtained with a catalyst loading of 0.20 mg Pt cm -2. A commercially available membrane under identical, albeit not optimized test conditions, showed about 7% greater power density. The objective of this work was to demonstrate some of the processing advantages of drop-on-demand technology for fabrication of MEAs. It remains to be determined if inkjet fabrication offers performance advantages or leads to more efficient utilization of expensive catalyst materials.

Recovery of Ni Metal from Spent Catalyst with Emulsion Liquid Membrane Using Cyanex 272 as Extractant

NASA Astrophysics Data System (ADS)

Yuliusman; Huda, M.; Ramadhan, I. T.; Farry, A. R.; Wulandari, P. T.; Alfia, R.

2018-03-01

In this study was conducted to recover nickel metal from spent nickel catalyst resulting from hydrotreating process in petroleum industry. The nickel extraction study with the emulsion liquid membrane using Cyanex 272 as an extractant to extract and separate nickel from the feed phase solution. Feed phase solution was preapred from spent catalyst using sulphuric acid. Liquid membrane consists of a kerosene as diluent, a Span 80 as surfactant, a Cyanex 272 as carrier and sulphuric acid solutions have been used as the stripping solution. The important parameters governing the permeation of nickel and their effect on the separation process have been studied. These parameters are surfactant concentration, extractant concentration feed phase pH. The optimum conditions of the emulsion membrane making process is using 0.06 M Cyanex 272, 8% w/v SPAN 80, 0.05 M H2SO4, internal phase extractant / phase volume ratio: 1/1, and stirring speed 1150 rpm for 60 Minute that can produce emulsion membrane with stability level above 90% after 4 hours. In the extraction process with optimum condition pH 6 for feed phase, ratio of phase emulsion/phase of feed: 1/2, and stirring speed 175 rpm for 15 minutes with result 81.51% nickel was extracted.

Open circuit voltage durability study and model of catalyst coated membranes at different humidification levels

NASA Astrophysics Data System (ADS)

Kundu, Sumit; Fowler, Michael W.; Simon, Leonardo C.; Abouatallah, Rami; Beydokhti, Natasha

Fuel cell material durability is an area of extensive research today. Chemical degradation of the ionomer membrane is one important degradation mechanism leading to overall failure of fuel cells. This study examined the effects of relative humidity on the chemical degradation of the membrane during open circuit voltage testing. Five Gore™ PRIMEA ® series 5510 catalyst coated membranes were degraded at 100%, 75%, 50%, and 20% RH. Open circuit potential and cumulative fluoride release were monitored over time. Additionally scanning electron microscopy images were taken at end of the test. The results showed that with decreasing RH fluoride release rate increased as did performance degradation. This was attributed to an increase in gas crossover with a decrease in RH. Further, it is also shown that interruptions in testing may heavily influence cumulative fluoride release measurements where frequent stoppages in testing will cause fluoride release to be underestimated. SEM analysis shows that degradation occurred in the ionomer layer close to the cathode catalyst. A chemical degradation model of the ionomer membrane was used to model the results. The model was able to predict fluoride release trends, including the effects of interruptions, showing that changes in gas crossover with RH could explain the experimental results.

A demonstration of the antimicrobial effectiveness of various copper surfaces

PubMed Central

2013-01-01

Background Bacterial contamination on touch surfaces results in increased risk of infection. In the last few decades, work has been done on the antimicrobial properties of copper and its alloys against a range of micro-organisms threatening public health in food processing, healthcare and air conditioning applications; however, an optimum copper method of surface deposition and mass structure has not been identified. Results A proof-of-concept study of the disinfection effectiveness of three copper surfaces was performed. The surfaces were produced by the deposition of copper using three methods of thermal spray, namely, plasma spray, wire arc spray and cold spray The surfaces were then inoculated with meticillin-resistant Staphylococcus aureus (MRSA). After a two hour exposure to the surfaces, the surviving MRSA were assayed and the results compared. The differences in the copper depositions produced by the three thermal spray methods were examined in order to explain the mechanism that causes the observed differences in MRSA killing efficiencies. The cold spray deposition method was significantly more effective than the other methods. It was determined that work hardening caused by the high velocity particle impacts created by the cold spray technique results in a copper microstructure that enhances ionic diffusion, and copper ions are principally responsible for antimicrobial activity. Conclusions This test showed significant microbiologic differences between coatings produced by different spray techniques and demonstrates the importance of the copper application technique. The cold spray technique shows superior anti-microbial effectiveness caused by the high impact velocity imparted to the sprayed particles which results in high dislocation density and high ionic diffusivity. PMID:23537176

Methods and apparatus for carbon dioxide removal from a fluid stream

DOEpatents

Wei, Wei; Ruud, James Anthony; Ku, Anthony Yu-Chung; Ramaswamy, Vidya; Liu, Ke

2010-01-19

An apparatus for producing hydrogen gas wherein the apparatus includes a reactor. In one embodiment, the reactor includes at least two conversion-removal portions. Each conversion-removal portion comprises a catalyst section configured to convert CO in the stream to CO.sub.2 and a membrane section located downstream of and in flow communication with the catalyst section. The membrane section is configured to selectively remove the CO.sub.2 from the stream and to be in flow communication with a sweep gas.

Insights on the SO2 Poisoning of Pt3Co/VC and Pt/VC Fuel Cell Catalysts

DTIC Science & Technology

2010-01-01

catalyst is performed at the cathode of proton exchange membrane fuel cells ( PEMFCs ) in order to link previously reported results at the elec- trode...stripping voltammetry and underpotential deposition (upd) of copper adatoms. Then the performance of PEMFC cathodes employing 30wt.% Pt3Co/VC and 50wt.% Pt/VC...proton exchange membrane fuel cells( PEMFCs )in order to link previously reported results at the elec- trode/solution interface to the FC environment. First

High performance and durability of order-structured cathode catalyst layer based on TiO2@PANI core-shell nanowire arrays

NASA Astrophysics Data System (ADS)

Chen, Ming; Wang, Meng; Yang, Zhaoyi; Wang, Xindong

2017-06-01

In this paper, an order-structured cathode catalyst layer consisting of Pt-TiO2@PANI core-shell nanowire arrays that in situ grown on commercial gas diffusion layer (GDL) are prepared and applied to membrane electrode assembly (MEA) of proton exchange membrane fuel cell (PEMFC). In order to prepare the TiO2@PANI core-shell nanowire arrays with suitable porosity and prominent conductivity, the morphologies of the TiO2 nanoarray and electrochemical polymerization process of aniline are schematically investigated. The MEA with order-structured cathode catalyst layer is assembled in the single cell to evaluate the electrochemical performance and durability of PEMFC. As a result, the PEMFC with order-structured cathode catalyst layer shows higher peak power density (773.54 mW cm-2) than conventional PEMFC (699.30 mW cm-2). Electrochemically active surface area (ECSA) and charge transfer impedance (Rct) are measured before and after accelerated degradation test (ADT), and the corresponding experimental results indicate the novel cathode structure exhibits a better stability with respect to conventional cathode. The enhanced electrochemical performance and durability toward PEMFC can be ascribed to the order-structured cathode nanoarray structure with high specific surface area increases the utilization of catalyst and reduces the tortuosity of transport pathways, and the synergistic effect between TiO2@PANI support and Pt nanoparticles promotes the high efficiency of electrochemical reaction and improves the stability of catalyst. This research provides a facile and controllable method to prepare order-structured membrane electrode with lower Pt loading for PEMFC in the future.

Enhanced MEA Performance for PEMFCs under Low Relative Humidity and Low Oxygen Content Conditions via Catalyst Functionalization

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xin, Le; Yang, Fan; Xie, Jian

2017-01-01

This work demonstrates that functionalizing annealed-Pt/Ketjen black EC300j (a-Pt/KB) and dealloyed-PtNi/Ketjen black EC300j (d-PtNi/KB) catalysts using p-phenyl sulfonic acid can effectively enhance performance in the membrane electrode assemblies (MEAs) of proton exchange membrane fuel cells (PEMFCs). The functionalization increased the size of both Pt and PtNi catalyst particles and resulted in the further leaching of Ni from the PtNi catalyst while promoting the formation of nanoporous PtNi nanoparticles. The size of the SO3H-Pt/KB and SO3H-PtNi/KB carbon-based aggregates decreased dramatically, leading to the formation of catalyst layers with narrower pore size distributions.MEA tests highlighted the benefits of the surface functionalization, inmore » which the cells with SO3H-Pt/KB and SO3H-PtNi/KB cathode catalysts showed superior high current density performance under reduced RH conditions, in comparison with cells containing annealed Pt/KB (a-Pt/KB) and de-alloyed PtNi/KB (d-PtNi/KB) catalysts. The performance improvement was particularly evident when using reactant gases with low relative humidity, indicating that the hydrophilic functional groups on the carbon improved the water retention in the cathode catalyst layer. These results show a new avenue for enhancing catalyst performance for the next generation of catalytic materials for PEMFCs.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

NONE

During this reporting period, there were three major thrusts in the WVU portion. First, we started a preliminary investigation on the use of a membrane reactor for HAS. Accordingly, the plug-flow reactor which had been isolated from sulfides was substituted by a membrane reactor. The tubular membrane was first characterized in terms of its permeation properties, i.e., the fluxes, permeances and selectivities of the components. After that, a BASF methanol-synthesis catalyst was tested under different conditions on the membrane reactor. The results will be compared with those from a non-permeable stainless steel tubular reactor under the same conditions. Second, wemore » started a detailed study of one of the catalysts tested during the screening runs. Accordingly, a carbon-supported potassium-doped molybdenum-cobalt catalyst was selected to be run in the Rotoberty reactor. Finally, we have started detailed analyses of reaction products from some earlier screening runs in which non-sulfide molybdenum-based catalysts were employed and much more complicated product distributions were generally observed. These products could not hitherto be analyzed using the gas chromatograph which was then available. A Varian gas chromatograph/mass spectrometer (GC/MS) is being used to characterize these liquid products. At UCC, we completed a screening of an Engelhard support impregnated with copper and cesium. We have met or exceeded three of four catalyst development targets. Oxygenate selectivity is our main hurdle. Further, we tested the effect of replacing stainless-steel reactor preheater tubing and fittings with titanium ones. We had hoped to reduce the yield of hydrocarbons which may have been produced at high temperatures due to Fischer-Tropsch catalysis with the iron and nickel in the preheater tube walls. Results showed that total hydrocarbon space time yield was actually increased with the titanium preheater, while total alcohol space time yield was not significantly affected.« less

Catalytic nanoporous membranes

DOEpatents

Pellin, Michael J; Hryn, John N; Elam, Jeffrey W

2013-08-27

A nanoporous catalytic membrane which displays several unique features Including pores which can go through the entire thickness of the membrane. The membrane has a higher catalytic and product selectivity than conventional catalysts. Anodic aluminum oxide (AAO) membranes serve as the catalyst substrate. This substrate is then subjected to Atomic Layer Deposition (ALD), which allows the controlled narrowing of the pores from 40 nm to 10 nm in the substrate by deposition of a preparatory material. Subsequent deposition of a catalytic layer on the inner surfaces of the pores reduces pore sizes to less than 10 nm and allows for a higher degree of reaction selectivity. The small pore sizes allow control over which molecules enter the pores, and the flow-through feature can allow for partial oxidation of reactant species as opposed to complete oxidation. A nanoporous separation membrane, produced by ALD is also provided for use in gaseous and liquid separations. The membrane has a high flow rate of material with 100% selectivity. Also provided is a method for producing a catalytic membrane having flow-through pores and discreet catalytic clusters adhering to the inside surfaces of the pores.

Graphene-supported platinum catalyst prepared with ionomer as surfactant for anion exchange membrane fuel cells

NASA Astrophysics Data System (ADS)

Zeng, L.; Zhao, T. S.; An, L.; Zhao, G.; Yan, X. H.; Jung, C. Y.

2015-02-01

In this work, we have synthesized an ionomer-coated graphene-supported platinum catalyst for anion exchange membrane fuel cells. Unlike the common surfactant stabilized colloidal method, we employ a home-made anion exchange ionomer (AEI), namely quaternary ammonia poly (2, 6-dimethyl-1, 4-phenylene oxide) (QAPPO), as the surfactant. The AEI coated on reduced graphene oxide (rGO) surfaces serves as a stabilizer to anchor the platinum precursor on rGO surfaces due to electrostatic interactions. As a result, platinum nanoparticles (Pt NPs) can be easily deposited onto rGO surfaces with a uniform distribution. The remarkable feature of the present synthesis method is that the surfactant, the coated AEI, does not need to be removed from the catalyst, but serves as hydroxide-conductive paths in the catalyst layer, leading to enhanced triple phase boundaries. It is demonstrated that the use of the catalyst obtained with the present method enables a H2/O2 AEMFC to yield a peak power density of 264.8 mW cm-2 at 60 °C, which is 30% higher than that produced from the same fuel cell but with the use of the catalyst synthesized by the conventional synthesis method.

Semipermeable polymers and method for producing same

DOEpatents

Buschmann, Wayne E [Boulder, CO

2012-04-03

A polyamide membrane comprising reaction product of an anhydrous solution comprising an anhydrous solvent, at least one polyfunctional secondary amine and a pre-polymer deposition catalyst; and an anhydrous, organic solvent solution comprising a polyfunctional aromatic amine-reactive reactant comprising one ring. A composite semipermeable membrane comprising the polyamide membrane on a porous support. A method of making a composite semipermeable membrane by coating a porous support with an anhydrous solution comprising an anhydrous solvent, a polyfunctional secondary amine and a pre-polymer deposition catalyst, to form an activated pre-polymer layer on the porous support and contacting the activated pre-polymer layer with an anhydrous, organic solvent solution comprising a polyfunctional amine-reactive reactant to interfacially condense the amine-reactive reactant with the polyfunctional secondary amine, thereby forming a cross-linked, interfacial polyamide layer on the porous support. A method of impregnating a composite semipermeable membrane with nanoparticles selected from heavy metals and/or oxides of heavy metals.

Slat templated formation of efficient oxygen reduction electrocatalyst with a fluidic precursor

NASA Astrophysics Data System (ADS)

Tan, Yao

2018-05-01

Development of cost-effective and efficient oxygen reduction catalyst is critical for the commercialization of proton exchange membrane fuel cell. Metal and nitrogen co-doped carbon is recognized as a promising alternative to traditional platinum-based oxygen reduction catalyst. Herein, we report a novel metal and nitrogen co-doped carbon catalyst with an ionic liquid precursor. Salt template, which can be easily removed with mild treatment after the synthesis, is used to generate abundant mesopores in the resulting catalyst. We show that the novel catalyst shows a superior activity comparable to commercial Pt/C catalyst. Furthermore, the important role of the mesopore for the activity of the catalyst is demonstrated.

Spongy Raney nickel hydrogen electrodes for alkaline fuel cells

NASA Astrophysics Data System (ADS)

Tomida, Tahei; Nakabayashi, Ichiro

1989-11-01

Spongy Raney nickel catalysts for use as hydrogen electrodes of fuel cells were prepared by a new method. In this method molten aluminum was sprayed on both sides of a spongy plate of nickel as substrate with an acetylene-oxygen flame gun. Then, the spongy nickel electrodes were activated by alloying at a given temperature of from 550 to 750 C, and leaching the aluminum from the alloy in alkaline solution. This type of catalyst showed good thermal and electrical conductivity and also mechanical strength by itself. Its polarization resistance was very low, and the characteristics of the electrodes improved with increase in the temperature of heat-treatment for alloying. The finding that activity depended on the alloying temperature was consistent with observations by scanning electron microscope on the surface textures of catalysts alloyed at different temperatures.

Catalytic oxidation for treatment of ECLSS and PMMS waste streams

NASA Technical Reports Server (NTRS)

Akse, James R.; Jolly, Clifford D.

1991-01-01

It is shown that catalytic oxidation is an effective technique for the removal of trace organic contaminants in a multifiltration potable processor's effluent. Essential elements of this technology are devices that deliver oxygen to the influent, and remove gaseous reaction byproducts from the effluent, via hollow-tube, gas-permeable membranes. Iodine, which poisons existing catalysis, is removed by a small deiodination bed prior to catalytic reactor entrance. The catalyst used is a mixture of Pt and Ru deposited on carbon, operating at 125-160 C and 39-90 psi pressures.

Nanostructured TiOx as a catalyst support material for proton exchange membrane fuel cells

NASA Astrophysics Data System (ADS)

Phillips, Richard S.

Recent interest in the development of new catalyst support materials for proton exchange membrane fuel cells (PEMFCs) has stimulated research into the viability of TiO2-based support structures. Specifically, substoichiometric TiO2 (TiOx) has been reported to exhibit a combination of high conductivity, stability, and corrosion resistance. These properties make TiOx-based support materials a promising prospect when considering the inferior corrosion resistance of traditional carbon-based supports. This document presents an investigation into the formation of conductive and stable TiOx thin films employing atomic layer deposition (ALD) and a post deposition oxygen reducing anneal (PDORA). Techniques for manufacturing TiOx-based catalyst support nanostructures by means of ALD in conjunction with carbon black (CB), anodic aluminum oxide (AAO) and silicon nanowires (SiNWs) will also be presented. The composition and thickness of resulting TiOx thin films was determined with the aid of Auger electron spectroscopy (AES), Rutherford backscattering spectrometry (RBS), X-ray photoelectron spectroscopy (XPS), energy-dispersive X-ray spectroscopy (EDS), and scanning electron microscopy (SEM). Film crystal structure was determined with X-ray diffraction (XRD) analysis. Film conductivity was calculated using four-point probe (4-PP) and film thickness measurement data. Resulting thin films show a significant decrease of oxygen in ALD TiOx films corresponding with a great increase in conductivity following the PDORA. The effectiveness of the PDORA was also found to be highly dependent on ALD process parameters. TiOx-based nanostructures were coated with platinum using one of three Pt deposition techniques. First, liquid phase deposition (LPD), which was performed at room temperature, provided equal access to catalyst support material surfaces which were suspended in solution. Second, plasma enhanced atomic layer deposition (PEALD), which was performed at 450°C, provided good Pt particle dispersion and particle size controllability. Third, physical vapor deposition (PVD), which was also performed at room temperature, was used as a low temperature vapor-phase deposition technique for comparison with PEALD Pt coated materials. The temperature of the Pt deposition technique is an important parameter to consider due to the potential adverse effects of the strong metal support interaction (SMSI) which may take place at temperatures above 200°C. Platinum coated nanostructures were analyzed electrochemically using cyclic voltammetry (CV), rotating disk electrode (RDE) and accelerated stress tests (ASTs). CV and RDE results generally show that platinum activity values are initially not as high as those typically observed for platinum on carbon; however, AST results indicate that TiO x-based materials are much more stable long-term and hence their level of activity is likely to overtake traditional platinum on carbon materials in a PEMFC system.

3D visualization of membrane failures in fuel cells

NASA Astrophysics Data System (ADS)

Singh, Yadvinder; Orfino, Francesco P.; Dutta, Monica; Kjeang, Erik

2017-03-01

Durability issues in fuel cells, due to chemical and mechanical degradation, are potential impediments in their commercialization. Hydrogen leak development across degraded fuel cell membranes is deemed a lifetime-limiting failure mode and potential safety issue that requires thorough characterization for devising effective mitigation strategies. The scope and depth of failure analysis has, however, been limited by the 2D nature of conventional imaging. In the present work, X-ray computed tomography is introduced as a novel, non-destructive technique for 3D failure analysis. Its capability to acquire true 3D images of membrane damage is demonstrated for the very first time. This approach has enabled unique and in-depth analysis resulting in novel findings regarding the membrane degradation mechanism; these are: significant, exclusive membrane fracture development independent of catalyst layers, localized thinning at crack sites, and demonstration of the critical impact of cracks on fuel cell durability. Evidence of crack initiation within the membrane is demonstrated, and a possible new failure mode different from typical mechanical crack development is identified. X-ray computed tomography is hereby established as a breakthrough approach for comprehensive 3D characterization and reliable failure analysis of fuel cell membranes, and could readily be extended to electrolyzers and flow batteries having similar structure.

Layered growth with bottom-spray granulation for spray deposition of drug.

PubMed

Er, Dawn Z L; Liew, Celine V; Heng, Paul W S

2009-07-30

The gap in scientific knowledge on bottom-spray fluidized bed granulation has emphasized the need for more studies in this area. This paper comparatively studied the applicability of a modified bottom-spray process and the conventional top-spray process for the spray deposition of a micronized drug during granulation. The differences in circulation pattern, mode of growth and resultant granule properties between the two processes were highlighted. The more ordered and consistent circulation pattern of particles in a bottom-spray fluidized bed was observed to give rise to layered granule growth. This resulted in better drug content uniformity among the granule batches and within a granule batch. The processes' sensitivities to wetting and feed material characteristics were also compared and found to differ markedly. Less robustness to differing process conditions was observed for the top-spray process. The resultant bottom-spray granules formed were observed to be less porous, more spherical and had good flow properties. The bottom-spray technique can thus be potentially applied for the spray deposition of drug during granulation and was observed to be a good alternative to the conventional technique for preparing granules.

Spray-on polyvinyl alcohol separators and impact on power production in air-cathode microbial fuel cells with different solution conductivities.

PubMed

Hoskins, Daniel L; Zhang, Xiaoyuan; Hickner, Michael A; Logan, Bruce E

2014-11-01

Separators are used to protect cathodes from biofouling and to avoid electrode short-circuiting, but they can adversely affect microbial fuel cell (MFC) performance. A spray method was used to apply a polyvinyl alcohol (PVA) separator to the cathode. Power densities were unaffected by the PVA separator (339±29mW/m(2)), compared to a control lacking a separator in a low conductivity solution (1mS/cm) similar to wastewater. Power was reduced with separators in solutions typical of laboratory tests (7-13mS/cm), compared to separatorless controls. The PVA separator produced more power in a separator assembly (SEA) configuration (444±8mW/m(2)) in the 1mS/cm solution, but power was reduced if a PVA or wipe separator was used in higher conductivity solutions with either Pt or activated carbon catalysts. Spray and cast PVA separators performed similarly, but the spray method is preferred as it was easier to apply and use. Copyright © 2014 Elsevier Ltd. All rights reserved.

Chemical routes to nanocrystalline and thin-film III-VI and I-III-VI semiconductors

NASA Astrophysics Data System (ADS)

Hollingsworth, Jennifer Ann

1999-11-01

The work encompasses: (1) catalyzed low-temperature, solution-based routes to nano- and microcrystalline III-VI semiconductor powders and (2) spray chemical vapor deposition (spray CVD) of I-III-VI semiconductor thin films. Prior to this work, few, if any, examples existed of chemical catalysis applied to the synthesis of nonmolecular, covalent solids. New crystallization strategies employing catalysts were developed for the regioselective syntheses of orthorhombic InS (beta-InS), the thermodynamic phase, and rhombohedral InS (R-InS), a new, metastable structural isomer. Growth of beta-InS was facilitated by a solvent-suspended, molten-metal flux in a process similar to the SolutionLiquid-Solid (SLS) growth of InP and GaAs fibers and single-crystal whiskers. In contrast, metastable R-InS, having a pseudo-graphitic layered structure, was prepared selectively when the molecular catalyst, benzenethiol, was present in solution and the inorganic "catalyst" (metal flux) was not present. In the absence of any crystal-growth facilitator, metal flux or benzenethiol, amorphous product was obtained under the mild reaction conditions employed (T ≤ 203°C). The inorganic and organic catalysts permitted the regio-selective syntheses of InS and were also successfully applied to the growth of network and layered InxSey compounds, respectively, as well as nanocrystalline In2S3. Extensive microstructural characterization demonstrated that the layered compounds grew as fullerene-like nanostructures and large, colloidal single crystals. Films of the I-III-VI compounds, CuInS2, CuGaS2, and Cu(In,Ga)S 2, were deposited by spray CVD using the known single-source metalorganic precursor, (Ph3P)2CuIn(SEt)4, a new precursor, (Ph3P)2CuGa(SEt)3, and a mixture of the two precursors, respectively. The CulnS2 films exhibited a variety of microstructures from dense and faceted or platelet-like to porous and dendritic. Crystallographic orientations ranged from strongly [112] to strongly [220] oriented. Microstructure, orientation, and growth kinetics were controlled by changing processing parameters: carrier-gas flow rate, substrate temperature, and precursor-solution concentration. Low resistivities (<50 O cm) were associated with [220]-oriented films. All CuInS2 films were approximately stoichiometric and had the desired bandgap (Eg ≅ 1.4 eV) for application as the absorber layer in thin-film photovoltaic devices.

Final Report - Advanced Cathode Catalysts and Supports for PEM Fuel Cells

DOE Office of Scientific and Technical Information (OSTI.GOV)

Debe, Mark

2012-09-28

The principal objectives of the program were development of a durable, low cost, high performance cathode electrode (catalyst and support), that is fully integrated into a fuel cell membrane electrode assembly with gas diffusion media, fabricated by high volume capable processes, and is able to meet or exceed the 2015 DOE targets. Work completed in this contract was an extension of the developments under three preceding cooperative agreements/grants Nos. DE-FC-02-97EE50473, DE-FC-99EE50582 and DE-FC36- 02AL67621 which investigated catalyzed membrane electrode assemblies for PEM fuel cells based on a fundamentally new, nanostructured thin film catalyst and support system, and demonstrated the feasibilitymore » for high volume manufacturability.« less

Evaluation of asphalt rubber membrane interlayer (ARMI) using the University of Florida's composite system interface cracking (CSIC) test.

DOT National Transportation Integrated Search

2012-05-01

Since the late 1970s, FDOT : has applied an interlayer : of Asphalt Rubber : Membrane Interlayer : (ARMI) to asphalt roadway : surfaces. ARMI layers are : constructed by spraying : asphalt rubber binder onto : the asphalt, covering the : layer with n...

Spray nozzle designs for agricultural aviation applications. [relation of drop size to spray characteristics and nozzle efficiency

NASA Technical Reports Server (NTRS)

Lee, K. W.; Putnam, A. A.; Gieseke, J. A.; Golovin, M. N.; Hale, J. A.

1979-01-01

Techniques of generating monodisperse sprays and information concerning chemical liquids used in agricultural aviation are surveyed. The periodic dispersion of liquid jet, the spinning disk method, and ultrasonic atomization are the techniques discussed. Conceptually designed spray nozzles for generating monodisperse sprays are assessed. These are based on the classification of the drops using centrifugal force, on using two opposing liquid laden air jets, and on operating a spinning disk at an overloaded flow. Performance requirements for the designs are described and estimates of the operational characteristics are presented.

Catalyst-layer ionomer imaging of fuel cells

DOE PAGES

Guetaz, Laure; Lopez-Haro, M.; Escribano, S.; ...

2015-09-14

Investigation of membrane/electrode assembly (MEA) microstructure has become an essential step to optimize the MEA components and manufacturing processes or to study the MEA degradation. For these investigations, transmission electron microscopy (TEM) is a tool of choice as it provides direct imaging of the different components. TEM is then widely used for analyzing the catalyst nanoparticles and their carbon support. However, the ionomer inside the electrode is more difficult to be imaged. The difficulties come from the fact that the ionomer forms an ultrathin layer surrounding the carbon particles and in addition, these two components, having similar density, present nomore » difference in contrast. In this paper, we show how the recent progresses in TEM techniques as spherical aberration (Cs) corrected HRTEM, electron tomography and X-EDS elemental mapping provide new possibilities for imaging this ionomer network and consequently to study its degradation.« less

Rapid growth and photoluminescence properties of doped ZnS one-dimensional nanostructures

NASA Astrophysics Data System (ADS)

Zhuo, R. F.; Feng, H. T.; Yan, D.; Chen, J. T.; Feng, J. J.; Liu, J. Z.; Yan, P. X.

2008-06-01

In this paper we report the synthesis of doped ZnS one-dimensional (1D) nanostructures by well-established technique of chemical vapor deposition using Zn and S powder as precursors. The ZnS 1D nanostructures were grown on the surface of Au particle-filled anodic aluminum oxide templates, catalyst-free graphite sheets and silicon substrates. ZnS 1D nanostructures with Mn, Cu and Fe as dopants were prepared via a rapid process of 15-20 min. The morphologies of ZnS nanostructures synthesized on different substrates and at different growth temperatures have distinct dissimilarities. The size of ZnS nanowires originated from the Au catalysts could be varied by altering the size of membrane nanopores as well as the embedded Au particles. Room-temperature photoluminescence measurements reveal strong blue, green and yellow-orange light emissions from the doped ZnS 1D nanostructures.

Controlled growth of CNT in mesoporous AAO through optimized conditions for membrane preparation and CVD operation

NASA Astrophysics Data System (ADS)

Ciambelli, P.; Arurault, L.; Sarno, M.; Fontorbes, S.; Leone, C.; Datas, L.; Sannino, D.; Lenormand, P.; Le Blond Du Plouy, S.

2011-07-01

Anodic aluminium oxide (RAAO) membranes with a mesoporous structure were prepared under strictly controlling experimental process conditions, and physically and chemically characterized by a wide range of experimental techniques. Commercial anodic aluminium oxide (CAAO) membranes were also investigated for comparison. We demonstrated that RAAO membranes have lower content of both water and phosphorus and showed better porosity shape than CAAO. The RAAO membranes were used for template growth of carbon nanotubes (CNT) inside its pores by ethylene chemical vapour deposition (CVD) in the absence of a catalyst. A composite material, containing one nanotube for each channel, having the same length as the membrane thickness and an external diameter close to the diameter of the membrane holes, was obtained. Yield, selectivity and quality of CNTs in terms of diameter, length and arrangement (i.e. number of tubes for each channel) were optimized by investigating the effect of changing the experimental conditions for the CVD process. We showed that upon thermal treatment RAAO membranes were made up of crystallized allotropic alumina phases, which govern the subsequent CNT growth, because of their catalytic activity, likely due to their Lewis acidity. The strict control of experimental conditions for membrane preparation and CNT growth allowed us to enhance the carbon structural order, which is a critical requisite for CNT application as a substitute for copper in novel nano-interconnects.

Controlled growth of CNT in mesoporous AAO through optimized conditions for membrane preparation and CVD operation.

PubMed

Ciambelli, P; Arurault, L; Sarno, M; Fontorbes, S; Leone, C; Datas, L; Sannino, D; Lenormand, P; Du Plouy, S Le Blond

2011-07-01

Anodic aluminium oxide (RAAO) membranes with a mesoporous structure were prepared under strictly controlling experimental process conditions, and physically and chemically characterized by a wide range of experimental techniques. Commercial anodic aluminium oxide (CAAO) membranes were also investigated for comparison. We demonstrated that RAAO membranes have lower content of both water and phosphorus and showed better porosity shape than CAAO. The RAAO membranes were used for template growth of carbon nanotubes (CNT) inside its pores by ethylene chemical vapour deposition (CVD) in the absence of a catalyst. A composite material, containing one nanotube for each channel, having the same length as the membrane thickness and an external diameter close to the diameter of the membrane holes, was obtained. Yield, selectivity and quality of CNTs in terms of diameter, length and arrangement (i.e. number of tubes for each channel) were optimized by investigating the effect of changing the experimental conditions for the CVD process. We showed that upon thermal treatment RAAO membranes were made up of crystallized allotropic alumina phases, which govern the subsequent CNT growth, because of their catalytic activity, likely due to their Lewis acidity. The strict control of experimental conditions for membrane preparation and CNT growth allowed us to enhance the carbon structural order, which is a critical requisite for CNT application as a substitute for copper in novel nano-interconnects.

Planar Laser Imaging of Sprays for Liquid Rocket Studies

NASA Technical Reports Server (NTRS)

Lee, W.; Pal, S.; Ryan, H. M.; Strakey, P. A.; Santoro, Robert J.

1990-01-01

A planar laser imaging technique which incorporates an optical polarization ratio technique for droplet size measurement was studied. A series of pressure atomized water sprays were studied with this technique and compared with measurements obtained using a Phase Doppler Particle Analyzer. In particular, the effects of assuming a logarithmic normal distribution function for the droplet size distribution within a spray was evaluated. Reasonable agreement between the instrument was obtained for the geometric mean diameter of the droplet distribution. However, comparisons based on the Sauter mean diameter show larger discrepancies, essentially because of uncertainties in the appropriate standard deviation to be applied for the polarization ratio technique. Comparisons were also made between single laser pulse (temporally resolved) measurements with multiple laser pulse visualizations of the spray.

Method of making metal-polymer composite catalysts

DOEpatents

Zelena, Piotr [Los Alamos, NM; Bashyam, Rajesh [Los Alamos, NM

2009-06-23

A metal-polymer-carbon composite catalyst for use as a cathode electrocatalyst in fuel cells. The catalyst includes a heteroatomic polymer; a transition metal linked to the heteroatomic polymer by one of nitrogen, sulfur, and phosphorus, and a recast ionomer dispersed throughout the heteroatomic polymer-carbon composite. The method includes forming a heteroatomic polymer-carbon composite and loading the transition metal onto the composite. The invention also provides a method of making a membrane electrode assembly for a fuel cell that includes the metal-polymer-carbon composite catalyst.

Activity and Stability of Dispersed Multi Metallic Pt-based Catalysts for CO Tolerance in Proton Exchange Membrane Fuel Cell Anodes.

PubMed

Hassan, Ayaz; Ticianelli, Edson A

2018-01-01

Studies aiming at improving the activity and stability of dispersed W and Mo containing Pt catalysts for the CO tolerance in proton exchange membrane fuel cell (PEMFC) anodes are revised for the following catalyst systems: (1) a carbon supported PtMo electrocatalyst submitted to heat treatments; (2) Pt and PtMo nanoparticles deposited on carbon-supported molybdenum carbides (Mo2C/C); (3) ternary and quaternary materials formed by PtMoFe/C, PtMoRu/C and PtMoRuFe/C and; (4) Pt nanoparticles supported on tungsten carbide/carbon catalysts and its parallel evaluation with carbon supported PtW catalyst. The heat-treated (600 oC) Pt-Mo/C catalyst showed higher hydrogen oxidation activity in the absence and in the presence of CO and better stability, compared to all other Mo-containing catalysts. PtMoRuFe, PtMoFe, PtMoRu supported on carbon and Pt supported on Mo2C/C exhibited similar CO tolerances but better stability, as compared to as-prepared PtMo supported on carbon. Among the tungsten-based catalysts, tungsten carbide supported Pt catalyst showed reasonable performance and reliable stability in comparison to simple carbon supported PtW catalyst, though an uneven level of catalytic activity towards H2 oxidation in presence of CO is observed for the former as compared to Mo containing catalyst. However, a small dissolution of Mo, Ru, Fe and W from the anodes and their migration toward cathodes during the cell operation is observed. These results indicate that the fuel cell performance and stability has been improved but not yet totally resolved.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Stariha, Sarah; Macauley, Natalia; Sneed, Brian T.

The U.S. Department of Energy (DOE) set the 2020 durability target for polymer electrolyte membrane fuel cell transportation applications at 5000 hours. Since it is impractical to test every fuel cell for this length of time, there is ever increasing interest in developing accelerated stress tests (ASTs) that can accurately simulate the material component degradation in the membrane electrode assembly (MEA) observed under automotive operating conditions, but over a much shorter time frame. In this study, a square-wave catalyst AST was examined that shows a 5X time acceleration factor over the triangle-wave catalyst AST and a 25X time acceleration factormore » over the modified wet drive-cycle catalyst durability protocol, significantly decreasing the testing time. These acceleration factors were correlated to the platinum (Pt) particle size increase and associated decrease in electrochemical surface area (ECSA). This square-wave AST has been adopted by the DOE as a standard protocol to evaluate catalyst durability. We also compare three catalyst-durability protocols using state-of-the-art platinum-cobalt catalysts supported on high surface area carbon (SOA Pt-Co/HSAC) in the cathode catalyst layer. The results for each of the three tests showed both catalyst particle size increase and transition metal leaching. Moreover the acceleration factors for the alloy catalysts were smaller due to Co leaching being the predominant mechanism of voltage decay in ~5 nm PtCo/C catalysts. Finally, an extremely harsh carbon corrosion AST was run using the same SOA Pt-Co/HSAC catalyst. This showed minimal change in particle size and a low percentage Co loss from the cathode catalyst particles, despite a significant loss in catalyst layer thickness and cell performance. The carbon corrosion rates during these various ASTs were directly measured by monitoring the CO 2 emission from the cathode, further confirming the ability of the square-wave AST to evaluate the electro-catalyst independently of the support.« less

Dynamic response performance of proton exchange membrane fuel cell stack with Pt/C-RuO2·xH2O electrode

NASA Astrophysics Data System (ADS)

Lu, Lu; Xu, Hongfeng; Zhao, Hong; Sun, Xin; Dong, Yiming; Ren, Ruiming

2013-11-01

The dynamic response performance of a proton exchange membrane fuel cell (PEMFC) significantly affects its durability and reliability. Thus, the improvement of the dynamic performance of PEMFC has become the key for prolonging the PEMFC life in fuel cell vehicle applications. In this study, RuO2·xH2O is prepared by sol-gel method, and then sprayed onto catalyst layers to promote PEMFC dynamic response performance. The prepared RuO2·xH2O is characterized by TEM, which shows that the average particle size of RuO2·xH2O is 8 nm and that the particulates are uniformly distributed. A 10-cell stack is assembled using membrane electrode assembly (MEA) with and without RuO2·xH2O. This stack is studied under various loading cycles and operating conditions, including different air stoichiometries, relative humidities, and loading degrees. Results show that the steady-state performance of the MEA with RuO2·xH2O is better than that in the MEA without RuO2·xH2O with a decreasing relative humidity from 80% to 20%. A slower and more unstable dynamic response of the MEA without RuO2·xH2O is observed as air stoichiometry and relative humidity decrease as well as the loading increase. Thus, RuO2·xH2O improves the dynamic response performance, indicating that RuO2·xH2O can buffer the voltage undershoot, improve the stability, and prolong the lifetime of the PEMFC stack.

Towards fully spray coated organic light emitting devices

NASA Astrophysics Data System (ADS)

Gilissen, Koen; Stryckers, Jeroen; Manca, Jean; Deferme, Wim

2014-10-01

Pi-conjugated polymer light emitting devices have the potential to be the next generation of solid state lighting. In order to achieve this goal, a low cost, efficient and large area production process is essential. Polymer based light emitting devices are generally deposited using techniques based on solution processing e.g.: spin coating, ink jet printing. These techniques are not well suited for cost-effective, high throughput, large area mass production of these organic devices. Ultrasonic spray deposition however, is a deposition technique that is fast, efficient and roll to roll compatible which can be easily scaled up for the production of large area polymer light emitting devices (PLEDs). This deposition technique has already successfully been employed to produce organic photovoltaic devices (OPV)1. Recently the electron blocking layer PEDOT:PSS2 and metal top contact3 have been successfully spray coated as part of the organic photovoltaic device stack. In this study, the effects of ultrasonic spray deposition of polymer light emitting devices are investigated. For the first time - to our knowledge -, spray coating of the active layer in PLED is demonstrated. Different solvents are tested to achieve the best possible spray-able dispersion. The active layer morphology is characterized and optimized to produce uniform films with optimal thickness. Furthermore these ultrasonic spray coated films are incorporated in the polymer light emitting device stack to investigate the device characteristics and efficiency. Our results show that after careful optimization of the active layer, ultrasonic spray coating is prime candidate as deposition technique for mass production of PLEDs.

A concise guide to sustainable PEMFCs: recent advances in improving both oxygen reduction catalysts and proton exchange membranes.

PubMed

Scofield, Megan E; Liu, Haiqing; Wong, Stanislaus S

2015-08-21

The rising interest in fuel cell vehicle technology (FCV) has engendered a growing need and realization to develop rational chemical strategies to create highly efficient, durable, and cost-effective fuel cells. Specifically, technical limitations associated with the major constituent components of the basic proton exchange membrane fuel cell (PEMFC), namely the cathode catalyst and the proton exchange membrane (PEM), have proven to be particularly demanding to overcome. Therefore, research trends within the community in recent years have focused on (i) accelerating the sluggish kinetics of the catalyst at the cathode and (ii) minimizing overall Pt content, while simultaneously (a) maximizing activity and durability as well as (b) increasing membrane proton conductivity without causing any concomitant loss in either stability or as a result of damage due to flooding. In this light, as an example, high temperature PEMFCs offer a promising avenue to improve the overall efficiency and marketability of fuel cell technology. In this Critical Review, recent advances in optimizing both cathode materials and PEMs as well as the future and peculiar challenges associated with each of these systems will be discussed.

Attrition Resistant Iron-Based Fischer-Tropsch Catalysts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jothimurugesan, K.; Goodwin, J.G.; Spivey, J.J.

1997-03-26

The Fischer-Tropsch (F-T) reaction provides a way of converting coal-derived synthesis gas (CO+H{sub 2}) to liquid fuels. Since the reaction is highly exothermic, one of the major problems in control of the reaction is heat removal. Recent work has shown that the use of slurry bubble column reactors (SBCRS) can largely solve this problem. Iron-based (Fe) catalysts are preferred catalysts for F-T when using low CO/H{sub 2} ratio synthesis gases derived from modem coal gasifiers. This is because in addition to reasonable F-T activity, the FT catalysts also possess high water gas shift (WGS) activity. However, a serious problem withmore » the use of Fe catalysts in a SBCR is their tendency to undergo attrition. This can cause fouling/plugging of downstream filters and equipment, making the separation of catalyst from the oil/wax product very difficult if not impossible, and results in a steady loss of catalyst from the reactor. The objectives of this research are to develop a better understanding of the parameters affecting attrition resistance of Fe F-T catalysts suitable for use in SBCRs and to incorporate this understanding into the design of novel Fe catalysts having superior attrition resistance. Catalyst preparations will be based on the use of spray drying and will be scalable using commercially available equipment. The research will employ among other measurements, attrition testing and F-T synthesis, including long duration slurry reactor runs in order to ascertain the degree of success of the various preparations. The goal is to develop an Fe catalyst which can be used in a SBCR having only an internal filter for separation of the catalyst from the liquid product, without sacrificing F-T activity and selectivity.« less

Attrition Resistant Iron-Based Fischer-Tropsch Catalysts.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jothimurugesan, K.; Goodwin, J.S.; Spivey, J.J.

1997-09-22

The Fischer-Tropsch (F-T) reaction provides a way of converting coal-derived synthesis gas (CO and H{sub 2}) to liquid fuels. Since the reaction is highly exothermic, one of the major problems in control of the reaction is heat removal. Recent work has shown that the use of slurry bubble column reactors (SBCRs) can largely solve this problem. Iron-based (Fe) catalysts are preferred catalysts for F-T when using low CO/H{sub 2} ratio synthesis gases derived from modern coal gasifiers. This is because in addition to reasonable F-T activity, the F-T catalysts also possess high water gas shift (WGS) activity. However, a seriousmore » problem with the use of Fe catalysts in a SBCR is their tendency to undergo attrition. This can cause fouling/plugging of downstream filters and equipment, making the separation of catalyst from the oil/wax product very difficult if not impossible, and results in a steady loss of catalyst from the reactor. The objectives of this research are to develop a better understanding of the parameters affecting attrition resistance of Fe F-T catalysts suitable for use in SBCRs and to incorporate this understanding into the design of novel Fe catalysts having superior attrition resistance. Catalyst preparations will be based on the use of spray drying and will be scalable using commercially available equipment. The research will employ among other measurements, attrition testing and F-T synthesis, including long duration slurry reactor runs in order to ascertain the degree of success of the various preparations. The goal is to develop an Fe catalyst which can be used in a SBCR having only an internal filter for separation of the catalyst from the liquid product, without sacrificing F-T activity and selectivity.« less

Fabrication of polymer/cadmium sulfide hybrid solar cells [P3HT:CdS and PCPDTBT:CdS] by spray deposition.

PubMed

Kumar, Neetesh; Dutta, Viresh

2014-11-15

This paper investigates fabrication of surfactant free CdS nanoparticles (NPs) and application in the fabrication of P3HT:CdS and PCPDTBT:CdS bulk-heterojunction hybrid solar cells using high-throughput, large-area, low cost spray deposition technique. Both the hybrid active layers and hole transport layers are deposited by spray technique. The CdS/Poly(3-hexylthiophene-2,5-diyl) (P3HT) and CdS/Poly[2,6-(4,4-bis-(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b']dithiophene)-alt-4,7(2,1,3-benzothiadiazole)] (PCPDTBT) hybrid devices are fabricated by spray deposition process at optimized conditions (i.e. film thickness, spray solution volume, distance between sample and spray nozzle, substrate temperature, etc.). The power conversion efficiency of η=0.6% and 1.02% is obtained for P3HT:CdS and PCPDTBT:CdS hybrid devices, respectively. Spray coating holds significant promise as a technique capable of fabricating large-area, high performance hybrid solar cells. Copyright © 2014 Elsevier Inc. All rights reserved.

Method of making chalcogen catalysts for polymer electrolyte fuel cells

DOEpatents

Choi, Jong-Ho; Zelenay, Piotr; Wieckowski, Andrzej; Cao, Dianxue

2010-12-14

A method of making an electrode catalyst material using aqueous solutions. The electrode catalyst material includes a support comprising at least one transition metal and at least one chalcogen disposed on a surface of the transition metal. The method includes reducing a metal powder, mixing the metal powder with an aqueous solution containing at least one inorganic compound of the chalcogen to form a mixture, and providing a reducing agent to the mixture to form nanoparticles of the electrode catalyst. The electrode catalyst may be used in a membrane electrode assembly for a fuel cell.

Evaluation of asphalt rubber membrane interlayer (ARMI) using the University of Florida's composite system interface cracking (CSIC) test [summary].

DOT National Transportation Integrated Search

2012-01-01

Since the late 1970s, FDOT : has applied an interlayer : of Asphalt Rubber : Membrane Interlayer : (ARMI) to asphalt roadway : surfaces. ARMI layers are : constructed by spraying : asphalt rubber binder onto : the asphalt, covering the : layer with n...

Polymer-silica hybrids for separation of CO2 and catalysis of organic reactions

NASA Astrophysics Data System (ADS)

Silva Mojica, Ernesto

Porous materials comprising polymeric and inorganic segments have attracted interest from the scientific community due to their unique properties and functionalities. The physical and chemical characteristics of these materials can be effectively exploited for adsorption applications. This dissertation covers the experimental techniques for fabrication of poly(vinyl alcohol) (PVA) and silica (SiO2) porous supports, and their functionalization with polyamines for developing adsorbents with potential applications in separation of CO2 and catalysis of organic reactions. The supports were synthesized by processes involving (i) covalent cross-linking of PVA, (ii) hydrolysis and poly-condensation of silica precursors (i,e,. sol-gel synthesis), and formation of porous structures via (iii) direct templating and (iv) phase inversion techniques. Their physical structure was controlled by the proper combination of the preparation procedures, which resulted in micro-structured porous materials in the form of micro-particles, membranes, and pellets. Their adsorption characteristics were tailored by functionalization with polyethyleneimine (PEI), and their physicochemical properties were characterized by vibrational spectroscopy (FTIR, UV-vis), microscopy (SEM), calorimetry (TGA, DSC), and adsorption techniques (BET, step-switch adsorption). Spectroscopic investigations of the interfacial cross-linking reactions of PEI and PVA with glutaraldehyde (GA) revealed that PEI catalyzes the cross-linking reactions of PVA in absence of external acid catalysts. In-situ IR spectroscopy coupled with a focal plane array (FPA) image detector allowed the characterization of a gradient interface on a PEI/PVA composite membrane and the investigation of the cross-linking reactions as a function of time and position. The results served as a basis to postulate possible intermediates, and propose the reaction mechanisms. The formulation of amine-functionalized CO2 capture sorbents was based on the spectroscopic investigation of the interactions of CO 2 with amine molecules under simulated CO2 capture conditions. Industrial CO2 capture processes involve fluidization and require degradation-resistant sorbents in the form of pellets. Agglomeration of silica-based CO2 capture sorbents involved the formulation of a polymer binder solution and the design of a scalable pelletization process. The characterization of these pellets revealed the formation of a CO 2-permeable polymer-silica network, which is resistant to attrition, and exhibits similar CO2 capture and degradation performance as the non-pelletized sorbents. The performance of these sorbents and pellets was tested in lab-scale and bench-scale adsorption units, using in-house fabricated fixed-bed and fluidized-bed reactors. A compartmental modeling technique was used to simulate the CO2 adsorption process and to elucidate the kinetic and thermodynamic parameters that impact the commercial viability of emerging CO2 capture technologies. The fundamental concepts and experimental techniques developed for the preparation of CO2 capture sorbents served as a basis for fabricating amine-functionalized polymer-silica hybrids for applications in catalysis of organic reactions. (i) Basic catalysts for carbon-carbon addition reactions were prepared by immobilization of amine molecules on silica supports. The activity of these catalysts and the mechanisms of base-catalyzed organic condensation reactions were investigated by an in-situ FTIR micro-scale reactor. (ii) Particle-loaded PVA composite membranes were selected for immobilization of glucose oxidase (GOx). GOx was immobilized by adsorption at pH values between 3.5 and 7.1. The results showed that adsorption was primarily achieved via hydrophobic interactions, and that PVA membranes loaded with amine-functionalized particles could help retain the activity of immobilized GOx by providing a proper hydrophilic/hydrophobic balance to the immobilized enzymes micro-environment.

Glycerin purification using asymmetric nano-structured ceramic membranes from production of waste fish oil biodiesel

NASA Astrophysics Data System (ADS)

Maghami, M.; Sadrameli, S. M.; Shamloo, M.

2018-02-01

Biodiesel is an environmental friendly alternative liquid transportation fuel that can be used in diesel engines without major modifications. The scope of this research work is to produce biodiesel from waste fish oil and its purification from the byproducts using a ceramic membrane. Transesterification of waste fish oil was applied for the biodiesel production using methanol in the presence of KOH as a catalyst. Effect of catalyst weight percent, temperature and methanol to oil molar ratio (MR) on the biodiesel yield have been studied and the results show that highest methyl ester yield of 79.2% has been obtained at 60 °C, MR: 6 and 1% KOH. The produced biodiesel purified by a ceramic membrane. Membrane flux and glycerin removal at different operating conditions such as temperature, trans-membrane pressures and cross flow velocities have been measured. Glycerin purity by membrane method is 99.97% by weight at the optimum condition. The highest membrane flux occurred at 50 °C temperature, 1 bar pressure and 3 m/s velocity.

Process for photosynthetically splitting water

DOEpatents

Greenbaum, Elias

1984-01-01

The invention is an improved process for producing gaseous hydrogen and oxygen from water. The process is conducted in a photolytic reactor which contains a water-suspension of a photoactive material containing a hydrogen-liberating catalyst. The reactor also includes a volume for receiving gaseous hydrogen and oxygen evolved from the liquid phase. To avoid oxygen-inactivation of the catalyst, the reactor is evacuated continuously by an external pump which circulates the evolved gases through means for selectively recovering hydrogen therefrom. The pump also cools the reactor by evaporating water from the liquid phase. Preferably, product recovery is effected by selectively diffusing the hydrogen through a heated semipermeable membrane, while maintaining across the membrane a magnetic field gradient which biases the oxygen away from the heated membrane. This promotes separation, minimizes the back-reaction of hydrogen and oxygen, and protects the membrane.

Hydrogen no-vent fill testing in a 5 cubic foot (142 liter) tank using spray nozzle and spray bar liquid injection

NASA Technical Reports Server (NTRS)

Moran, Matthew E.; Nyland, Ted W.

1992-01-01

A total of 38 hydrogen no-vent fill tests were performed in this test series using various size spray nozzles and a spray bar with different hole sizes in a 5 cubic foot receiver tank. Fill levels of 90 percent by volume or greater were achieved in 26 of the tests while maintaining a receiver tank pressure below 30 psia. Spray nozzles were mounted at the top of the tank, whereas, the spray bar was centered in the tank axially. The spray nozzle no-vent fills demonstrated tank pressure and temperature responses comparable to previous test series. Receiver tank pressure responses for the spray bar configuration were similar to the spray nozzle tests with the pressure initially rising rapidly, then leveling off as vapor condenses onto the discharging liquid streams, and finally ramping up near the end of the test due to ullage compression. Both liquid injection techniques tested were capable of filling the receiver tank to 90 percent under variable test conditions. Comparisons between the spray nozzle and spray bar configurations for well matched test conditions indicate the spray nozzle injection technique is more effective in minimizing the receiving tank pressure throughout a no-vent fill compared to the spray bar under normal gravity conditions.

Effect of polymer binders in anode catalyst layer on performance of alkaline direct ethanol fuel cells

NASA Astrophysics Data System (ADS)

Li, Y. S.; Zhao, T. S.; Liang, Z. X.

In preparing low-temperature fuel cell electrodes, a polymer binder is essential to bind discrete catalyst particles to form a porous catalyst layer that simultaneously facilitates the transfer of ions, electrons, and reactants/products. For two types of polymer binder, namely, an A3-an anion conducting ionomer and a PTFE-a neutral polymer, an investigation is made of the effect of the content of each binder in the anode catalyst layer on the performance of an alkaline direct ethanol fuel cell (DEFC) with an anion-exchange membrane and non-platinum (non-Pt) catalysts. Experiments are performed by feeding either ethanol (C 2H 5OH) solution or ethanol-potassium hydroxide (C 2H 5OH-KOH) solution. The experimental results for the case of feeding C 2H 5OH solution without added KOH indicate that the cell performance varies with the A3 ionomer content in the anode catalyst layer, and a content of 10 wt.% exhibits the best performance. When feeding C 2H 5OH-KOH solution, the results show that: (i) in the region of low current density, the best performance is achieved for a membrane electrode assembly without any binder in the anode catalyst layer; (ii) in the region of high current density, the performance is improved with incorporation of PTFE binder in the anode catalyst layer; (iii) the PTFE binder yields better performance than does the A3 binder.

Surface modification of poly(vinylidene fluoride) hollow fibre membranes for biogas purification in a gas-liquid membrane contactor system.

PubMed

Jin, Pengrui; Huang, Chuan; Li, Jiaxiang; Shen, Yadong; Wang, Liao

2017-11-01

The wetting of hollow fibre membranes decreases the performance of the liquid-gas membrane contactor for CO 2 capture in biogas upgrading. To solve this problem, in this work, a poly(vinylidene fluoride) (PVDF) hollow fibre membrane for a liquid-gas membrane contactor was coated with a superhydrophobic layer composed of a combination of hydrophobic SiO 2 nanoparticles and polydimethylsiloxane (PDMS) by the method of spray deposition. A rough layer of SiO 2 deposited on the PVDF membrane resulted in an enhanced surface hydrophobicity. The surface structure of the pristine PVDF significantly affected the homogeneity of the generated SiO 2 layer. A uniform surface coating on the PVDF upper layer resulted from the presence of micrometre and nanometre-sized roughness on the surface of the PVDF membrane, which was achieved with a SiO 2 concentration of 4.44 mg ml -1 (0.2 g/45 ml) in the coating solution. As a result, the water contact angle of the modified surface was recorded as 155 ± 3°, which is higher than that of the pristine surface. The high contact angle is advantageous for reducing the wetting of the membrane. Additional mass transfer resistance was introduced by the superhydrophobic layer. In addition, continuous CO 2 absorption tests were carried out in original and modified PVDF hollow fibre membrane contactors, using monoethanolamine (MEA) solution as the absorbent. A long-term stability test revealed that the modified PVDF hollow fibre membrane contactor was able to outperform the original membrane contactor and demonstrated outstanding long-term stability, suggesting that spray deposition is a promising approach to obtain superhydrophobic PVDF membranes for liquid-gas membrane absorption.

Surface modification of poly(vinylidene fluoride) hollow fibre membranes for biogas purification in a gas–liquid membrane contactor system

PubMed Central

Huang, Chuan; Li, Jiaxiang; Shen, Yadong; Wang, Liao

2017-01-01

The wetting of hollow fibre membranes decreases the performance of the liquid–gas membrane contactor for CO2 capture in biogas upgrading. To solve this problem, in this work, a poly(vinylidene fluoride) (PVDF) hollow fibre membrane for a liquid–gas membrane contactor was coated with a superhydrophobic layer composed of a combination of hydrophobic SiO2 nanoparticles and polydimethylsiloxane (PDMS) by the method of spray deposition. A rough layer of SiO2 deposited on the PVDF membrane resulted in an enhanced surface hydrophobicity. The surface structure of the pristine PVDF significantly affected the homogeneity of the generated SiO2 layer. A uniform surface coating on the PVDF upper layer resulted from the presence of micrometre and nanometre-sized roughness on the surface of the PVDF membrane, which was achieved with a SiO2 concentration of 4.44 mg ml−1 (0.2 g/45 ml) in the coating solution. As a result, the water contact angle of the modified surface was recorded as 155 ± 3°, which is higher than that of the pristine surface. The high contact angle is advantageous for reducing the wetting of the membrane. Additional mass transfer resistance was introduced by the superhydrophobic layer. In addition, continuous CO2 absorption tests were carried out in original and modified PVDF hollow fibre membrane contactors, using monoethanolamine (MEA) solution as the absorbent. A long-term stability test revealed that the modified PVDF hollow fibre membrane contactor was able to outperform the original membrane contactor and demonstrated outstanding long-term stability, suggesting that spray deposition is a promising approach to obtain superhydrophobic PVDF membranes for liquid–gas membrane absorption. PMID:29291117

Catalytic performance of strong acid catalyst: Methyl modified SBA-15 loaded perfluorinated sulfonic acid obtained by the waste perfluorinated sulfonic acid ion exchange membrane

NASA Astrophysics Data System (ADS)

Jiang, Tingshun; Huang, Qiuyan; Li, Yingying; Fang, Minglan; Zhao, Qian

2018-02-01

Mesoporous molecular sieve (SBA-15) was modified using the trimethylchlorosilane as functional agent and the silylation SBA-15 mesoporous material was prepared in this work. The alcohol solution of perfluorinated sulfonic acid dissolved from the waste perfluorinated sulfonic acid ion exchange membrane (PFSIEM) was loaded onto the resulting mesoporous material by the impregnation method and their physicochemical properties were characterized by FT-IR, N2-physisorption, XRD, TG-DSC and TEM. The catalytic activities of these synthesized solid acid catalysts were evaluated by alkylation of phenol with tert-butyl alcohol. The influence of reaction temperature, weight hour space velocity (WHSV) and reaction time on the phenol conversion and product selectivity were assessed by means of a series of experiments. The results showed that with the increase of the active component of the catalyst, these catalysts still remained good mesoporous structure, but the mesoporous ordering decreased to some extent. These catalysts exhibited good catalytic performance for the alkylation of phenol with tert-butanol. The maximum phenol conversion of 89.3% with 70.9% selectivity to 4-t-butyl phenol (4-TBP) was achieved at 120 °C and the WHSV is 4 h-1. The methyl group was loaded on the surface of the catalyst by trimethylchlorosilane. This is beneficial to retard the deactivation of the catalyst. In this work, the alkylation of phenol with tert-butyl alcohol were carried out using the methyl modified SBA-15 mesoporous materials loaded perfluorinated sulfonic acid as catalysts. The results show that the resulting catalyst exhibited high catalytic activity.

Activity targets for nanostructured platinum-group-metal-free catalysts in hydroxide exchange membrane fuel cells.

PubMed

Setzler, Brian P; Zhuang, Zhongbin; Wittkopf, Jarrid A; Yan, Yushan

2016-12-06

Fuel cells are the zero-emission automotive power source that best preserves the advantages of gasoline automobiles: low upfront cost, long driving range and fast refuelling. To make fuel-cell cars a reality, the US Department of Energy has set a fuel cell system cost target of US$30 kW -1 in the long-term, which equates to US$2,400 per vehicle, excluding several major powertrain components (in comparison, a basic, but complete, internal combustion engine system costs approximately US$3,000). To date, most research for automotive applications has focused on proton exchange membrane fuel cells (PEMFCs), because these systems have demonstrated the highest power density. Recently, however, an alternative technology, hydroxide exchange membrane fuel cells (HEMFCs), has gained significant attention, because of the possibility to use stable platinum-group-metal-free catalysts, with inherent, long-term cost advantages. In this Perspective, we discuss the cost profile of PEMFCs and the advantages offered by HEMFCs. In particular, we discuss catalyst development needs for HEMFCs and set catalyst activity targets to achieve performance parity with state-of-the-art automotive PEMFCs. Meeting these targets requires careful optimization of nanostructures to pack high surface areas into a small volume, while maintaining high area-specific activity and favourable pore-transport properties.

Activity targets for nanostructured platinum-group-metal-free catalysts in hydroxide exchange membrane fuel cells

NASA Astrophysics Data System (ADS)

Setzler, Brian P.; Zhuang, Zhongbin; Wittkopf, Jarrid A.; Yan, Yushan

2016-12-01

Fuel cells are the zero-emission automotive power source that best preserves the advantages of gasoline automobiles: low upfront cost, long driving range and fast refuelling. To make fuel-cell cars a reality, the US Department of Energy has set a fuel cell system cost target of US$30 kW-1 in the long-term, which equates to US$2,400 per vehicle, excluding several major powertrain components (in comparison, a basic, but complete, internal combustion engine system costs approximately US$3,000). To date, most research for automotive applications has focused on proton exchange membrane fuel cells (PEMFCs), because these systems have demonstrated the highest power density. Recently, however, an alternative technology, hydroxide exchange membrane fuel cells (HEMFCs), has gained significant attention, because of the possibility to use stable platinum-group-metal-free catalysts, with inherent, long-term cost advantages. In this Perspective, we discuss the cost profile of PEMFCs and the advantages offered by HEMFCs. In particular, we discuss catalyst development needs for HEMFCs and set catalyst activity targets to achieve performance parity with state-of-the-art automotive PEMFCs. Meeting these targets requires careful optimization of nanostructures to pack high surface areas into a small volume, while maintaining high area-specific activity and favourable pore-transport properties.

Improved Anode for a Direct Methanol Fuel Cell

NASA Technical Reports Server (NTRS)

Valdez, Thomas; Narayanan, Sekharipuram

2005-01-01

A modified chemical composition has been devised to improve the performance of the anode of a direct methanol fuel cell. The main feature of the modified composition is the incorporation of hydrous ruthenium oxide into the anode structure. This modification can reduce the internal electrical resistance of the cell and increase the degree of utilization of the anode catalyst. As a result, a higher anode current density can be sustained with a smaller amount of anode catalyst. These improvements can translate into a smaller fuel-cell system and higher efficiency of conversion. Some background information is helpful for understanding the benefit afforded by the addition of hydrous ruthenium oxide. The anode of a direct methanol fuel cell sustains the electro-oxidation of methanol to carbon dioxide in the reaction CH3OH + H2O--->CO2 + 6H(+) + 6e(-). An electrocatalyst is needed to enable this reaction to occur. The catalyst that offers the highest activity is an alloy of approximately equal numbers of atoms of the noble metals platinum and ruthenium. The anode is made of a composite material that includes high-surface-area Pt/Ru alloy particles and a proton-conducting ionomeric material. This composite is usually deposited onto a polymer-electrolyte (proton-conducting) membrane and onto an anode gas-diffusion/current-collector sheet that is subsequently bonded to the proton-conducting membrane by hot pressing. Heretofore, the areal density of noble-metal catalyst typically needed for high performance has been about 8 mg/cm2. However, not all of the catalyst has been utilized in the catalyzed electro-oxidation reaction. Increasing the degree of utilization of the catalyst would make it possible to improve the performance of the cell for a given catalyst loading and/or reduce the catalyst loading (thereby reducing the cost of the cell). The use of carbon and possibly other electronic conductors in the catalyst layer has been proposed for increasing the utilization of the catalyst by increasing electrical connectivity between catalyst particles. However, the relatively low density of carbon results in thick catalyst layers that impede the mass transport of methanol to the catalytic sites. Also, the electrical conductivity of carbon is less than 1/300th of typical metals. Furthermore, the polymer-electrolyte membrane material is acidic and most metals are not chemically stable in contact with it. Finally, a material that conducts electrons (but not protons) does not contribute to the needed transport of protons produced in the electro-oxidation reaction.

Comparison of preparation techniques for CoFeNb/CNTs catalyst

NASA Astrophysics Data System (ADS)

Hamid, Hami Haslinda; Zabidi, Noor Asmawati Mohd; Gholami, Zahra; Shaharun, Maizatul Shima

2016-11-01

CoFe-based catalysts were prepared using reverse-microemulsion and co-impregnation method. Effect of different preparation techniques on morphology and physiochemical properties of the FTS catalyst CoFeNb/CNTs was investigated. TEM analyses show that the morphological properties of catalysts were affected by preparation techniques. Reverse-micremulsion and co-impregnation method resulted in average particle size of 5.61 nm and 6.20 nm respectively. CoFe-impregnation catalyst is reducible at lower temperature compared to that of reverse-microemulsion catalyst. Acid and thermal treatment of CNTs created defects onto CNTs-support.

Application of graphene oxide in water treatment

NASA Astrophysics Data System (ADS)

Liu, Yongchen

2017-11-01

Graphene oxide has good hydrophilicity and has been tried to use it into thin films for water treatment in recent years. In this paper, the preparation methods of graphene oxide membrane are reviewed, including vacuum suction filtration, spray coating, spin coating, dip coating and the layer by layer method. Secondly, the mechanism of mass transfer of graphene membrane is introduced in detail. The application of the graphene oxide membrane, modified graphene oxide membrane and graphene hybrid membranes were discussed in RO, vaporization, nanofiltration and other aspects. Finally, the development and application of graphene membrane in water treatment were discussed.

Highly efficient nonprecious metal catalyst prepared with metal–organic framework in a continuous carbon nanofibrous network

PubMed Central

Shui, Jianglan; Chen, Chen; Grabstanowicz, Lauren; Zhao, Dan; Liu, Di-Jia

2015-01-01

Fuel cell vehicles, the only all-electric technology with a demonstrated >300 miles per fill travel range, use Pt as the electrode catalyst. The high price of Pt creates a major cost barrier for large-scale implementation of polymer electrolyte membrane fuel cells. Nonprecious metal catalysts (NPMCs) represent attractive low-cost alternatives. However, a significantly lower turnover frequency at the individual catalytic site renders the traditional carbon-supported NPMCs inadequate in reaching the desired performance afforded by Pt. Unconventional catalyst design aiming at maximizing the active site density at much improved mass and charge transports is essential for the next-generation NPMC. We report here a method of preparing highly efficient, nanofibrous NPMC for cathodic oxygen reduction reaction by electrospinning a polymer solution containing ferrous organometallics and zeolitic imidazolate framework followed by thermal activation. The catalyst offers a carbon nanonetwork architecture made of microporous nanofibers decorated by uniformly distributed high-density active sites. In a single-cell test, the membrane electrode containing such a catalyst delivered unprecedented volumetric activities of 3.3 A⋅cm−3 at 0.9 V or 450 A⋅cm−3 extrapolated at 0.8 V, representing the highest reported value in the literature. Improved fuel cell durability was also observed. PMID:26261338

Highly efficient nonprecious metal catalyst prepared with metal–organic framework in a continuous carbon nanofibrous network

DOE PAGES

Shui, Jianglan; Chen, Chen; Grabstanowicz, Lauren; ...

2015-08-25

Fuel cell vehicles, the only all-electric technology with a demonstrated >300 miles per fill travel range, use Pt as the electrode catalyst. The high price of Pt creates a major cost barrier for large-scale implementation of polymer electrolyte membrane fuel cells. Nonprecious metal catalysts (NPMCs) represent attractive low-cost alternatives. However, a significantly lower turnover frequency at the individual catalytic site renders the traditional carbon-supported NPMCs inadequate in reaching the desired performance afforded by Pt. Unconventional catalyst design aiming at maximizing the active site density at much improved mass and charge transports is essential for the next-generation NPMC. We report heremore » a method of preparing highly efficient, nanofibrous NPMC for cathodic oxygen reduction reaction by electrospinning a polymer solution containing ferrous organometallics and zeolitic imidazolate framework followed by thermal activation. The catalyst offers a carbon nanonetwork architecture made of microporous nanofibers decorated by uniformly distributed high-density active sites. In a single-cell test, the membrane electrode containing such a catalyst delivered unprecedented volumetric activities of 3.3 A∙cm -3 at 0.9 V or 450 A∙cm -3 extrapolated at 0.8 V, representing the highest reported value in the literature. Improved fuel cell durability was also observed.« less

Highly efficient nonprecious metal catalyst prepared with metal-organic framework in a continuous carbon nanofibrous network.

PubMed

Shui, Jianglan; Chen, Chen; Grabstanowicz, Lauren; Zhao, Dan; Liu, Di-Jia

2015-08-25

Fuel cell vehicles, the only all-electric technology with a demonstrated >300 miles per fill travel range, use Pt as the electrode catalyst. The high price of Pt creates a major cost barrier for large-scale implementation of polymer electrolyte membrane fuel cells. Nonprecious metal catalysts (NPMCs) represent attractive low-cost alternatives. However, a significantly lower turnover frequency at the individual catalytic site renders the traditional carbon-supported NPMCs inadequate in reaching the desired performance afforded by Pt. Unconventional catalyst design aiming at maximizing the active site density at much improved mass and charge transports is essential for the next-generation NPMC. We report here a method of preparing highly efficient, nanofibrous NPMC for cathodic oxygen reduction reaction by electrospinning a polymer solution containing ferrous organometallics and zeolitic imidazolate framework followed by thermal activation. The catalyst offers a carbon nanonetwork architecture made of microporous nanofibers decorated by uniformly distributed high-density active sites. In a single-cell test, the membrane electrode containing such a catalyst delivered unprecedented volumetric activities of 3.3 A ⋅ cm(-3) at 0.9 V or 450 A ⋅ cm(-3) extrapolated at 0.8 V, representing the highest reported value in the literature. Improved fuel cell durability was also observed.

Same-View Nano-XAFS/STEM-EDS Imagings of Pt Chemical Species in Pt/C Cathode Catalyst Layers of a Polymer Electrolyte Fuel Cell.

PubMed

Takao, Shinobu; Sekizawa, Oki; Samjeské, Gabor; Nagamatsu, Shin-ichi; Kaneko, Takuma; Yamamoto, Takashi; Higashi, Kotaro; Nagasawa, Kensaku; Uruga, Tomoya; Iwasawa, Yasuhiro

2015-06-04

We have made the first success in the same-view imagings of 2D nano-XAFS and TEM/STEM-EDS under a humid N2 atmosphere for Pt/C cathode catalyst layers in membrane electrode assemblies (MEAs) of polymer electrolyte fuel cells (PEFCs) with Nafion membrane to examine the degradation of Pt/C cathodes by anode gas exchange cycles (start-up/shut-down simulations of PEFC vehicles). The same-view imaging under the humid N2 atmosphere provided unprecedented spatial information on the distribution of Pt nanoparticles and oxidation states in the Pt/C cathode catalyst layer as well as Nafion ionomer-filled nanoholes of carbon support in the wet MEA, which evidence the origin of the formation of Pt oxidation species and isolated Pt nanoparticles in the nanohole areas of the cathode layer with different Pt/ionomer ratios, relevant to the degradation of PEFC catalysts.

Percolation in a Proton Exchange Membrane Fuel Cell Catalyst Layer

DOE Office of Scientific and Technical Information (OSTI.GOV)

Stacy, Stephen; Allen, Jeffrey

Water management in the catalyst layers of proton exchange membrane fuel cells (PEMFC) is confronted by two issues, flooding and dry out, both of which result in improper functioning of the fuel cell and lead to poor performance and degradation. At the present time, the data that has been reported about water percolation and wettability within a fuel cell catalyst layer is limited. A method and apparatus for measuring the percolation pressure in the catalyst layer has been developed based upon an experimental apparatus used to test water percolation in porous transport layers (PTL). The experimental setup uses a pseudomore » Hele-Shaw type testing where samples are compressed and a fluid is injected into the sample. Testing the samples gives percolation pressure plots which show trends in increasing percolation pressure with an increase in flow rate. A decrease in pressure was seen as percolation occurred in one sample, however the pressure only had a rising effect in the other sample.« less

Deoxygenation of Palmitic and Lauric Acids over Pt/ZIF-67 Membrane/Zeolite 5A Bead Catalysts.

PubMed

Yang, Liqiu; Carreon, Moises A

2017-09-20

The deoxygenation of palmitic and lauric acids over 0.5 wt % Pt/ZIF-67 membrane/zeolite 5A bead catalysts is demonstrated. Almost complete conversion (% deoxygenation of ≥95%) of these two fatty acids was observed over both fresh and recycled catalyst after a 2 h reaction time. The catalysts displayed high selectivity to pentadecane and undecane via decarboxylation reaction pathway even at low 0.5 wt % Pt loading. Selectivity to pentadecane and undecane as high as ∼92% and ∼94% was observed under CO 2 atmosphere when palmitic and lauric acids were used respectively as reactants. Depending on the reaction gas atmosphere, two distinctive reaction pathways were observed: decarboxylation and hydrodeoxygenation. Specifically, it was found that decarboxylation reaction pathway was more favorable in the presence of helium and CO 2 , while hydrodeoxygenation pathway strongly competed against the decarboxylation pathway when hydrogen was employed during the deoxygenation reactions. Esters were identified as the key reaction intermediates leading to decarboxylation and hydrodeoxygenation pathways.

NASA Astrophysics Data System (ADS)

McHugh, K. M.; Key, J. F.

1994-06-01

Spray forming is a near- net- shape fabrication technology in which a spray of finely atomized liquid droplets is deposited onto a suitably shaped substrate or pattern to produce a coherent solid. The technology offers unique opportunities for simplifying materials processing, often while substantially improving product quality. Spray forming is applicable to a wide range of metals and nonmetals and offers property improvements resulting from rapid solidification (e.g., refined microstructures, extended solid solubilities, and reduced segregation). Economic benefits result from process simplification and the elimination of unit operations. Researchers at the Idaho National Engineering Laboratory (INEL) are developing spray forming technology for producing near- net- shape solids and coatings of a variety of metals, polymers, and composite materials using de Laval nozzles. This article briefly describes the atomization behavior of liquid metals in linear de Laval nozzles and illustrates the versatility of the process by summarizing results from two spray forming programs. In one program, low-carbon steel strip >0.75 mm thick was produced; in the other, polymer membranes ˜5 μm thick were spray formed.

Freestanding eggshell membrane-based electrodes for high-performance supercapacitors and oxygen evolution reaction

NASA Astrophysics Data System (ADS)

Geng, Jing; Wu, Hao; Al-Enizi, Abdullah M.; Elzatahry, Ahmed A.; Zheng, Gengfeng

2015-08-01

A type of freestanding, light-weight eggshell membrane-based electrode is demonstrated for supercapacitors and for oxygen evolution reaction (OER) catalysis. As a widely available daily waste, eggshell membranes have unique porous three-dimensional grid-like fibrous structures with relatively high surface area and abundant macropores, allowing for effective conjugation of carbon nanotubes and growth of NiCo2O4 nanowire arrays, an effective supercapacitor material and OER catalyst. The three-dimensional fibrous eggshell membrane frameworks with carbon nanotubes offer efficient pathways for charge transport, and the macropores between adjacent fibers are fully accessible for electrolytes and bubble evolution. As a supercapacitor, the eggshell membrane/carbon nanotube/NiCo2O4 electrode shows high specific capacitances at current densities from 1 to 20 A g-1, with excellent capacitance retention (>90%) at 10 A g-1 for over 10 000 cycles. When employed as an OER catalyst, this eggshell membrane-based electrode exhibits an OER onset potential of 1.53 V vs. the reversible hydrogen electrode (RHE), and a stable catalytic current density of 20 mA cm-2 at 1.65 V vs. the RHE.A type of freestanding, light-weight eggshell membrane-based electrode is demonstrated for supercapacitors and for oxygen evolution reaction (OER) catalysis. As a widely available daily waste, eggshell membranes have unique porous three-dimensional grid-like fibrous structures with relatively high surface area and abundant macropores, allowing for effective conjugation of carbon nanotubes and growth of NiCo2O4 nanowire arrays, an effective supercapacitor material and OER catalyst. The three-dimensional fibrous eggshell membrane frameworks with carbon nanotubes offer efficient pathways for charge transport, and the macropores between adjacent fibers are fully accessible for electrolytes and bubble evolution. As a supercapacitor, the eggshell membrane/carbon nanotube/NiCo2O4 electrode shows high specific capacitances at current densities from 1 to 20 A g-1, with excellent capacitance retention (>90%) at 10 A g-1 for over 10 000 cycles. When employed as an OER catalyst, this eggshell membrane-based electrode exhibits an OER onset potential of 1.53 V vs. the reversible hydrogen electrode (RHE), and a stable catalytic current density of 20 mA cm-2 at 1.65 V vs. the RHE. Electronic supplementary information (ESI) available: Supporting figures, with additional SEM images, EDS spectra, N2 sorption isotherms, charge-discharge curves, cycling performance, Ragone plot, Nyquist plots and linear scan voltammogram plots. See DOI: 10.1039/c5nr04603c

Improving the biocontrol potential of entomopathogenic nematodes against Mamestra brassicae: effect of spray application technique, adjuvants and an attractant.

PubMed

Beck, Bert; Brusselman, Eva; Nuyttens, David; Moens, Maurice; Temmerman, Femke; Pollet, Sabien; Van Weyenberg, Stephanie; Spanoghe, Pieter

2014-01-01

Steinernema carpocapsae Weiser, an entomopathogenic nematode (EPN), is a potential biological control agent for the cabbage moth (Mamestra brassicae L.). This research aimed to identify a suitable spray application technique, and to determine whether yeast extract added to an EPN spray has an attracting and/or a feeding stimulant effect on M. brassicae. The biological control capabilities of EPN against this pest were examined in the field. Good coverage of the underside of cauliflower leaves, the habitat of young instar larvae (L1-L4) of M. brassicae was obtained using different spray boom configurations with vertical extensions that carried underleaf spraying nozzles. One of the configurations was selected for field testing with an EPN spray. Brewer's yeast extract stimulated larval feeding on leaves, and increased the mortality of these larvae when exposed to EPN. The field trial showed that a spray application with S. carpocapsae, Addit and xanthan gum can effectively lower the numbers of cabbage heads damaged by M. brassicae. Brewer's yeast extract did not significantly increase this field performance of EPN. Steinernema carpocapsae, applied with an appropriate spray technique, can be used within biological control schemes as part of a resistance management programme for Bt. © 2013 Society of Chemical Industry.

Measurement of Ambient Air Motion of D. I. Gasoline Spray by LIF-PIV

NASA Astrophysics Data System (ADS)

Yamakawa, Masahisa; Isshiki, Seiji; Yoshizaki, Takuo; Nishida, Keiya

Ambient air velocity distributions in and around a D. I. gasoline spray were measured using a combination of LIF and PIV techniques. A rhodamine and water solution was injected into ambient air to disperse the fine fluorescent liquid particles used as tracers. A fuel spray was injected into the fluorescent tracer cloud and was illuminated by an Nd: YAG laser light sheet (532nm). The scattered light from the spray droplets and tracers was cut off by a high-pass filter (>560nm). As the fluorescence (>600nm) was transmitted through the high-pass filter, the tracer images were captured using a CCD camera and the ambient air velocity distribution could be obtained by PIV based on the images. This technique was applied to a D. I. gasoline spray. The ambient air flowed up around the spray and entered into the tail of the spray. Furthermore, the relative velocity between the spray and ambient air was investigated.

Mass Spectrometry of Polymer Electrolyte Membrane Fuel Cells.

PubMed

Johánek, Viktor; Ostroverkh, Anna; Fiala, Roman; Rednyk, Andrii; Matolín, Vladimír

2016-01-01

The chemical analysis of processes inside fuel cells under operating conditions in either direct or inverted (electrolysis) mode and their correlation with potentiostatic measurements is a crucial part of understanding fuel cell electrochemistry. We present a relatively simple yet powerful experimental setup for online monitoring of the fuel cell exhaust (of either cathode or anode side) downstream by mass spectrometry. The influence of a variety of parameters (composition of the catalyst, fuel type or its concentration, cell temperature, level of humidification, mass flow rate, power load, cell potential, etc.) on the fuel cell operation can be easily investigated separately or in a combined fashion. We demonstrate the application of this technique on a few examples of low-temperature (70°C herein) polymer electrolyte membrane fuel cells (both alcohol- and hydrogen-fed) subjected to a wide range of conditions.

Mass Spectrometry of Polymer Electrolyte Membrane Fuel Cells

PubMed Central

Ostroverkh, Anna; Fiala, Roman; Rednyk, Andrii; Matolín, Vladimír

2016-01-01

The chemical analysis of processes inside fuel cells under operating conditions in either direct or inverted (electrolysis) mode and their correlation with potentiostatic measurements is a crucial part of understanding fuel cell electrochemistry. We present a relatively simple yet powerful experimental setup for online monitoring of the fuel cell exhaust (of either cathode or anode side) downstream by mass spectrometry. The influence of a variety of parameters (composition of the catalyst, fuel type or its concentration, cell temperature, level of humidification, mass flow rate, power load, cell potential, etc.) on the fuel cell operation can be easily investigated separately or in a combined fashion. We demonstrate the application of this technique on a few examples of low-temperature (70°C herein) polymer electrolyte membrane fuel cells (both alcohol- and hydrogen-fed) subjected to a wide range of conditions. PMID:28042492

3D Polymer Hydrogel for High-Performance Atomic Fe and Mn Catalysts for Oxygen Reduction in Challenging Acids

NASA Astrophysics Data System (ADS)

Qiao, Zhi

Current platinum group metal (PGM)-free carbon nanocomposite catalysts for the oxygen reduction reaction (ORR) in acidic electrolyte often suffer from rapid degradation associated with carbon corrosion due to the use of large amount of the amorphoous carbon black supports. Here, we developed a new concept of using freestanding 3D hydrogel to design support-free Fe-N-C catalysts. A 3D polyaniline (PANI)-based hydrogel approach was used for preparing a new type of single atomic iron site-rich catalyst, which has exhibited exceptionally enhanced activity and stability compared to conventional Fe-N-C catalysts supported on amorphous carbon blacks. The achieved performance metric on the hydrogel PANI-Fe catalysts is one of the best ever reported PGM-free catalysts, reaching a half-wave potential up to 0.83 V vs. RHE and only leaving 30 mV gap with Pt/C catalysts (60mugPt/cm 2) in challenging acidic media. Remarkable ORR stability was accomplished as well on the same catalyst evidenced by using harsh potential cycling tests. The well dispersion of atomic iron into partially graphitized carbon, featured with dominance of micropores and porous network structures, is capable of accommodating increased number of active sites, strengthening local bonding among iron, nitrogen and carbon, and facilitating mass transfer. On the other hand, in order to decrease the produced Fenton reagent, which will oxidize the proton exchange membrane and ionomer in membrane electrode assembly (MEA), we produce Mn-based catalysts by this novel hydrogel method. This is the first time that Mn-based catalysts can show such outstanding performance in acid media, whose half-wave potential is up to 0.80 V vs. RHE. The work related to the performance improvement is still in processing. We believe the 3D polymer hydrogel approach would be a new pathway to advance PGM-free catalysts.

Operando fuel cell spectroscopy

NASA Astrophysics Data System (ADS)

Kendrick, Ian Michael

The active state of a catalyst only exists during catalysis (1) provided the motivation for developing operando spectroscopic techniques. A polymer electrolyte membrane fuel cell (PEMFC) was designed to interface with commercially available instruments for acquisition of infrared spectra of the catalytic surface of the membrane electrode assembly (MEA) during normal operation. This technique has provided insight of the complex processes occurring at the electrode surface. Nafion, the solid electrolyte used in most modern-day polymer electrolyte membrane fuel cells (PEMFC), serves many purposes in fuel cell operation. However, there is little known of the interface between Nafion and the electrode surface. Previous studies of complex Stark tuning curves of carbon monoxide on the surface of a platinum electrode were attributed the co-adsorption of bisulfite ions originating from the 0.5M H2SO4 electrolyte used in the study(2). Similar tuning curves obtained on a fuel cell MEA despite the absence of supplemental electrolytes suggest the adsorption of Nafion onto platinum (3). The correlation of spectra obtained using attenuated total reflectance spectroscopy (ATR) and polarization modulated IR reflection-absorption spectroscopy (PM-IRRAS) to a theoretical spectrum generated using density functional theory (DFT) lead to development of a model of Nafion and platinum interaction which identified participation of the SO3- and CF3 groups in Nafion adsorption. The use of ethanol as a fuel stream in proton exchange membrane fuel cells provides a promising alternative to methanol. Relative to methanol, ethanol has a greater energy density, lower toxicity and can be made from the fermentation of biomass(4). Operando IR spectroscopy was used to study the oxidation pathway of ethanol and Stark tuning behavior of carbon monoxide on Pt, Ru, and PtRu electrodes. Potential dependent products such as acetaldehyde, acetic acid and carbon monoxide are identified as well as previously unobserved peaks corresponding to adsorbed ethanol. A modification to the operando fuel cell design allowed for acquisition of Raman spectra. A confocal Raman microscope enabled characterization of the MEA through depth profiling. The potential dependent peaks of an Fe-N x/C catalyst were identified and compared to the theoretical spectra of the proposed active sites. It was determined that oxygen adsorbed onto iron/iron oxide carbon nanostructures were responsible for the experimentally obtained peaks. This finding was supported by additional Raman studies carried out on a catalyst with these active sites removed through peroxide treatments. 1 Topsoe, H., Developments in operando studies and in situ characterization of heterogeneous catalysts. Journal of Catalysis, 2003. 216(1-2): p. 155-164. 2 Stamenkovic, V., et al., Vibrational properties of CO at the Pt(111)-solution interface: the anomalous stark-tuning slope. Journal of Physical Chemistry B, 2005. 109(2): p. 678-680. 3 Kendrick, I., et al., Elucidating the Ionomer-Electrified Metal Interface. J. Am. Chem. Soc., 2010. 132(49): p. 17611-17616. 4 Lamy, C. and Leger, J.M., FUEL-CELLS - APPLICATION TO ELECTRIC VEHICLES. Journal De Physique Iv, 1994. 4(C1): p. 253-281.

Development testing of large volume water sprays for warm fog dispersal

NASA Technical Reports Server (NTRS)

Keller, V. W.; Anderson, B. J.; Burns, R. A.; Lala, G. G.; Meyer, M. B.; Beard, K. V.

1986-01-01

A new brute-force method of warm fog dispersal is described. The method uses large volume recycled water sprays to create curtains of falling drops through which the fog is processed by the ambient wind and spray induced air flow. Fog droplets are removed by coalescence/rainout. The efficiency of the technique depends upon the drop size spectra in the spray, the height to which the spray can be projected, the efficiency with which fog laden air is processed through the curtain of spray, and the rate at which new fog may be formed due to temperature differences between the air and spray water. Results of a field test program, implemented to develop the data base necessary to assess the proposed method, are presented. Analytical calculations based upon the field test results indicate that this proposed method of warm fog dispersal is feasible. Even more convincingly, the technique was successfully demonstrated in the one natural fog event which occurred during the test program. Energy requirements for this technique are an order of magnitude less than those to operate a thermokinetic system. An important side benefit is the considerable emergency fire extinguishing capability it provides along the runway.

Spray- and spin-assisted layer-by-layer assembly of copper nanoparticles on thin-film composite reverse osmosis membrane for biofouling mitigation.

PubMed

Ma, Wen; Soroush, Adel; Van Anh Luong, Tran; Brennan, Gregory; Rahaman, Md Saifur; Asadishad, Bahareh; Tufenkji, Nathalie

2016-08-01

Copper nanoparticles (CuNPs) have long been considered as highly effective biocides; however, the lack of suitable methods for loading CuNPs onto polymeric membranes is recognized as being one of the primary reasons for the limited research concerning their application in membrane industries. A highly efficient spray- and spin-assisted layer-by-layer (SSLbL) method was developed to functionalize the TFC polyamide RO membranes with controllable loading of CuNPs for biofouling control. The SSLbL method was able to produce a uniform bilayer of polyethyleneimine-coated CuNPs and poly(acrylic) acid in less than 1 min, which is far more efficient than the traditional dipping approach (25-60 min). The successful loading of CuNPs onto the membrane surface was confirmed by XPS analysis. Increasing the number of bilayers from 2 to 10 led to an increased quantity of CuNPs on the membrane surface, from 1.75 to 23.7 μg cm(-2). Multi-layer coating exhibited minor impact on the membrane water permeation flux (13.3% reduction) while retaining the original salt rejection ability. Both static bacterial inactivation and cross-flow filtration tests demonstrated that CuNPs could significantly improve anti-biofouling property of a polyamide membrane and effectively inhibit the permeate flux reduction caused by bacterial deposition on the membrane surface. Once depleted, CuNPs can also be potentially regenerated on the membrane surface via the same SSLbL method. Copyright © 2016 Elsevier Ltd. All rights reserved.

Diamond nanoparticles as a support for Pt and PtRu catalysts for direct methanol fuel cells.

PubMed

La-Torre-Riveros, Lyda; Guzman-Blas, Rolando; Méndez-Torres, Adrián E; Prelas, Mark; Tryk, Donald A; Cabrera, Carlos R

2012-02-01

Diamond in nanoparticle form is a promising material that can be used as a robust and chemically stable catalyst support in fuel cells. It has been studied and characterized physically and electrochemically, in its thin film and powder forms, as reported in the literature. In the present work, the electrochemical properties of undoped and boron-doped diamond nanoparticle electrodes, fabricated using the ink-paste method, were investigated. Methanol oxidation experiments were carried out in both half-cell and full fuel cell modes. Platinum and ruthenium nanoparticles were chemically deposited on undoped and boron doped diamond nanoparticles through the use of NaBH(4) as reducing agent and sodium dodecyl benzene sulfonate (SDBS) as a surfactant. Before and after the reduction process, samples were characterized by electron microscopy and spectroscopic techniques. The ink-paste method was also used to prepare the membrane electrode assembly with Pt and Pt-Ru modified undoped and boron-doped diamond nanoparticle catalytic systems, to perform the electrochemical experiments in a direct methanol fuel cell system. The results obtained demonstrate that diamond supported catalyst nanomaterials are promising for methanol fuel cells.

H2O2 sensing using HRP modified catalyst-free ZnO nanorods synthesized by RF sputtering

NASA Astrophysics Data System (ADS)

Srivastava, Amit; Kumar, Naresh; Singh, Priti; Singh, Sunil Kumar

2017-06-01

Catalyst-free ( 00 l) oriented ZnO nanorods (NRs) -based biosensor for the H2O2 sensing has been reported. The (002) oriented ZnO NRs as confirmed by X-ray diffraction were successfully grown on indium tin oxide (ITO) coated glass substrate by radio frequency (RF) sputtering technique without using any catalyst. Horseradish peroxidase (HRP) enzyme was immobilized on ZnO NRs by physical adsorption technique to prepare the biosensor. In this HRP/ZnO NR/ITO bioelectrode, nafion solution was added to form a tight membrane on surface. The prepared bioelectrode has been used for biosensing measurements by electrochemical analyzer. The electrochemical studies reveal that the prepared HRP/ZnO NR/ITO biosensor is highly sensitive to the detection of H2O2 over a linear range of 0.250-10 μM. The ZnO NR-based biosensor showed lower value of detection limit (0.125 μM) and higher sensitivity (13.40 µA/µM cm2) towards H2O2. The observed value of higher sensitivity attributed to larger surface area of ZnO nanostructure for effective loading of HRP besides its high electron communication capability. In addition, the biosensor also shows lower value of enzyme's kinetic parameter (Michaelis-Menten constant, K m) of 0.262 μM which indicates enhanced enzyme affinity of HRP to H2O2. The reported biosensor may be useful for various applications in biosensing, clinical, food, and beverage industry.

Carbon corrosion of proton exchange membrane fuel cell catalyst layers studied by scanning transmission X-ray microscopy

NASA Astrophysics Data System (ADS)

Hitchcock, Adam P.; Berejnov, Viatcheslav; Lee, Vincent; West, Marcia; Colbow, Vesna; Dutta, Monica; Wessel, Silvia

2014-11-01

Scanning Transmission X-ray Microscopy (STXM) at the C 1s, F 1s and S 2p edges has been used to investigate degradation of proton exchange membrane fuel cell (PEM-FC) membrane electrode assemblies (MEA) subjected to accelerated testing protocols. Quantitative chemical maps of the catalyst, carbon support and ionomer in the cathode layer are reported for beginning-of-test (BOT), and end-of-test (EOT) samples for two types of carbon support, low surface area carbon (LSAC) and medium surface area carbon (MSAC), that were exposed to accelerated stress testing with upper potentials (UPL) of 1.0, 1.2, and 1.3 V. The results are compared in order to characterize catalyst layer degradation in terms of the amounts and spatial distributions of these species. Pt agglomeration, Pt migration and corrosion of the carbon support are all visualized, and contribute to differing degrees in these samples. It is found that there is formation of a distinct Pt-in-membrane (PTIM) band for all EOT samples. The cathode thickness shrinks due to loss of the carbon support for all MSAC samples that were exposed to the different upper potentials, but only for the most aggressive testing protocol for the LSAC support. The amount of ionomer per unit volume significantly increases indicating it is being concentrated in the cathode as the carbon corrosion takes place. S 2p spectra and mapping of the cathode catalyst layer indicates there are still sulfonate groups present, even in the most damaged material.

Palladium-Zeolite nanofiber as an effective recyclable catalyst membrane for water treatment.

PubMed

Choi, Jungsu; Chan, Sophia; Yip, Garriott; Joo, Hyunjong; Yang, Heejae; Ko, Frank K

2016-09-15

Zeolite is an exciting natural material due to its unique capability of ammonium nitrogen (NH3N) adsorption in water. In this study, multifunctional hybrid composites of zeolite/palladium (Ze/Pd) on polymer nanofiber membranes were fabricated and explored for sustainable contaminant removal. SEM and XRD demonstrated that zeolite and palladium nanoparticles were uniformly distributed and deposited on the nanofibers. NH3N recovery rate was increased from 23 to 92% when palladium coated zeolite was embedded on the nanofiber. Multifunctional nanofibers of Ze/Pd membranes were able to adsorb NH3N on the zeolites placed on the surface of fibers and palladium catalysts were capable of selective oxidation of NH3N to N2 gas. The cycling of NH3N adsorption-oxidation, high flux, hydrophilicity, and flexibility of the membrane makes it a strong candidate for water treatment. Copyright © 2016 Elsevier Ltd. All rights reserved.

Synthesis of cerium and nickel doped titanium nanofibers for hydrolysis of sodium borohydride.

PubMed

Tamboli, Ashif H; Gosavi, S W; Terashima, Chiaki; Fujishima, Akira; Pawar, Atul A; Kim, Hern

2018-07-01

A recyclable titanium nanofibers, doped with cerium and nickel doped was successfully synthesized by using sol-gel and electrospinning method for hydrogen generation from alkali free hydrolysis of NaBH 4 . The resultant nanocomposite was characterized to find out the structural and physical-chemical properties by a series of analytical techniques such as FT-IR (Fourier transform infrared spectroscopy), XRD (X-ray diffraction), SEM (scanning electron microscope), EDX (energy-dispersive X-ray spectroscopy),N 2 adsorption-desorption and BET (Brunauer-Emmett-Teller), etc. The results revealed that cerium and nickel nanoparticles were homogeneously distributed on the surface of the TiO 2 nanofibers due to having similar oxidation state and atomic radium of TiO 2 nanofibers with CeO 2 and NiO for the effective immobilization of metal ions. The NiO doped catalyst showed superior catalytic performance towards the hydrolysis reaction of NaBH 4 at room temperature. These catalysts have ability to produce 305 mL of H 2 within the time of 160 min at room temperature. Additionally, reusability test revealed that the catalyst is active even after five runs of hydrolytic reaction, implying the as-prepared NiO doped TiO 2 nanofibers could be considered as a potential candidate catalyst for portable hydrogen fuel system such as PEMFC (proton exchange membrane fuel cells). Copyright © 2018 Elsevier Ltd. All rights reserved.

Membrane microreactors: gas-liquid reactions made easy.

PubMed

Noël, Timothy; Hessel, Volker

2013-03-01

Getting phases together: Membrane microreactors provide new opportunities for gas-liquid reactions. The advantages of this microreactor concept are a large interfacial area, a greater flexibility with regard to flow rates, and the opportunity to immobilize a catalyst on the membrane. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Stable catalyst layers for hydrogen permeable composite membranes

DOEpatents

Way, J. Douglas; Wolden, Colin A

2014-01-07

The present invention provides a hydrogen separation membrane based on nanoporous, composite metal carbide or metal sulfide coated membranes capable of high flux and permselectivity for hydrogen without platinum group metals. The present invention is capable of being operated over a broad temperature range, including at elevated temperatures, while maintaining hydrogen selectivity.

An XAS experimental approach to study low Pt content electrocatalysts operating in PEM fuel cells.

PubMed

Principi, Emiliano; Witkowska, Agnieszka; Dsoke, Sonia; Marassi, Roberto; Di Cicco, Andrea

2009-11-21

We present an X-ray absorption spectroscopy (XAS) study of a low Pt content catalyst layer (Pt loading 0.1 mg cm(-2)) operating at the cathode of a proton exchange membrane fuel cell (PEMFC). This catalyst is based on the use of a mesoporous inorganic matrix as a support for the catalyst Pt nanoparticles. Due to the high Pt dilution, in situ measurements of its structural properties by XAS are challenging and suitable experimental strategies must be devised for this purpose. In particular, we show that accurate XAS in situ fluorescence measurements can be obtained using an optimized fuel cell, suitable protocols for alignment of a focused X-ray beam and an appropriate filter for the background signal of the other atomic species contained in the electrodes. Details, advantages and limitations of the XAS technique for in situ measurements are discussed. Analysis of the near-edge XAS and EXAFS (extended X-ray absorption fine structure) data, corroborated by a HRTEM (high-resolution transmission electron microscopy) study, shows that the Pt particles have a local structure compatible with that of bulk Pt (fcc) and coordination numbers match those expected for particles with typical sizes in the 1.5-2.0 nm range. Substantial changes in the oxidation state and in local atomic arrangement of the Pt particles are found for different applied potentials. The catalyst support, containing W atoms, exhibits a partial reduction upon PEMFC activation, thus mimicking the catalyst behavior. This indicates a possible role of the mesoporous matrix in favouring the oxygen reduction reaction (ORR) and stimulates further research on active catalyst supports.

Health of tree swallows (Tachycineta bicolor) nesting in pesticide-sprayed apple orchards in Ontario, Canada. II. Sex and thyroid hormone concentrations and testes development.

PubMed

Bishop, C A; Van Der Kraak, G J; Ng, P; Smits, J E; Hontela, A

1998-12-25

To investigate the effects of pesticides on wild birds, sex (17beta-estradiol; testosterone) and thyroid (triiodothyronine (T3) hormone concentrations, body mass, and testes mass were measured and the development of testes was evaluated in wild tree swallows (Tachycineta bicolor) nesting in four sprayed apple orchards and three nonsprayed sites in southern Ontario, Canada, in 1995-1996. In orchards, birds were exposed to asmany as 11 individual spray events and five sprays of mixtures of chemicals. Residues of organochlorine pesticides, PCBs, lead, and arsenic concentrations were low and not variable among sites except p,p'-DDE concentrations, which ranged from 0.36 to 2.23 microg/g wet weight in eggs. These persistent compounds were not correlated with any endocrine response measured in tree swallows. In 16-d-old male tree swallow chicks, body mass and concentrations of 17beta-estradiol (estradiol), testosterone, and T3 in plasma showed no significant differences between sprayed and nonsprayed groups and among sites within those groups. However, T3 concentrations were slightly elevated in the sprayed group compared to the nonsprayed group, and there was a significant and positive correlation between T3 and the number of mixtures of sprays applied during egg incubation through chick rearing. In 16-d-old female chicks, there were no significant differences among spray treatments or sites and no correlations with spray exposure for testosterone, estradiol, or T3 in plasma. Body mass was correlated positively with T3 and negatively with estradiol but showed no differences among spray exposure groups or sites. Histology of testes of 16-d-old male chicks indicated there were no significant differences among sprayed and nonsprayed birds in testes mass, area, or diameter, or the presence of Leydig cells in the interstitium, the distribution of the Sertoli cells, or the occurrence of heterophils in the testicular interstitium. For the percentage of spermatogonia present on the basement membrane, there were significant differences among sites, but these differences were not specifically associated with spray exposure. However, there was a marginally significant trend between increasing occurrence of a disrupted Sertoli cell population on the seminiferous tubular basement membranes as the number of mixtures of pesticides sprayed during chick rearing increased. In adult male and female parent tree swallows, there were no differences in hormone concentrations between birds from sprayed and nonsprayed sites. Nor were there any significant correlations between the concentration of any hormone and collection date, body mass, or any type of spray exposure for adults. The correlations between increasing pesticide exposure and abnormal thyroid hormone and testes development in male chicks indicate that further reductions of pesticide use in orchards may benefit the health of birds that nest there. However, it is unclear which of these pesticides or spray mixtures are responsible for these effects, and this needs to be examined in future studies.

Effect of Fibrin Glue on the Biomechanical Properties of Human Descemet's Membrane

PubMed Central

Chaurasia, Shyam S.; Champakalakshmi, Ravi; Li, Ang; Poh, Rebekah; Tan, Xiao Wei; Lakshminarayanan, Rajamani; Lim, Chwee T.; Tan, Donald T.; Mehta, Jodhbir S.

2012-01-01

Background Corneal transplantation has rapidly evolved from full-thickness penetrating keratoplasty (PK) to selective tissue corneal transplantation, where only the diseased portions of the patient's corneal tissue are replaced with healthy donor tissue. Descemet's membrane endothelial keratoplasty (DMEK) performed in patients with corneal endothelial dysfunction is one such example where only a single layer of endothelial cells with its basement membrane (10–15 µm in thickness), Descemet's membrane (DM) is replaced. It is challenging to replace this membrane due to its intrinsic property to roll in an aqueous environment. The main objective of this study was to determine the effects of fibrin glue (FG) on the biomechanical properties of DM using atomic force microscopy (AFM) and relates these properties to membrane folding propensity. Methodology/Principal Findings Fibrin glue was sprayed using the EasySpray applicator system, and the biomechanical properties of human DM were determined by AFM. We studied the changes in the “rolling up” tendency of DM by examining the changes in the elasticity and flexural rigidity after the application of FG. Surface topography was assessed using scanning electron microscopy (SEM) and AFM imaging. Treatment with FG not only stabilized and stiffened DM but also led to a significant increase in hysteresis of the glue-treated membrane. In addition, flexural or bending rigidity values also increased in FG-treated membranes. Conclusions/Significance Our results suggest that fibrin glue provides rigidity to the DM/endothelial cell complex that may aid in subsequent manipulation by maintaining tissue integrity. PMID:22662156

Oxygen Reduction Reaction Measurements on Platinum Electrocatalysts Utilizing Rotating Disk Electrode Technique: II. Influence of Ink Formulation, Catalyst Layer Uniformity and Thickness

DOE PAGES

Shinozaki, Kazuma; Zack, Jason W.; Pylypenko, Svitlana; ...

2015-09-17

Platinum electrocatalysts supported on high surface area and Vulcan carbon blacks (Pt/HSC, Pt/V) were characterized in rotating disk electrode (RDE) setups for electrochemical area (ECA) and oxygen reduction reaction (ORR) area specific activity (SA) and mass specific activity (MA) at 0.9 V. Films fabricated using several ink formulations and film-drying techniques were characterized for a statistically significant number of independent samples. The highest quality Pt/HSC films exhibited MA 870 ± 91 mA/mgPt and SA 864 ± 56 μA/cm 2 Pt while Pt/V had MA 706 ± 42 mA/mgPt and SA 1120 ± 70 μA/cm 2 Pt when measured in 0.1more » M HClO 4, 20 mV/s, 100 kPa O 2 and 23±2°C. An enhancement factor of 2.8 in themeasured SA was observable on eliminating Nafion ionomer and employing extremely thin, uniform films (~4.5 μg/cm 2 Pt) of Pt/HSC. The ECA for Pt/HSC (99 ± 7 m2/gPt) and Pt/V (65 ± 5 m 2/gPt) were statistically invariant and insensitive to film uniformity/thickness/fabrication technique; accordingly, enhancements in MA are wholly attributable to increases in SA. Impedance measurements coupled with scanning electron microscopy were used to de-convolute the losses within the catalyst layer and ascribed to the catalyst layer resistance, oxygen diffusion, and sulfonate anion adsorption/blocking. The ramifications of these results for proton exchange membrane fuel cells have also been examined.« less

Oxygen Reduction Reaction Measurements on Platinum Electrocatalysts Utilizing Rotating Disk Electrode Technique: II. Influence of Ink Formulation, Catalyst Layer Uniformity and Thickness

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shinozaki, Kazuma; Zack, Jason W.; Pylypenko, Svitlana

Platinum electrocatalysts supported on high surface area and Vulcan carbon blacks (Pt/HSC, Pt/V) were characterized in rotating disk electrode (RDE) setups for electrochemical area (ECA) and oxygen reduction reaction (ORR) area specific activity (SA) and mass specific activity (MA) at 0.9 V. Films fabricated using several ink formulations and film-drying techniques were characterized for a statistically significant number of independent samples. The highest quality Pt/HSC films exhibited MA 870 ± 91 mA/mgPt and SA 864 ± 56 μA/cm 2 Pt while Pt/V had MA 706 ± 42 mA/mgPt and SA 1120 ± 70 μA/cm 2 Pt when measured in 0.1more » M HClO 4, 20 mV/s, 100 kPa O 2 and 23±2°C. An enhancement factor of 2.8 in themeasured SA was observable on eliminating Nafion ionomer and employing extremely thin, uniform films (~4.5 μg/cm 2 Pt) of Pt/HSC. The ECA for Pt/HSC (99 ± 7 m2/gPt) and Pt/V (65 ± 5 m 2/gPt) were statistically invariant and insensitive to film uniformity/thickness/fabrication technique; accordingly, enhancements in MA are wholly attributable to increases in SA. Impedance measurements coupled with scanning electron microscopy were used to de-convolute the losses within the catalyst layer and ascribed to the catalyst layer resistance, oxygen diffusion, and sulfonate anion adsorption/blocking. The ramifications of these results for proton exchange membrane fuel cells have also been examined.« less

A Pd/C-CeO2 Anode Catalyst for High-Performance Platinum-Free Anion Exchange Membrane Fuel Cells.

PubMed

Miller, Hamish A; Lavacchi, Alessandro; Vizza, Francesco; Marelli, Marcello; Di Benedetto, Francesco; D'Acapito, Francesco; Paska, Yair; Page, Miles; Dekel, Dario R

2016-05-10

One of the biggest obstacles to the dissemination of fuel cells is their cost, a large part of which is due to platinum (Pt) electrocatalysts. Complete removal of Pt is a difficult if not impossible task for proton exchange membrane fuel cells (PEM-FCs). The anion exchange membrane fuel cell (AEM-FC) has long been proposed as a solution as non-Pt metals may be employed. Despite this, few examples of Pt-free AEM-FCs have been demonstrated with modest power output. The main obstacle preventing the realization of a high power density Pt-free AEM-FC is sluggish hydrogen oxidation (HOR) kinetics of the anode catalyst. Here we describe a Pt-free AEM-FC that employs a mixed carbon-CeO2 supported palladium (Pd) anode catalyst that exhibits enhanced kinetics for the HOR. AEM-FC tests run on dry H2 and pure air show peak power densities of more than 500 mW cm(-2) . © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Anion exchange membrane fuel cells: Current status and remaining challenges

NASA Astrophysics Data System (ADS)

Gottesfeld, Shimshon; Dekel, Dario R.; Page, Miles; Bae, Chulsung; Yan, Yushan; Zelenay, Piotr; Kim, Yu Seung

2018-01-01

The anion exchange membrane fuel cell (AEMFC) is an attractive alternative to acidic proton exchange membrane fuel cells, which to date have required platinum-based catalysts, as well as acid-tolerant stack hardware. The AEMFC could use non-platinum-group metal catalysts and less expensive metal hardware thanks to the high pH of the electrolyte. Over the last decade, substantial progress has been made in improving the performance and durability of the AEMFC through the development of new materials and the optimization of system design and operation conditions. In this perspective article, we describe the current status of AEMFCs as having reached beginning of life performance very close to that of PEMFCs when using ultra-low loadings of Pt, while advancing towards operation on non-platinum-group metal catalysts alone. In the latter sections, we identify the remaining technical challenges, which require further research and development, focusing on the materials and operational factors that critically impact AEMFC performance and/or durability. These perspectives may provide useful insights for the development of next-generation of AEMFCs.

Anion exchange membrane fuel cells: Current status and remaining challenges

DOE PAGES

Gottesfeld, Shimshon; Dekel, Dario R.; Page, Miles; ...

2017-09-01

The anion exchange membrane fuel cell (AEMFC) is an attractive alternative to acidic proton exchange membrane fuel cells, which to date have required platinum-based catalysts, as well as acid-tolerant stack hardware. The AEMFC could use non-platinum-group metal catalysts and less expensive metal hardware thanks to the high pH of the electrolyte. Over the last decade, substantial progress has been made in improving the performance and durability of the AEMFC through the development of new materials and the optimization of system design and operation conditions. Here in this perspective article, we describe the current status of AEMFCs as having reached beginningmore » of life performance very close to that of PEMFCs when using ultra-low loadings of Pt, while advancing towards operation on non-platinum-group metal catalysts alone. In the latter sections, we identify the remaining technical challenges, which require further research and development, focusing on the materials and operational factors that critically impact AEMFC performance and/or durability. Finally, these perspectives may provide useful insights for the development of next-generation of AEMFCs.« less

Analyzing Structural Changes of Fe-N-C Cathode Catalysts in PEM Fuel Cell by Mößbauer Spectroscopy of Complete Membrane Electrode Assemblies.

PubMed

Kramm, Ulrike I; Lefèvre, Michel; Bogdanoff, Peter; Schmeißer, Dieter; Dodelet, Jean-Pol

2014-11-06

The applicability of analyzing by Mößbauer spectroscopy the structural changes of Fe-N-C catalysts that have been tested at the cathode of membrane electrode assemblies in proton exchange membrane (PEM) fuel cells is demonstrated. The Mößbauer characterization of powders of the same catalysts was recently described in our previous publication. A possible change of the iron species upon testing in fuel cell was investigated here by Mößbauer spectroscopy, energy-dispersive X-ray cross-sectional imaging, and neutron activation analysis. Our results show that the absorption probability of γ rays by the iron nuclei in Fe-N-C is strongly affected by the presence of Nafion and water content. A detailed investigation of the effect of an oxidizing treatment (1.2 V) of the non-noble cathode in PEM fuel cell indicates that the observed activity decay is mainly attributable to carbon oxidation causing a leaching of active iron sites hosted in the carbon matrix.

Novel Spray Dried Glycerol 2-Phosphate Cross-Linked Chitosan Microparticulate Vaginal Delivery System—Development, Characterization and Cytotoxicity Studies

PubMed Central

Szymańska, Emilia; Szekalska, Marta; Czarnomysy, Robert; Lavrič, Zoran; Srčič, Stane; Miltyk, Wojciech; Winnicka, Katarzyna

2016-01-01

Chitosan microparticulate delivery systems containing clotrimazole were prepared by a spray drying technique using glycerol 2-phosphate as an ion cross-linker. The impact of a cross-linking ratio on microparticle characteristics was evaluated. Drug-free and drug-loaded unmodified or ion cross-linked chitosan microparticles were examined for the in vitro cytotoxicity in VK2/E6E7 human vaginal epithelial cells. The presence of glycerol 2-phosphate influenced drug loading and encapsulation efficacy in chitosan microparticles. By increasing the cross-linking ratio, the microparticles with lower diameter, moisture content and smoother surface were observed. Mucoadhesive studies displayed that all formulations possessed mucoadhesive properties. The in vitro release profile of clotrimazole was found to alter considerably by changing the glycerol 2-phosphate/chitosan ratio. Results from cytotoxicity studies showed occurrence of apoptotic cells in the presence of chitosan and ion cross-linked chitosan microparticles, followed by a loss of membrane potential suggesting that cell death might go through the mitochondrial apoptotic pathway. PMID:27690062

Application of Ionic Liquids in Pot-in-Pot Reactions.

PubMed

Çınar, Simge; Schulz, Michael D; Oyola-Reynoso, Stephanie; Bwambok, David K; Gathiaka, Symon M; Thuo, Martin

2016-02-26

Pot-in-pot reactions are designed such that two reaction media (solvents, catalysts and reagents) are isolated from each other by a polymeric membrane similar to matryoshka dolls (Russian nesting dolls). The first reaction is allowed to progress to completion before triggering the second reaction in which all necessary solvents, reactants, or catalysts are placed except for the starting reagent for the target reaction. With the appropriate trigger, in most cases unidirectional flux, the product of the first reaction is introduced to the second medium allowing a second transformation in the same glass reaction pot--albeit separated by a polymeric membrane. The basis of these reaction systems is the controlled selective flux of one reagent over the other components of the first reaction while maintaining steady-state catalyst concentration in the first "pot". The use of ionic liquids as tools to control chemical potential across the polymeric membranes making the first pot is discussed based on standard diffusion models--Fickian and Payne's models. Besides chemical potential, use of ionic liquids as delivery agent for a small amount of a solvent that slightly swells the polymeric membrane, hence increasing flux, is highlighted. This review highlights the critical role ionic liquids play in site-isolation of multiple catalyzed reactions in a standard pot-in-pot reaction.

Performance of a passive direct ethanol fuel cell

NASA Astrophysics Data System (ADS)

Pereira, J. P.; Falcão, D. S.; Oliveira, V. B.; Pinto, A. M. F. R.

2014-06-01

Ethanol emerges as an attractive fuel since it is less toxic and has higher energy density than methanol and can be produced from biomass. Direct ethanol fuel cells (DEFCs) appear as a good choice for producing sustainable energy for portable applications. However, they are still far from attaining acceptable levels of power output, since their performance is affected by the slow electrochemical ethanol oxidation and water and ethanol crossover. In the present work, an experimental study on the performance of a passive DEFC is described. Tailored MEAs (membrane electrode assembly) with different catalyst loadings, anode diffusion layers and membranes were tested in order to select optimal working conditions at high ethanol concentrations and low ethanol crossover. The performance increased with an increase of membrane and anode diffusion layer thicknesses and anode catalyst loading. A maximum power density of 1.33 mW cm-2, was obtained using a Nafion 117 membrane, 4 mg cm-2 of Pt-Ru and 2 mg cm-2 of Pt on the anode and cathode catalyst layers, ELAT as anode diffusion layer, carbon cloth as cathode diffusion layer and an ethanol concentration of 2 M. As far as the authors are aware this is the first work reporting an experimental optimization of passive DEFCs.

pH matters: The influence of the catalyst ink on the oxygen reduction activity determined in thin film rotating disk electrode measurements

NASA Astrophysics Data System (ADS)

Inaba, Masanori; Quinson, Jonathan; Arenz, Matthias

2017-06-01

We investigated the influence of the ink properties of proton exchange membrane fuel cell (PEMFC) catalysts on the oxygen reduction reaction (ORR) activity determined in thin film rotating disk electrode (TF-RDE) measurements. It was found that the adaption of a previously reported ink recipe to home-made catalysts does not lead to satisfying results, although reported work could be reproduced using commercial catalyst samples. It is demonstrated that the pH of the catalyst ink, which has not been addressed in previous TF-RDE studies, is an important parameter that needs to be carefully controlled to determine the intrinsic ORR activity of high surface area catalysts.

Mechanical alloying of a hydrogenation catalyst used for the remediation of contaminated compounds

NASA Technical Reports Server (NTRS)

Quinn, Jacqueline W. (Inventor); Geiger, Cherie L. (Inventor); Aitken, Brian S. (Inventor); Clausen, Christian A. (Inventor)

2012-01-01

A hydrogenation catalyst including a base material coated with a catalytic metal is made using mechanical milling techniques. The hydrogenation catalysts are used as an excellent catalyst for the dehalogenation of contaminated compounds and the remediation of other industrial compounds. Preferably, the hydrogenation catalyst is a bimetallic particle including zero-valent metal particles coated with a catalytic material. The mechanical milling technique is simpler and cheaper than previously used methods for producing hydrogenation catalysts.

Mechanical alloying of a hydrogenation catalyst used for the remediation of contaminated compounds

NASA Technical Reports Server (NTRS)

Quinn, Jacqueline W. (Inventor); Aitken, Brian S. (Inventor); Clausen, Christian A. (Inventor); Geiger, Cherie L. (Inventor)

2010-01-01

A hydrogenation catalyst including a base material coated with a catalytic metal is made using mechanical milling techniques. The hydrogenation catalysts are used as an excellent catalyst for the dehalogenation of contaminated compounds and the remediation of other industrial compounds. Preferably, the hydrogenation catalyst is a bimetallic particle including zero-valent metal particles coated with a catalytic material. The mechanical milling technique is simpler and cheaper than previously used methods for producing hydrogenation catalysts.

Three-Dimensional Networks of S-Doped Fe/N/C with Hierarchical Porosity for Efficient Oxygen Reduction in Polymer Electrolyte Membrane Fuel Cells.

PubMed

Wu, Yi-Jin; Wang, Yu-Cheng; Wang, Rui-Xiang; Zhang, Peng-Fang; Yang, Xiao-Dong; Yang, Hui-Juan; Li, Jun-Tao; Zhou, Yao; Zhou, Zhi-You; Sun, Shi-Gang

2018-05-02

Reasonable design and synthesis of Fe/N/C-based catalysts is one of the most promising way for developing precious metal-free oxygen reduction reaction (ORR) catalysts in acidic mediums. Herein, we developed a highly active metal-organic framework-derived S-doped Fe/N/C catalyst [S-Fe/Z8/2-aminothiazole (2-AT)] prepared by thermal treatment. The S-Fe/Z8/2-AT catalyst with uniform S-doping possesses a three-dimensional macro-meso-micro hierarchically porous structure. Moreover, the chemical composition and structural features have been well-optimized and characterized for such S-Fe/Z8/2-AT catalysts; and their formation mechanism was also revealed. Significantly, applying the optimal S-Fe/Z8/2-AT catalysts into electrocatalytic test exhibits remarkable ORR catalytic activity with a half-wave potential of 0.82 V (vs reversible hydrogen electrode) and a mass activity of 18.3 A g -1 at 0.8 V in 0.1 M H 2 SO 4 solution; the polymer electrolyte membrane fuel cell test also confirmed their excellent catalytic activity, which gives a maximal power density as high as 800 mW cm -2 at 1 bar. A series of designed experiments disclosed that the favorable structural merits and desirable chemical compositions of S-Fe/Z8/2-AT catalysts are critical factors for efficient electrocatalytic performance. The work provides a new approach to open an avenue for accurately controlling the composition and structure of Fe/N/C catalysts with highly activity for ORR.

Dense, layered membranes for hydrogen separation

DOEpatents

Roark, Shane E.; MacKay, Richard; Mundschau, Michael V.

2006-02-21

This invention provides hydrogen-permeable membranes for separation of hydrogen from hydrogen-containing gases. The membranes are multi-layer having a central hydrogen-permeable layer with one or more catalyst layers, barrier layers, and/or protective layers. The invention also relates to membrane reactors employing the hydrogen-permeable membranes of the invention and to methods for separation of hydrogen from a hydrogen-containing gas using the membranes and reactors. The reactors of this invention can be combined with additional reactor systems for direct use of the separated hydrogen.

Membrane electrode assembly for a fuel cell

NASA Technical Reports Server (NTRS)

Prakash, Surya (Inventor); Narayanan, Sekharipuram R. (Inventor); Atti, Anthony (Inventor); Olah, George (Inventor); Smart, Marshall C. (Inventor)

2006-01-01

A catalyst ink for a fuel cell including a catalytic material and poly(vinylidene fluoride). The ink may be applied to a substrate to form an electrode, or bonded with other electrode layers to form a membrane electrode assembly (MEA).

Open-source FCPEM-Performance & Durability Model Consideration of Membrane Properties on Cathode Degradation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Knights, Shanna; Harvey, David

The durability of PEM fuel cells is a primary requirement for large scale commercialization of these power systems in transportation and stationary market applications which target operational lifetimes of 5,000 hours and 60,000 hours by 2020, respectively. Key degradation modes contributing to fuel cell lifetime limitations have been largely associated with the platinum-based cathode catalyst layer. Furthermore, as fuel cells are driven to low cost materials and lower catalyst loadings in order to meet the cost targets for commercialization, the catalyst durability has become even more important. While over the past few years significant progress has been made in identifyingmore » the underlying causes of fuel cell degradation and key parameters that greatly influence the degradation rates, many gaps with respect to knowledge of the driving mechanisms still exist; in particular, the acceleration of the mechanisms due to different membrane compositions remains an area not well understood. The focus of this project extension was to enhance the predictive capability of the PEM Fuel Cell Performance & Durability Model called FC-APOLLO (Application Package for Open-source Long Life Operation) by including interaction effects of membrane transport properties such as water transport, changes in proton conductivity, and overall water uptake/adsorption and the state of the catalyst layer local conditions to further understand the driving forces for platinum dissolution.« less

Dimensionless numbers and correlating equations for the analysis of the membrane-gas diffusion electrode assembly in polymer electrolyte fuel cells

NASA Astrophysics Data System (ADS)

Gyenge, E. L.

The Quraishi-Fahidy method [Can. J. Chem. Eng. 59 (1981) 563] was employed to derive characteristic dimensionless numbers for the membrane-electrolyte, cathode catalyst layer and gas diffuser, respectively, based on the model presented by Bernardi and Verbrugge for polymer electrolyte fuel cells [AIChE J. 37 (1991) 1151]. Monomial correlations among dimensionless numbers were developed and tested against experimental and mathematical modeling results. Dimensionless numbers comparing the bulk and surface-convective ionic conductivities, the electric and viscous forces and the current density and the fixed surface charges, were employed to describe the membrane ohmic drop and its non-linear dependence on current density due to membrane dehydration. The analysis of the catalyst layer yielded electrode kinetic equivalents of the second Damköhler number and Thiele modulus, influencing the penetration depth of the oxygen reduction front based on the pseudohomogeneous film model. The correlating equations for the catalyst layer could describe in a general analytical form, all the possible electrode polarization scenarios such as electrode kinetic control coupled or not with ionic and/or oxygen mass transport limitation. For the gas diffusion-backing layer correlations are presented in terms of the Nusselt number for mass transfer in electrochemical systems. The dimensionless number-based correlating equations for the membrane electrode assembly (MEA) could provide a practical approach to quantify single-cell polarization results obtained under a variety of experimental conditions and to implement them in models of the fuel cell stack.

Analysis of Deactivation Mechanism on a Multi-Component Sulfur-Tolerant Steam Reforming Catalyst

DTIC Science & Technology

2010-08-01

Alkaline Fuel Cells (AFC) .............................................................................. 4 1.1.2. Proton Exchange Membrane Fuel Cells ( PEMFC ...temperature fuel cells. Alkaline Fuel Cell (AFC), Proton Exchange Membrane Fuel Cell ( PEMFC ), DMFC and Phosphoric Acid Fuel Cell (PAFC) are low...1960s. 1.1.2. Proton Exchange Membrane Fuel Cells ( PEMFC ) Proton exchange membrane fuel cells are said to be the best type of fuel cells to replace

Light extinction method on high-pressure diesel injection

NASA Astrophysics Data System (ADS)

Su, Tzay-Fa; El-Beshbeeshy, Mahmound S.; Corradini, Michael L.; Farrell, Patrick V.

1995-09-01

A two dimensional optical diagnostic technique based on light extinction was improved and demonstrated in an investigation of diesel spray characteristics at high injection pressures. Traditional light extinction methods require the spray image to be perpendicular to the light path. In the improved light extinction scheme, a tilted spray image which has an angle with the light path is still capable of being processed. This technique utilizes high speed photography and digital image analysis to obtain qualitative and quantitative information of the spray characteristics. The injection system used was an electronically controlled common rail unit injector system with injection pressures up to 100 MPa. The nozzle of the injector was a mini-sac type with six holes on the nozzle tip. Two different injection angle nozzles, 125 degree(s) and 140 degree(s), producing an in-plane tilted spray and an out of plane tilted spray were investigated. The experiments were conducted on a constant volume spray chamber with the injector mounted tilted at an angle of 62.5 degree(s)$. Only one spray plume was viewed, and other sprays were free to inject to the chamber. The spray chamber was pressurized with argon and air under room temperature to match the combustion chamber density at the start of the injection. The experimental results show that the difference in the spray tip penetration length, spray angle, and overall average Sauter mean diameter is small between the in- plane tilted spray and the out of plane tilted spray. The results also show that in-plane tilted spray has a slightly larger axial cross- section Sauter mean diameter than the out of plane tilted spray.

Effect of formulation- and administration-related variables on deposition pattern of nasal spray pumps evaluated using a nasal cast.

PubMed

Kundoor, Vipra; Dalby, Richard N

2011-08-01

To systematically evaluate the effect of formulation- and administration-related variables on nasal spray deposition using a nasal cast. Deposition pattern was assessed by uniformly coating a transparent nose model with Sar-Gel®, which changes from white to purple on contact with water. Sprays were subsequently discharged into the cast, which was then digitally photographed. Images were quantified using Adobe® Photoshop. The effects of formulation viscosity (which influences droplet size), simulated administration techniques (head orientation, spray administration angle, spray nozzle insertion depth), spray pump design and metering volume on nasal deposition pattern were investigated. There was a significant decrease in the deposition area associated with sprays of increasing viscosity. This appeared to be mediated by an increase in droplet size and a narrowing of the spray plume. Administration techniques and nasal spray pump design also had a significant effect on the deposition pattern. This simple color-based method provides quantitative estimates of the effects that different formulation and administration variables may have on the nasal deposition area, and provides a rational basis on which manufacturers of nasal sprays can base their patient instructions or post approval changes when it is impractical to optimize these using a clinical study.

Process simulation and economic analysis of biodiesel production from waste cooking oil with membrane bioreactor

NASA Astrophysics Data System (ADS)

Abdurakhman, Yuanita Budiman; Putra, Zulfan Adi; Bilad, Muhammad Roil

2017-10-01

Pollution and shortage of clean energy supply are among major problems that are caused by rapid population growth. Due to this growth, waste cooking oil is one of the pollution sources. On the other hand, biodiesel appears to be one of the most promising and feasible energy sources as it emits less toxic pollutants and greenhouse gases than petroleum diesel. Thus, biodiesel production using waste cooking oil offers a two-in-one solution to cater pollution and energy issues. However, the conventional biodiesel production process using homogeneous base catalyst and stirred tank reactor is unable to produce high purity of biodiesel from waste cooking oil. It is due its sensitivity to free fatty acid (FFA) content in waste cooking oil and purification difficulties. Therefore, biodiesel production using heterogeneous acid catalyst in membrane reactor is suggested. The product of this process is fatty acid methyl esters (FAME) or biodiesel with glycerol as by-product. This project is aimed to study techno-economic feasibility of biodiesel production from waste cooking oil via heterogeneous acid catalyst in membrane reactor. Aspen HYSYS is used to accomplish this aim. Several cases, such as considering different residence times and the production of pharmaceutical (USP) grade glycerol, are evaluated and compared. Economic potential of these cases is calculated by considering capital expenditure, utilities cost, product and by-product sales, as well as raw material costs. Waste cooking oil, inorganic pressure-driven membrane and WAl is used as raw material, type of membrane and heterogeneous acid catalyst respectively. Based on literature data, FAME yield formulation is developed and used in the reactor simulation. Simulation results shows that economic potential increases by 30% if pharmaceutical (USP) grade glycerol is produced regardless the residence time of the reactor. In addition, there is no significant effect of residence time on the economic potential.

Highly Dispersed Alloy Catalyst for Durability

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vivek S. Murthi; Izzo, Elise; Bi, Wu

2013-01-08

Achieving DOE's stated 5000-hr durability goal for light-duty vehicles by 2015 will require MEAs with characteristics that are beyond the current state of the art. Significant effort was placed on developing advanced durable cathode catalysts to arrive at the best possible electrode for high performance and durability, as well as developing manufacturing processes that yield significant cost benefit. Accordingly, the overall goal of this project was to develop and construct advanced MEAs that will improve performance and durability while reducing the cost of PEMFC stacks. The project, led by UTC Power, focused on developing new catalysts/supports and integrating them withmore » existing materials (membranes and gas diffusion layers (GDLs)) using state-of-the-art fabrication methods capable of meeting the durability requirements essential for automotive applications. Specifically, the project work aimed to lower platinum group metals (PGM) loading while increasing performance and durability. Appropriate catalysts and MEA configuration were down-selected that protects the membrane, and the layers were tailored to optimize the movements of reactants and product water through the cell to maximize performance while maintaining durability.« less

Highly active non-PGM catalysts prepared from metal organic frameworks

DOE PAGES

Barkholtz, Heather M.; Chong, Lina; Kaiser, Zachary B.; ...

2015-06-11

Finding inexpensive alternatives to platinum group metals (PGMs) is essential for reducing the cost of proton exchange membrane fuel cells (PEMFCs). Numerous materials have been investigated as potential replacements of Pt, of which the transition metal and nitrogen-doped carbon composites (TM/N x/C) prepared from iron doped zeolitic imidazolate frameworks (ZIFs) are among the most active ones in catalyzing the oxygen reduction reaction based on recent studies. In this report, we demonstrate that the catalytic activity of ZIF-based TM/N x/C composites can be substantially improved through optimization of synthesis and post-treatment processing conditions. Ultimately, oxygen reduction reaction (ORR) electrocatalytic activity mustmore » be demonstrated in membrane-electrode assemblies (MEAs) of fuel cells. The process of preparing MEAs using ZIF-based non-PGM electrocatalysts involves many additional factors which may influence the overall catalytic activity at the fuel cell level. Evaluation of parameters such as catalyst loading and perfluorosulfonic acid ionomer to catalyst ratio were optimized. Our overall efforts to optimize both the catalyst and MEA construction process have yielded impressive ORR activity when tested in a fuel cell system.« less

XAS Investigations of PEM Fuel Cells

NASA Astrophysics Data System (ADS)

Roth, Christina; Ramaker, David E.

Polymer-electrolyte membrane (PEM) fuel cells are still far from an area-wide market launch due in part to long-term stability, reliability and cost issues. A more detailed knowledge of the underlying reaction mechanisms is expected to further their application, as it would allow for the design of tailor-made catalysts. However, this will only be possible by complementing traditional in situ studies on single-crystals in electrochemical cells with more sophisticated metal/electrolyte interfacial studies by novel spectroscopic methodologies, which can provide complementary insights into the behaviour of commercial catalysts under real fuel cell operating conditions. This review will focus on the advances of Xray absorption spectroscopy (XAS) in applied fuel cell research utilizing several examples. XAS enables both the nanoparticle morphology and the adsorbate coverage and binding site to be investigated with just one technique. The latter is possible when complementing the conventional extended X-ray absorption fine structure (EXAFS) analysis with the more novel Δμ XANES approach.

Experimental investigation of atomization characteristics of swirling spray by ADN gelled propellant

NASA Astrophysics Data System (ADS)

Guan, Hao-Sen; Li, Guo-Xiu; Zhang, Nai-Yuan

2018-03-01

Due to the current global energy shortage and increasingly serious environmental issues, green propellants are attracting more attention. In particular, the ammonium dinitramide (ADN)-based monopropellant thruster is gaining world-wide attention as a green, non-polluting and high specific impulse propellant. Gel propellants combine the advantages of liquid and solid propellants, and are becoming popular in the field of spaceflight. In this paper, a swirling atomization experimental study was carried out using an ADN aqueous gel propellant under different injection pressures. A high-speed camera and a Malvern laser particle size analyzer were used to study the spray process. The flow coefficient, cone angle of swirl atomizing spray, breakup length of spray membrane, and droplet size distribution were analyzed. Furthermore, the effects of different injection pressures on the swirling atomization characteristics were studied.

Ordered macroporous platinum electrode and enhanced mass transfer in fuel cells using inverse opal structure.

PubMed

Kim, Ok-Hee; Cho, Yong-Hun; Kang, Soon Hyung; Park, Hee-Young; Kim, Minhyoung; Lim, Ju Wan; Chung, Dong Young; Lee, Myeong Jae; Choe, Heeman; Sung, Yung-Eun

2013-01-01

Three-dimensional, ordered macroporous materials such as inverse opal structures are attractive materials for various applications in electrochemical devices because of the benefits derived from their periodic structures: relatively large surface areas, large voidage, low tortuosity and interconnected macropores. However, a direct application of an inverse opal structure in membrane electrode assemblies has been considered impractical because of the limitations in fabrication routes including an unsuitable substrate. Here we report the demonstration of a single cell that maintains an inverse opal structure entirely within a membrane electrode assembly. Compared with the conventional catalyst slurry, an ink-based assembly, this modified assembly has a robust and integrated configuration of catalyst layers; therefore, the loss of catalyst particles can be minimized. Furthermore, the inverse-opal-structure electrode maintains an effective porosity, an enhanced performance, as well as an improved mass transfer and more effective water management, owing to its morphological advantages.

Electrode assembly for use in a solid polymer electrolyte fuel cell

DOEpatents

Raistrick, Ian D.

1989-01-01

A gas reaction fuel cell may be provided with a solid polymer electrolyte membrane. Porous gas diffusion electrodes are formed of carbon particles supporting a catalyst which is effective to enhance the gas reactions. The carbon particles define interstitial spaces exposing the catalyst on a large surface area of the carbon particles. A proton conducting material, such as a perfluorocarbon copolymer or ruthenium dioxide contacts the surface areas of the carbon particles adjacent the interstitial spaces. The proton conducting material enables protons produced by the gas reactions adjacent the supported catalyst to have a conductive path with the electrolyte membrane. The carbon particles provide a conductive path for electrons. A suitable electrode may be formed by dispersing a solution containing a proton conducting material over the surface of the electrode in a manner effective to coat carbon surfaces adjacent the interstitial spaces without impeding gas flow into the interstitial spaces.

Statistical Simulation of the Performance and Degradation of a PEMFC Membrane Electrode Assembly

DOE Office of Scientific and Technical Information (OSTI.GOV)

Harvey, David; Bellemare-Davis, Alexander; Karan, Kunal

2012-07-01

A 1-D MEA Performance model was developed that considered transport of liquid water, agglomerate catalyst structure, and the statistical variation of the MEA characteristic parameters. The model was validated against a low surface area carbon supported catalyst across various platinum loadings and operational conditions. The statistical variation was found to play a significant role in creating noise in the validation data and that there was a coupling effect between movement in material properties with liquid water transport. Further, in studying the low platinum loaded catalyst layers it was found that liquid water played a significant role in the increasing themore » overall transport losses. The model was then further applied to study platinum dissolution via potential cycling accelerated stress tests, in which the platinum was found to dissolve nearest the membrane effectively resulting in reaction distribution shifts within the layer.« less

Fixation of revision implants is improved by new surgical technique to crack the sclerotic endosteal rim.

PubMed

Kold, S; Soballe, K; Mouzin, O; Chen, Xiangmei; Toft, M; Bechtold, J

2002-01-01

We used an experimental model producing a tissue response with a sclerotic endosteal neo-cortical rim associated with implant loosening in humans: a 6 mm PMMA cylinder pistoned 500 m concentrically in a 7.5 mm hole, with polyethylene particles. At a second operation at eight weeks, the standard revision procedure removed the fibrous membrane in one knee, and the crack revision procedure was used to crack the sclerotic endosteal rim in the contralateral knee. Once stability was achieved following the revision procedures, loaded Ti plasma sprayed implants were inserted into the revision cavities of 8 dogs for an additional 4 weeks. Revision implant fixation (ultimate shear strength and energy absorption) was significantly enhanced by cracking the sclerotic endosteal rim. In conclusion, we demonstrated a simple technique of cracking the sclerotic endosteal rim as an additional method for improving revision fixation. (Hip International 2002; 2: 77-9).

Systems and methods for rebalancing redox flow battery electrolytes

DOEpatents

Pham, Ai Quoc; Chang, On Kok

2015-03-17

Various methods of rebalancing electrolytes in a redox flow battery system include various systems using a catalyzed hydrogen rebalance cell configured to minimize the risk of dissolved catalyst negatively affecting flow battery performance. Some systems described herein reduce the chance of catalyst contamination of RFB electrolytes by employing a mediator solution to eliminate direct contact between the catalyzed membrane and the RFB electrolyte. Other methods use a rebalance cell chemistry that maintains the catalyzed electrode at a potential low enough to prevent the catalyst from dissolving.

The Role of Non-Conventional Supports for Single-Atom Platinum-Based Catalysts in Fuel-Cell Technology: A Theoretical Surface Science Approach

DTIC Science & Technology

2013-02-05

could be a promising catalyst for PEM fuel cells. Introduction: Proton exchange membrane fuel cells ( PEMFCs ) have found wide potential...Unfortunately, due to their high cost and low lifespan, wide-scale commercialization of PEMFCs has been greatly impeded and much effort has been made to...lower its cost as well as to improve its durability over time. In an attempt to alleviate the high-cost associated with conventional PEMFC catalysts

Method of improving fuel cell performance by removing at least one metal oxide contaminant from a fuel cell electrode

DOEpatents

Kim, Yu Seung [Los Alamos, NM; Choi, Jong-Ho [Los Alamos, NM; Zelenay, Piotr [Los Alamos, NM

2009-08-18

A method of removing contaminants from a fuel cell catalyst electrode. The method includes providing a getter electrode and a fuel cell catalyst electrode having at least one contaminant to a bath and applying a voltage sufficient to drive the contaminant from the fuel cell catalyst electrode to the getter electrode. Methods of removing contaminants from a membrane electrode assembly of a fuel cell and of improving performance of a fuel cell are also provided.

Alternate Spray-coating for the Direct Fabrication of Hydroxyapatite Films without Crystal Growth Step in Solution.

PubMed

Watanabe, Satoshi; Kashiwagi, Rei; Matsumoto, Mutsuyoshi

2017-03-01

We discuss an alternate spray-coating technique for the direct fabrication of hydroxyapatite films using metal masks, suction-type spray nozzles and two calcification solutions of calcium hydroxide and phosphoric acid aqueous solutions. Hydroxyapatite films were formed only on the hydrophobic surface of the substrates. Scanning electron microscopy and energy dispersive X-ray spectroscopy showed that the spray-coated films consisted of hydroxyapatite nanoparticles. The Ca/P ratio was estimated to be about 1.26. X-ray diffraction patterns of the spray-coated films almost coincided with those of the hydroxyapatite powders, showing that the spray-coated films consisted of hydroxyapatite nanoparticles. Dot arrays of hydroxyapatite films at a diameter of 100 μm were formed by tuning the concentrations of calcium hydroxide and phosphoric acid aqueous solutions. This technique allows for the direct fabrication of the hydroxyapatite films without crystal growth process in hydroxyapatite precursors, the scaffolds of crystal growth such as biocompatibility SiO 2 -CaO glasses, or electrophoresis processes. By using this technique, large-area ceramic films with biocompatibility will be micropatterned with minimized material consumption, short fabrication time, and reduced equipment investments.

Quantification of sauter mean diameter in diesel sprays using scattering-absorption extinction measurements

DOE Office of Scientific and Technical Information (OSTI.GOV)

Martinez, Gabrielle L; Magnotti, Gina M; Knox, Benjamin W

Quantitative measurements of the primary breakup process in diesel sprays are lacking due to a range of experimental and diagnostic challenges, including: high droplet number density environments, very small characteristic drop size scales (~1-10 μm), and high characteristic velocities in the primary breakup region (~600 m/s). Due to these challenges, existing measurement techniques have failed to resolve a sufficient range of the temporal and spatial scales involved and much remains unknown about the primary atomization process in practical diesel sprays. To gain a better insight into this process, we have developed a joint visible and x-ray extinction measurement technique tomore » quantify axial and radial distributions of the path-integrated Sauter Mean Diameter (SMD) and Liquid Volume Fraction (LVF) for diesel-like sprays. This technique enables measurement of the SMD in regions of moderate droplet number density, enabling construction of the temporal history of drop size development within practical diesel sprays. The experimental campaign was conducted jointly at the Georgia Institute of Technology and Argonne National Laboratory using the Engine Combustion Network “Spray D” injector. X-ray radiography liquid absorption measurements, conducted at the Advanced Photon Source at Argonne, quantify the liquid-fuel mass and volume distribution in the spray. Diffused back-illumination liquid scattering measurements were conducted at Georgia Tech to quantify the optical thickness throughout the spray. By application of Mie-scatter equations, the ratio of the absorption and scattering extinction measurements is demonstrated to yield solutions for the SMD. This work introduces the newly developed scattering-absorption measurement technique and highlights the important considerations that must be taken into account when jointly processing these measurements to extract the SMD. These considerations include co-alignment of measurements taken at different institutions, identification of viable regions where the measurement ratio can be accurately interpreted, and uncertainty analysis in the measurement ratio and resulting SMD. Because the measurement technique provides the spatial history of the SMD development, it is expected to be especially informative to the diesel spray modeling community. Results from this work will aid in understanding the effect of ambient densities and injection pressures on primary breakup and help assess the appropriateness of spray submodels for engine computational fluid dynamics codes.« less

Introducing catalyst in alkaline membrane for improved performance direct borohydride fuel cells

NASA Astrophysics Data System (ADS)

Qin, Haiying; Lin, Longxia; Chu, Wen; Jiang, Wei; He, Yan; Shi, Qiao; Deng, Yonghong; Ji, Zhenguo; Liu, Jiabin; Tao, Shanwen

2018-01-01

A catalytic material is introduced into the polymer matrix to prepare a novel polymeric alkaline electrolyte membrane (AEM) which simultaneously increases ionic conductivity, reduces the fuel cross-over. In this work, the hydroxide anion exchange membrane is mainly composed of poly(vinylalcohol) and alkaline exchange resin. CoCl2 is added into the poly(vinylalcohol) and alkaline exchange resin gel before casting the membrane to introduce catalytic materials. CoCl2 is converted into CoOOH after the reaction with KOH solution. The crystallinity of the polymer matrix decreases and the ionic conductivity of the composite membrane is notably improved by the introduction of Co-species. A direct borohydride fuel cell using the composite membrane exhibits an open circuit voltage of 1.11 V at 30 °C, which is notably higher than that of cells using other AEMs. The cell using the composite membrane achieves a maximum power density of 283 mW cm-2 at 60 °C while the cell using the membrane without Co-species only reaches 117 mW cm-2 at the same conditions. The outstanding performance of the cell using the composite membrane benefits from impregnation of the catalytic Co-species in the membrane, which not only increases the ionic conductivity but also reduces electrode polarization thus improves the fuel cell performance. This work provides a new approach to develop high-performance fuel cells through adding catalysts in the electrolyte membrane.

Membrane technology as a promising alternative in biodiesel production: a review.

PubMed

Shuit, Siew Hoong; Ong, Yit Thai; Lee, Keat Teong; Subhash, Bhatia; Tan, Soon Huat

2012-01-01

In recent years, environmental problems caused by the use of fossil fuels and the depletion of petroleum reserves have driven the world to adopt biodiesel as an alternative energy source to replace conventional petroleum-derived fuels because of biodiesel's clean and renewable nature. Biodiesel is conventionally produced in homogeneous, heterogeneous, and enzymatic catalysed processes, as well as by supercritical technology. All of these processes have their own limitations, such as wastewater generation and high energy consumption. In this context, the membrane reactor appears to be the perfect candidate to produce biodiesel because of its ability to overcome the limitations encountered by conventional production methods. Thus, the aim of this paper is to review the production of biodiesel with a membrane reactor by examining the fundamental concepts of the membrane reactor, its operating principles and the combination of membrane and catalyst in the catalytic membrane. In addition, the potential of functionalised carbon nanotubes to serve as catalysts while being incorporated into the membrane for transesterification is discussed. Furthermore, this paper will also discuss the effects of process parameters for transesterification in a membrane reactor and the advantages offered by membrane reactors for biodiesel production. This discussion is followed by some limitations faced in membrane technology. Nevertheless, based on the findings presented in this review, it is clear that the membrane reactor has the potential to be a breakthrough technology for the biodiesel industry. Copyright © 2012 Elsevier Inc. All rights reserved.

Gram-level synthesis of core-shell structured catalysts for the oxygen reduction reaction in proton exchange membrane fuel cells

NASA Astrophysics Data System (ADS)

Luo, Mingchuan; Wei, Lingli; Wang, Fanghui; Han, Kefei; Zhu, Hong

2014-12-01

Over the past decade, Pt based core-shell structured alloys have been studied extensively as oxygen reduction reaction (ORR) catalysts for proton exchange membrane fuel cells (PEMFCs) because of their distinctive electrochemical performance and low Pt loading. In this paper, a facile route based on microwave-assisted polyol method and chemical dealloying process is proposed to synthesize carbon supported core-shell structured nanoparticles (NPs) in gram-level for ORR electrocatalysis in PEMFCs. The obtained samples are characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDX), inductively coupled plasma atomic emission spectroscopy (ICP-AES), and X-ray photoelectron spectroscopy (XPS). These physical characterization indicate that the final synthesized NPs are highly dispersed on the carbon support, and in a core-shell structure with CuPt alloy as the core and Pt as the shell. Electrochemical measurements, conducted by cyclic voltammetry (CV) and rotating disk electrode (RDE) tests, show the core-shell structured catalyst exhibit a 3× increase in mass activity and a 2× increase in specific activity over the commercial Pt/C catalyst, respectively. These results demonstrate that this route can be a reliable way to synthesize low-Pt catalyst in large-scale for PEMFCs.

Defense Nanotechnology Research and Development Programs

DTIC Science & Technology

2005-05-17

Laser has been achieved with SBIR support. • Thermal spray ceramic nanocomposite alumina - titania has been commercialized for wear resistant...additives have been developed that, during membrane formation, self-assemble a low-fouling hydrophilic surface on all membrane surfaces (both...macroscopic and pore surfaces). • A new method for processing of ceramic nanocomposites has been demonstrated, in which a homogeneous, metastable powder is

Spray drying of a phenolic-rich membrane filtration fraction of olive mill wastewater: Optimization and dried product quality

USDA-ARS?s Scientific Manuscript database

Olive mill wastewater (OMWW) from two California mills (3-phase and 2-phase) was subjected to a two-step membrane filtration process using a novel vibratory system. The obtained reverse osmosis retentate (RO-R) is a phenolic-rich co-product stream, and the reverse osmosis permeate is a near-pure wat...

Development of an imaging system for single droplet characterization using a droplet generator.

PubMed

Minov, S Vulgarakis; Cointault, F; Vangeyte, J; Pieters, J G; Hijazi, B; Nuyttens, D

2012-01-01

The spray droplets generated by agricultural nozzles play an important role in the application accuracy and efficiency of plant protection products. The limitations of the non-imaging techniques and the recent improvements in digital image acquisition and processing increased the interest in using high speed imaging techniques in pesticide spray characterisation. The goal of this study was to develop an imaging technique to evaluate the characteristics of a single spray droplet using a piezoelectric single droplet generator and a high speed imaging technique. Tests were done with different camera settings, lenses, diffusers and light sources. The experiments have shown the necessity for having a good image acquisition and processing system. Image analysis results contributed in selecting the optimal set-up for measuring droplet size and velocity which consisted of a high speed camera with a 6 micros exposure time, a microscope lens at a working distance of 43 cm resulting in a field of view of 1.0 cm x 0.8 cm and a Xenon light source without diffuser used as a backlight. For measuring macro-spray characteristics as the droplet trajectory, the spray angle and the spray shape, a Macro Video Zoom lens at a working distance of 14.3 cm with a bigger field of view of 7.5 cm x 9.5 cm in combination with a halogen spotlight with a diffuser and the high speed camera can be used.

The Use of Spray-Dried Mn₃O₄/C Composites as Electrocatalysts for Li-O₂ Batteries.

PubMed

Yang, Hong-Kai; Chin, Chih-Chun; Chen, Jenn-Shing

2016-11-07

The electrocatalytic activities of Mn₃O₄/C composites are studied in lithium-oxygen (Li-O₂) batteries as cathode catalysts. The Mn₃O₄/C composites are fabricated using ultrasonic spray pyrolysis (USP) with organic surfactants as the carbon sources. The physical and electrochemical performance of the composites is characterized by X-ray diffraction, scanning electron microscopy, particle size analysis, Brunauer-Emmett-Teller (BET) measurements, elemental analysis, galvanostatic charge-discharge methods and rotating ring-disk electrode (RRDE) measurements. The electrochemical tests demonstrate that the Mn₃O₄/C composite that is prepared using Trition X-114 (TX114) surfactant has higher activity as a bi-functional catalyst and delivers better oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) catalytic performance in Li-O₂ batteries because there is a larger surface area and particles are homogeneous with a meso/macro porous structure. The rate constant ( k f ) for the production of superoxide radical (O₂ • - ) and the propylene carbonate (PC)-electrolyte decomposition rate constant ( k ) for M₃O₄/C and Super P electrodes are measured using RRDE experiments and analysis in the 0.1 M tetrabutylammonium hexafluorophosphate (TBAPF₆)/PC electrolyte. The results show that TX114 has higher electrocatalytic activity for the first step of ORR to generate O₂ • - and produces a faster PC-electrolyte decomposition rate.

Simplified process for leaching precious metals from fuel cell membrane electrode assemblies

DOEpatents

Shore, Lawrence [Edison, NJ; Matlin, Ramail [Berkeley Heights, NJ

2009-12-22

The membrane electrode assemblies of fuel cells are recycled to recover the catalyst precious metals from the assemblies. The assemblies are cryogenically embrittled and pulverized to form a powder. The pulverized assemblies are then mixed with a surfactant to form a paste which is contacted with an acid solution to leach precious metals from the pulverized membranes.

Optimization of Fibrin Glue Spray Systems for Ophthalmic Surgery

PubMed Central

Chaurasia, Shyam S.; Champakalakshmi, Ravi; Angunawela, Romesh I.; Tan, Donald T.; Mehta, Jodhbir S.

2012-01-01

Purpose To optimize fibrin glue (FG) spray for ophthalmic surgery using two spray applicators, EasySpray and DuploSpray systems, by varying the distance from point of application and the pressure/flow rate, and to compare the adhesive strength of sutured and sutureless (FG sprayed) conjunctival graft surgery in a rabbit model. Methods FG was sprayed on a 0.2 mm-thick sheet of paper using EasySpray by variously combining application distances of 2.5, 5, 7.5, and 10 cm with pressures of 10, 15, and 20 psi. DuploSpray was used at the same distances but with varying flow rates of 1 and 2 L/min. Subsequently, FG was sprayed on porcine corneas and FG thickness was analyzed by histology. In addition, adhesive strength of the conjunctival graft (0.5 × 0.5 cm) attached to the rabbit cornea by sutured and sutureless surgery (FG spray) was compared using a tension meter. Results Histology measurements revealed that the FG thickness decreased with increases in distance and pressure of spray using the EasySpray applicator on paper and porcine corneal sections. The adhesive strength of the sutured conjunctival graft (41 ± 4.85 [kilopascal] KPa) was found to be higher than the graft attached by spraying (10 ± 2.3 KPa) and the sequential addition of FG (6 ± 0.714 KPa). Conclusions The EasySpray applicator formed a uniform spread of FG at a distance-pressure combination of 5 cm and 20 psi. The conjunctival graft attached with sutures had higher adhesive strength compared with grafts glued with a spray applicator. Although the adhesive strength of FG applied through the applicator was similar to the drop-wise sequential technique, the former was more cost effective because more samples could be sprayed compared with the sequential manual technique. Translational Relevance The standardization of the spray system for the application of FG in ophthalmology will provide an economical method for delivering consistent healing results after surgery. PMID:24049702

Freestanding eggshell membrane-based electrodes for high-performance supercapacitors and oxygen evolution reaction.

PubMed

Geng, Jing; Wu, Hao; Al-Enizi, Abdullah M; Elzatahry, Ahmed A; Zheng, Gengfeng

2015-09-14

A type of freestanding, light-weight eggshell membrane-based electrode is demonstrated for supercapacitors and for oxygen evolution reaction (OER) catalysis. As a widely available daily waste, eggshell membranes have unique porous three-dimensional grid-like fibrous structures with relatively high surface area and abundant macropores, allowing for effective conjugation of carbon nanotubes and growth of NiCo2O4 nanowire arrays, an effective supercapacitor material and OER catalyst. The three-dimensional fibrous eggshell membrane frameworks with carbon nanotubes offer efficient pathways for charge transport, and the macropores between adjacent fibers are fully accessible for electrolytes and bubble evolution. As a supercapacitor, the eggshell membrane/carbon nanotube/NiCo2O4 electrode shows high specific capacitances at current densities from 1 to 20 A g(-1), with excellent capacitance retention (>90%) at 10 A g(-1) for over 10,000 cycles. When employed as an OER catalyst, this eggshell membrane-based electrode exhibits an OER onset potential of 1.53 V vs. the reversible hydrogen electrode (RHE), and a stable catalytic current density of 20 mA cm(-2) at 1.65 V vs. the RHE.

Method of fabricating electrode catalyst layers with directionally oriented carbon support for proton exchange membrane fuel cell

DOEpatents

Liu, Di-Jia [Naperville, IL; Yang, Junbing [Bolingbrook, IL

2012-03-20

A membrane electrode assembly (MEA) of the invention comprises an anode and a cathode and a proton conductive membrane therebetween, the anode and the cathode each comprising a patterned sheet of longitudinally aligned transition metal-containing carbon nanotubes, wherein the carbon nanotubes are in contact with and are aligned generally perpendicular to the membrane, wherein a catalytically active transition metal is incorporated throughout the nanotubes.

Progress on Zeolite-membrane-aided Organic Acid Esterification

NASA Astrophysics Data System (ADS)

Makertiharta, I. G. B. N.; Dharmawijaya, P. T.

2017-07-01

Esterification is a common route to produce carboxylic acid esters as important intermediates in chemical and pharmaceutical industries. However, the reaction is equilibrium limited and needs to be driven forward by selective removal one of the products. There have been some efforts to selectively remove water from reaction mixture via several separation processes (such as pervaporation and reactive distillation). Integrated pervaporation and esterification has gained increasing attention towards. Inorganic zeolite is the most popular material for pervaporation due to its high chemical resistant and separation performance towards water. Zeolite also has proven to be an effective material in removing water from organic compound. Zeolite can act not only as selective layer but also simultaneously act as a catalyst on promoting the reaction. Hence, there are many configurations in integrating zeolite membrane for esterification reaction. As a selective layer to remove water from reaction mixture, high Si/Al zeolite is preferred to enhance its hydrophilicity. However, low Si/Al zeolite is unstable in acid condition due to dealumination thus eliminate its advantages. As a catalyst, acid zeolites (e.g. H-ZSM-5) provide protons for autoprotolysis of the carboxylic acid similar to other catalyst for esterification (e.g. inorganic acid, and ion exchange resins). There are many studies related to zeolite membrane aided esterification. This paper will give brief information related to zeolite membrane role in esterification and also research trend towards it.

Investigations of direct methanol fuel cell (DMFC) fading mechanisms

NASA Astrophysics Data System (ADS)

Sarma, Loka Subramanyam; Chen, Ching-Hsiang; Wang, Guo-Rung; Hsueh, Kan-Lin; Huang, Chiou-Ping; Sheu, Hwo-Shuenn; Liu, Ding-Goa; Lee, Jyh-Fu; Hwang, Bing-Joe

In this report, we present the microscopic investigations on various fading mechanisms of a direct methanol fuel cell (DMFC). High energy X-ray diffraction (XRD), X-ray absorption spectroscopy (XAS), energy dispersive X-ray spectroscopy (EDX), and Raman spectroscopic analysis were applied to a membrane-electrode-assembly (MEA) before and after fuel cell operation to figure out the various factors causing its fading. High energy XRD analysis of the fresh and faded MEA revealed that the agglomeration of the catalyst particles in the cathode layer of the faded MEA was more significant than in the anode layer of the faded MEA. The XAS analysis demonstrated that the alloying extent of Pt (J Pt) and Ru (J Ru) in the anode catalyst was increased and decreased, respectively, from the fresh to the faded MEA, indicating that the Ru environment in the anode catalyst was significantly changed after the fuel cell operation. Based on the X-ray absorption edge jump measurements at the Ru K-edge on the anode catalyst of the fresh and the faded MEA it was found that Ru was dissolved from the Pt-Ru catalyst after the fuel cell operation. Both the Ru K-edge XAS and EDX analysis on the cathode catalyst layer of the faded MEA confirms the presence of Ru environment in the cathode catalyst due to the Ru crossover from the anode to the cathode side. The changes in the membrane and the gas diffusion layer (GDL) after the fuel cell operation were observed from the Raman spectroscopy analysis.

Porous Anodic Aluminum Oxide with Serrated Nanochannels

NASA Astrophysics Data System (ADS)

Li, Dongdong; Zhao, Liang; Lu, Jia G.

2010-03-01

Self-assembled nanoporous anodic aluminum oxide (AAO) membrane with straight channels has long been an important tool in synthesizing highly ordered and vertically aligned quasi-1D nanostructures for various applications. Recently shape-selective nanomaterials have been achieved using AAO as a template. It is envisioned that nanowires with multi-branches will significantly increase the active functional sites for applications as sensors, catalysts, chemical cells, etc. Here AAO membranes with serrated nanochannels have been successfully fabricated via a two-step annodization method. The serrated channels with periodic intervals are aligned at an angle of ˜25^circ along the stem channels. The formation of the serrated channels is attributed to the evolution of oxygen gas bubbles and the resulted plastic deformation in oxide membrane. In order to reveal the inside channel structure, Platinum are electrodeposited into the AAO template. The as-synthesized serrated Pt nanowires demonstrate a superior electrocatalytic activity. This is attributed to the enhanced electric field strength around serrated tips as shown in the electric field simulation by COMOSL. Moreover, hierarchical serrated/straight hybrid structures can be constructed using this simple and novel self assembly technique.

A hybrid process combining homogeneous catalytic ozonation and membrane distillation for wastewater treatment.

PubMed

Zhang, Yong; Zhao, Peng; Li, Jie; Hou, Deyin; Wang, Jun; Liu, Huijuan

2016-10-01

A novel catalytic ozonation membrane reactor (COMR) coupling homogeneous catalytic ozonation and direct contact membrane distillation (DCMD) was developed for refractory saline organic pollutant treatment from wastewater. An ozonation process took place in the reactor to degrade organic pollutants, whilst the DCMD process was used to recover ionic catalysts and produce clean water. It was found that 98.6% total organic carbon (TOC) and almost 100% salt were removed and almost 100% metal ion catalyst was recovered. TOC in the permeate water was less than 16 mg/L after 5 h operation, which was considered satisfactory as the TOC in the potassium hydrogen phthalate (KHP) feed water was as high as 1000 mg/L. Meanwhile, the membrane distillation flux in the COMR process was 49.8% higher than that in DCMD process alone after 60 h operation. Further, scanning electron microscope images showed less amount and smaller size of contaminants on the membrane surface, which indicated the mitigation of membrane fouling. The tensile strength and FT-IR spectra tests did not reveal obvious changes for the polyvinylidene fluoride membrane after 60 h operation, which indicated the good durability. This novel COMR hybrid process exhibited promising application prospects for saline organic wastewater treatment. Copyright © 2016 Elsevier Ltd. All rights reserved.

Development of membrane electrode assembly for high temperature proton exchange membrane fuel cell by catalyst coating membrane method

NASA Astrophysics Data System (ADS)

Liang, Huagen; Su, Huaneng; Pollet, Bruno G.; Pasupathi, Sivakumar

2015-08-01

Membrane electrode assembly (MEA), which contains cathode and anode catalytic layer, gas diffusion layers (GDL) and electrolyte membrane, is the key unit of a PEMFC. An attempt to develop MEA for ABPBI membrane based high temperature (HT) PEMFC is conducted in this work by catalyst coating membrane (CCM) method. The structure and performance of the MEA are examined by scanning electron microscopy (SEM), electrochemical impedance spectroscopy (EIS) and I-V curve. Effects of the CCM preparation method, Pt loading and binder type are investigated for the optimization of the single cell performance. Under 160 °C and atmospheric pressure, the peak power density of the MEA, with Pt loading of 0.5 mg cm-2 and 0.3 mg cm-2 for the cathode and the anode, can reach 277 mW cm-2, while a current density of 620 A cm-2 is delivered at the working voltage of 0.4 V. The MEA prepared by CCM method shows good stability operating in a short term durability test: the cell voltage maintained at ∼0.45 V without obvious drop when operated at a constant current density of 300 mA cm-2 and 160 °C under ambient pressure for 140 h.

Fabrication of silica ceramic membrane via sol-gel dip-coating method at different nitric acid amount

NASA Astrophysics Data System (ADS)

Kahlib, N. A. Z.; Daud, F. D. M.; Mel, M.; Hairin, A. L. N.; Azhar, A. Z. A.; Hassan, N. A.

2018-01-01

Fabrication of silica ceramics via the sol-gel method has offered more advantages over other methods in the fabrication of ceramic membrane, such as simple operation, high purity homogeneous, well defined-structure and complex shapes of end products. This work presents the fabrication of silica ceramic membrane via sol-gel dip-coating methods by varying nitric acid amount. The nitric acid plays an important role as catalyst in fabrication reaction which involved hydrolysis and condensation process. The tubular ceramic support, used as the substrate, was dipped into the sol of Tetrethylorthosilicate (TEOS), distilled water and ethanol with the addition of nitric acid. The fabricated silica membrane was then characterized by (Field Emission Scanning Electron Microscope) FESEM and (Fourier transform infrared spectroscopy) FTIR to determine structural and chemical properties at different amount of acids. From the XRD analysis, the fabricated silica ceramic membrane showed the existence of silicate hydrate in the final product. FESEM images indicated that the silica ceramic membrane has been deposited on the tubular ceramic support as a substrate and penetrate into the pore walls. The intensity peak of FTIR decreased with increasing of amount of acids. Hence, the 8 ml of acid has demonstrated the appropriate amount of catalyst in fabricating good physical and chemical characteristic of silica ceramic membrane.

Pheromone-assisted techniques to improve the efficacy of insecticide sprays against Linepithema humile (Hymenoptera: Formicidae).

PubMed

Choe, Dong-Hwan; Tsai, Kasumi; Lopez, Carlos M; Campbell, Kathleen

2014-02-01

Outdoor residual sprays are among the most common methods for targeting pestiferous ants in urban pest management programs. If impervious surfaces such as concrete are treated with these insecticides, the active ingredients can be washed from the surface by rain or irrigation. As a result, residual sprays with fipronil and pyrethroids are found in urban waterways and aquatic sediments. Given the amount of insecticides applied to urban settings for ant control and their possible impact on urban waterways, the development of alternative strategies is critical to decrease the overall amounts of insecticides applied, while still achieving effective control of target ant species. Herein we report a "pheromone-assisted technique" as an economically viable approach to maximize the efficacy of conventional sprays targeting the Argentine ant. By applying insecticide sprays supplemented with an attractive pheromone compound, (Z)-9-hexadecenal, Argentine ants were diverted from nearby trails and nest entrances and subsequently exposed to insecticide residues. Laboratory experiments with fipronil and bifenthrin sprays indicated that the overall kill of the insecticides on Argentine ant colonies was significantly improved (57-142% increase) by incorporating (Z)-9-hexadecenal in the insecticide sprays. This technique, once it is successfully implemented in practical pest management programs, has the potential of providing maximum control efficacy with reduced amount of insecticides applied in the environment.

Antibody immobilization using pneumatic spray: comparison with the avidin-biotin bridge immobilization method.

PubMed

Figueroa, Jhon; Magaña, Sonia; Lim, Daniel V; Schlaf, Rudy

2012-12-14

The formation of a thin antibody film on a glass surface using pneumatic spray was investigated as a potential immobilization technique for capturing pathogenic targets. Goat-Escherichia coli O157:H7 IgG films were made by pneumatic spray and compared against the avidin-biotin bridge immobilized films by assaying with green fluorescent protein (GFP) transformed E. coli O157:H7 cells and fluorescent reporter antibodies. Functionality, stability, and immobilization of the films were tested. The pneumatic spray films had lower fluorescence intensity values than the avidin-biotin bridge films but resulted in similar detection for E. coli O157:H7 at 10(5)-10(7)cells/ml sample concentrations with no detection of non-E. coli O157:H7 strains. Both methods also resulted in similar percent capture efficiencies. The results demonstrated that immobilization of antibody via pneumatic spray did not render the antibody non-functional and produced stable antibody films. The amount of time necessary for immobilization of the antibody was reduced significantly from 24h for the avidin-biotin bridge to 7 min using the pneumatic spray technique, with additional benefits of greatly reduced use of materials and chemicals. The pneumatic spray technique promises to be an alternative for the immobilization of antibodies on glass slides for capturing pathogenic targets and use in biosensor type devices. Copyright © 2012. Published by Elsevier B.V.

Characteristics of Subfreezing Operation of Polymer Electrolyte Membrane Fuel Cells

NASA Astrophysics Data System (ADS)

Mishler, Jeffrey Harris

Polymer Electrolyte Membrane (PEM) Fuel Cells are capable of high efficiency operation, and are free of NOx, SOx, and CO2 emissions when using hydrogen fuel, and ideally suited for use in transportation applications due to their high power density and low operating temperatures. However, under subfreezing conditions which may be encountered during winter seasons in some areas, product water will freeze within the membrane, cathode side catalyst layer and gas diffusion media, leading to voltage loss and operation failure. Experiments were undertaken in order to characterize the amount and location of water during fuel cell operation. First, in-situ neutron radiography was undertaken on the fuel cells at a normal operating temperature for various operating current densities, inlet relative humidities, and diffusion media hydrophobicities. It was found that more hydrophobic cathode microporous layer (MPL) or hydrophilic anode MPL may result in a larger amount of water transporting back to the anode. The water profiles along the channels were measured and the point of liquid water emergence, where two phase flow begins, was compared to previous models. Secondly, under subfreezing temperatures, neutron imaging showed that water ice product accumulates because of lack of a water removal mechanism. Water was observed under both the lands and channels, and increased almost linearly with time. It is found that most ice exists in the cathode side. With evidence from experimental observation, a cold start model was developed and explained, following existing approaches in the literature. Three stages of cold start are explained: membrane saturation, ice storage in catalyst layer pores, and then ice melting. The voltage losses due to temperature change, increased transport resistance, and reduced electrochemical surface area. The ionic conductivity of the membrane at subfreezing temperatures was modeled. Voltage evolution over time for isothermal cold starts was predicted and validated against experimental data. The ice coverage coefficient was shown to be a key variable in matching with experimental data. From model analysis, it appears that the coulombs of charge passed before operation failure is an important parameter characterizing PEM fuel cell cold start. To investigate the coulombs of charge and its determining factors, PEM fuel cells were constructed to measure the effects of membrane configuration (thickness and initial state), catalyst layer configuration (thickness and ionomer-carbon ratio), current density, and temperature on the quantity. It was found that subfreezing temperature, ionomer-catalyst ratio, and catalyst-layer thickness significantly affect the amount of charge transferred before operational failure, whereas the membrane thickness and initial hydration level have limited effect for the considered cases. In addition, degradation of the catalyst layer was observed and quantified. These results improve the fundamental understanding of characteristics of subfreezing operation and thus are valuable for automobile applications of PEM fuel cells. The model directly relates the material properties to voltage loss, and predicts voltage evolution, thus providing a way for material optimization and diagnostics. Additionally, insights into component design and operating conditions can be used to better optimize the fuel cell for cold start-up of the vehicle.

A New Way to Spray

NASA Technical Reports Server (NTRS)

2000-01-01

A NASA SBIR contract provided the funding for a new nozzle shape to be used in plasma spray techniques. The new design, a bell shape, reduces overspray. The result is a significant decrease in the cost of plasma spraying and a higher quality, more pure coating.

Cold Spray Repair of Martensitic Stainless Steel Components

NASA Astrophysics Data System (ADS)

Faccoli, M.; Cornacchia, G.; Maestrini, D.; Marconi, G. P.; Roberti, R.

2014-12-01

The possibility of using cold spray as repair technique of martensitic stainless steel components was evaluated through laboratory investigations. An austenitic stainless steel feedstock powder was chosen, instead of soft metals powders like nickel, copper, or aluminum, used for repairing components made in light alloy or cast iron. The present study directly compares the microstructure, the residual stresses, and the micro-hardness of repairs obtained by cold spray and by TIG welding, that is commonly used as repair technique in large steel components. XRD and optical metallographic analysis of the repairs showed that cold spray offers some advantages, inducing compressive residual stresses in the repair and avoiding alterations of the interface between repair and base material. For these reasons, a heat treatment after the cold spray repair is not required to restore the base material properties, whereas a post-weld heat treatment is needed after the welding repair. Cold spray repair also exhibits a higher micro-hardness than the welding repair. In addition, the cavitation erosion resistance of a cold spray coating was investigated through ultrasonic cavitation tests, and the samples worn surfaces were observed by scanning electron microscopy.

Durability of De-Alloyed Platinum-Nickel Cathode Catalyst in Low Platinum Loading Membrane-Electrode Assemblies Subjected to Accelerated Stress Tests

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ahluwalia, R. K.; Wang, X.; Peng, J. -K.

Here, the durability of de-alloyed platinum-nickel catalysts supported on high-surface area carbon (d-PtNi/C) in optimized electrodes and membrane electrode assemblies (MEAs) under an accelerated stress test (AST) protocol is investigated with the objective of developing a quantitative understanding of the degradation mechanisms and their relationship to the electrode structure, pre-conditioning, and operating conditions. It is found that the cell degradation can be mitigated by controlling the voltage cycle, acid washing the MEA to remove Ni contaminants that enter the electrode and membrane during fabrication, and monitoring the operating conditions. For example, the electrochemical surface area (ECSA) loss is <25% aftermore » 30,000 triangle cycles with 0.925 V upper potential limit if the MEA is acid washed and extensive diagnostics are avoided. The parameters that exacerbate the cell degradation also accelerate the rate at which Ni leaches out from the catalyst. A mechanistic model is presented for the degradation in performance of d-PtNi/C electrodes. The model correlates a) the degradation in ORR mass and specific activities with ECSA and Ni losses, b) the decrease in limiting current density ( iL), which is inversely proportional to the O 2 mass transport resistance, with the degradation in catalyst roughness factor, and c) the increase in mass transfer overpotentials with the reduced current density, i/iL .« less

Fabrication of Mediatorless/Membraneless Glucose/Oxygen Based Biofuel Cell using Biocatalysts Including Glucose Oxidase and Laccase Enzymes.

PubMed

Christwardana, Marcelinus; Kim, Ki Jae; Kwon, Yongchai

2016-07-18

Mediatorless and membraneless enzymatic biofuel cells (EBCs) employing new catalytic structure are fabricated. Regarding anodic catalyst, structure consisting of glucose oxidase (GOx), poly(ethylenimine) (PEI) and carbon nanotube (CNT) is considered, while three cathodic catalysts consist of glutaraldehyde (GA), laccase (Lac), PEI and CNT that are stacked together in different ways. Catalytic activities of the catalysts for glucose oxidation and oxygen reduction reactions (GOR and ORR) are evaluated. As a result, it is confirmed that the catalysts work well for promotion of GOR and ORR. In EBC tests, performances of EBCs including 150 μm-thick membrane are measured as references, while those of membraneless EBCs are measured depending on parameters like glucose flow rate, glucose concentration, distance between two electrodes and electrolyte pH. With the measurements, how the parameters affect EBC performance and their optimal conditions are determined. Based on that, best maximum power density (MPD) of membraneless EBC is 102 ± 5.1 μW · cm(-2) with values of 0.5 cc · min(-1) (glucose flow rate), 40 mM (glucose concentration), 1 mm (distance between electrodes) and pH 3. When membrane and membraneless EBCs are compared, MPD of the membraneless EBC that is run at the similar operating condition to EBC including membrane is speculated as about 134 μW · cm(-2).

Fabrication of Mediatorless/Membraneless Glucose/Oxygen Based Biofuel Cell using Biocatalysts Including Glucose Oxidase and Laccase Enzymes

NASA Astrophysics Data System (ADS)

Christwardana, Marcelinus; Kim, Ki Jae; Kwon, Yongchai

2016-07-01

Mediatorless and membraneless enzymatic biofuel cells (EBCs) employing new catalytic structure are fabricated. Regarding anodic catalyst, structure consisting of glucose oxidase (GOx), poly(ethylenimine) (PEI) and carbon nanotube (CNT) is considered, while three cathodic catalysts consist of glutaraldehyde (GA), laccase (Lac), PEI and CNT that are stacked together in different ways. Catalytic activities of the catalysts for glucose oxidation and oxygen reduction reactions (GOR and ORR) are evaluated. As a result, it is confirmed that the catalysts work well for promotion of GOR and ORR. In EBC tests, performances of EBCs including 150 μm-thick membrane are measured as references, while those of membraneless EBCs are measured depending on parameters like glucose flow rate, glucose concentration, distance between two electrodes and electrolyte pH. With the measurements, how the parameters affect EBC performance and their optimal conditions are determined. Based on that, best maximum power density (MPD) of membraneless EBC is 102 ± 5.1 μW · cm-2 with values of 0.5 cc · min-1 (glucose flow rate), 40 mM (glucose concentration), 1 mm (distance between electrodes) and pH 3. When membrane and membraneless EBCs are compared, MPD of the membraneless EBC that is run at the similar operating condition to EBC including membrane is speculated as about 134 μW · cm-2.

Durability of De-Alloyed Platinum-Nickel Cathode Catalyst in Low Platinum Loading Membrane-Electrode Assemblies Subjected to Accelerated Stress Tests

DOE PAGES

Ahluwalia, R. K.; Wang, X.; Peng, J. -K.; ...

2018-04-25

Here, the durability of de-alloyed platinum-nickel catalysts supported on high-surface area carbon (d-PtNi/C) in optimized electrodes and membrane electrode assemblies (MEAs) under an accelerated stress test (AST) protocol is investigated with the objective of developing a quantitative understanding of the degradation mechanisms and their relationship to the electrode structure, pre-conditioning, and operating conditions. It is found that the cell degradation can be mitigated by controlling the voltage cycle, acid washing the MEA to remove Ni contaminants that enter the electrode and membrane during fabrication, and monitoring the operating conditions. For example, the electrochemical surface area (ECSA) loss is <25% aftermore » 30,000 triangle cycles with 0.925 V upper potential limit if the MEA is acid washed and extensive diagnostics are avoided. The parameters that exacerbate the cell degradation also accelerate the rate at which Ni leaches out from the catalyst. A mechanistic model is presented for the degradation in performance of d-PtNi/C electrodes. The model correlates a) the degradation in ORR mass and specific activities with ECSA and Ni losses, b) the decrease in limiting current density ( iL), which is inversely proportional to the O 2 mass transport resistance, with the degradation in catalyst roughness factor, and c) the increase in mass transfer overpotentials with the reduced current density, i/iL .« less

Bioinspired Synthesis of Photocatalytic Nanocomposite Membranes Based on Synergy of Au-TiO2 and Polydopamine for Degradation of Tetracycline under Visible Light.

PubMed

Wang, Chen; Wu, Yilin; Lu, Jian; Zhao, Juan; Cui, Jiuyun; Wu, Xiuling; Yan, Yongsheng; Huo, Pengwei

2017-07-19

A bioinspired photocatalytic nanocomposite membrane was successfully prepared via polydopamine (pDA)-coated poly(vinylidene fluoride) (PVDF) membrane, as a secondary platform for vacuum-filtrated Au-TiO 2 nanocomposites, with enhanced photocatalytic activity. The degradation efficiency of Au-TiO 2 /pDA/PVDF membranes reached 92% when exposed to visible light for 120 min, and the degradation efficiency of Au-TiO 2 /pDA/PVDF membranes increased by 26% compared to that of Au-TiO 2 powder and increased by 51% compared to that of TiO 2 /pDA/PVDF nanocomposite membranes. The degradation efficiency remained about 90% after five cycle experiments, and the Au-TiO 2 /pDA/PVDF nanocomposite membranes showed good stability, regeneration performance, and easy recycling. The pDA coating not only served as a bioadhesion interface to improve the bonding force between the catalyst and the membrane substrate but also acted as a photosensitizer to broaden the wavelength response range of TiO 2 , and the structure of Au-TiO 2 /pDA/PVDF also improves the transfer rate of photogenerated electrons; the surface plasmon resonance effect of Au also played a positive role in improving the activity of the catalyst. Therefore, we believe that this study opens up a new strategy in preparing the bioinspired photocatalytic nanocomposite membrane for potential wastewater purification, catalysis, and as a membrane separation field.

The Experimental Measurement of Local and Bulk Oxygen Transport Resistances in the Catalyst Layer of Proton Exchange Membrane Fuel Cells.

PubMed

Wang, Chao; Cheng, Xiaojing; Lu, Jiabin; Shen, Shuiyun; Yan, Xiaohui; Yin, Jiewei; Wei, Guanghua; Zhang, Junliang

2017-12-07

Remarkable progress has been made in reducing the cathodic Pt loading of PEMFCs; however, a huge performance loss appears at high current densities, indicating the existence of a large oxygen transport resistance associated with the ultralow Pt loading catalyst layer. To reduce the Pt loading without sacrificing cell performance, it is essential to illuminate the oxygen transport mechanism in the catalyst layer. Toward this goal, an experimental approach to measure the oxygen transport resistance in catalyst layers is proposed and realized for the first time in this study. The measuring approach involves a dual-layer catalyst layer design, which consists of a dummy catalyst layer and a practical catalyst layer, followed by changing the thickness of dummy layer to respectively quantify the local and bulk resistances via limiting current measurements combined with linear extrapolation. The experimental results clearly reveal that the local resistance dominates the total resistance in the catalyst layer.

Rotating bubble membrane radiator

DOEpatents

Webb, Brent J.; Coomes, Edmund P.

1988-12-06

A heat radiator useful for expelling waste heat from a power generating system aboard a space vehicle is disclosed. Liquid to be cooled is passed to the interior of a rotating bubble membrane radiator, where it is sprayed into the interior of the bubble. Liquid impacting upon the interior surface of the bubble is cooled and the heat radiated from the outer surface of the membrane. Cooled liquid is collected by the action of centrifical force about the equator of the rotating membrane and returned to the power system. Details regarding a complete space power system employing the radiator are given.

Electrochemical study of highly durable cathode with Pt supported on ITO-CNT composite for proton exchange membrane fuel cells

DOE Office of Scientific and Technical Information (OSTI.GOV)

Park, Sehkyu; Shao, Yuyan; Viswanathan, Vilayanur V.

2016-10-01

In this paper, we describe a highly stable cathode containing a Pt catalyst supported on an indium tin oxide (ITO) and carbon nanotube (CNT) composite. The dependence of cathode performance and durability on the ITO content and the diameter of the CNTs were investigated by electrochemical techniques. The cathode with 30 wt% ITO and CNTs with diameters 10–20 nm in the composite offered preferred locations for Pt stabilization and was very resistant to carbon corrosion (i.e., 82.7% ESA retention and 105.7% mass activity retention after an accelerated stress test for 400 h).

Reliability of high-strain ionomeric polymer transducers fabricated using the novel direct assembly process

NASA Astrophysics Data System (ADS)

Akle, Barbar; Nawshin, Saila; Leo, Donald

2006-03-01

Ionomeric polymer transducers have received considerable attention in the past several years. These actuators, sometimes referred to as artificial muscles, have the ability to generate large bending strain and moderate stress at low applied voltages. Typically, ionic polymer actuators are composed of Nafion-117 membranes with platinum electrodes and are saturated with water diluents. Recently the authors have developed a novel fabrication technique named the Direct Assembly Process (DAP), which allowed good control on electrode morphology and composition. The DAP consists of spraying two high surface area metal-ionomer electrodes on a Nafion membrane. A single- walled carbon nanotubes (SWNT) and ruthenium dioxide (RuO II) hybrid electrode was sprayed on a Formamide hydrated Nafion-117 membrane using the DAP method. This transducer was shown to generate 9.4% peak-peak strain under the application of +/-2V at a strain rate of 1%/sec. Furthermore using the DAP one is capable of incorporating several types of diluents in ionomeric polymer transducers. Transducers with ionic liquid diluents are demonstrated to operate in air for long periods of time. In this work we will present a reliability study of transducers fabricated using the DAP. Each transducer is tested under a frequency range of 0.2Hz to 1Hz, and a potential of +/-1V to +/-3V. Water hydrated transducers dehydrates and stop moving within 5 minutes while operating in air under +/-2V. Transducers with Formamide diluents operate for 20,000 cycles under +/-1.5V and 0.5Hz (around 11hrs), while they degrade in less than 3000 cycles under +/-2V and 0.5Hz. Ionic liquid based transducers are demonstrated to operate in air for over 400,000 with little loss in performance, and over 1 million cycle with a loss of only 43%. Actuators with several electrode compositions are fabricated and a correlation between the reliability of ionic liquid-ionic polymer transducers and maximum strain will be presented. This correlation will be used to assess the adhesion between the high surface area electrodes and the Nafion membrane. SEM images of tested transducers will be presented.

New catalyst supports prepared by surface modification of graphene- and carbon nanotube structures with nitrogen containing carbon coatings

NASA Astrophysics Data System (ADS)

Oh, Eun-Jin; Hempelmann, Rolf; Nica, Valentin; Radev, Ivan; Natter, Harald

2017-02-01

We present a new and facile method for preparation of nitrogen containing carbon coatings (NCC) on the surface of graphene- and carbon nanotubes (CNT), which has an increased electronic conductivity. The modified carbon system can be used as catalyst support for electrocatalytic applications, especially for polymer electrolyte membrane fuel cells (PEMFC). The surface modification is performed by impregnating carbon structures with a nitrogen containing ionic liquid (IL) with a defined C:N ratio, followed by a thermal treatment under ambient conditions. We investigate the influence of the main experimental parameters (IL amount, temperature, substrate morphology) on the formation of the NCC. Additionally, the structure and the chemical composition of the resulting products are analyzed by electron microscopic techniques (SEM, TEM), energy disperse X-ray analysis (EDX), X-ray photoelectron spectroscopy (XPS) and hot extraction analysis. The modified surface has a nitrogen content of 29 wt% which decreases strongly at temperatures above 600 °C. The new catalyst supports are used for the preparation of PEMFC anodes which are characterized by polarization measurements and electrochemical impedance spectroscopy (EIS). Compared to unmodified graphene and CNT samples the electronic conductivity of the modified systems is increased by a factor of 2 and shows improved mass transport properties.

Measurements in liquid fuel sprays

NASA Technical Reports Server (NTRS)

Chigier, N.

1984-01-01

Techniques for studying the events directly preceding combustion in the liquid fuel sprays are being used to provide information as a function of space and time on droplet size, shape, number density, position, angle of flight and velocity. Spray chambers were designed and constructed for: (1) air-assist liquid fuel research sprays; (2) high pressure and temperature chamber for pulsed diesel fuel sprays; and (3) coal-water slurry sprays. Recent results utilizing photography, cinematography, and calibration of the Malvern particle sizer are reported. Systems for simultaneous measurement of velocity and particle size distributions using laser Doppler anemometry interferometry and the application of holography in liquid fuel sprays are being calibrated.

Nanoalloy catalysts inside fuel cells: An atomic-level perspective on the functionality by combined in operando x-ray spectroscopy and total scattering

DOE Office of Scientific and Technical Information (OSTI.GOV)

Petkov, Valeri; Maswadeh, Yazan; Zhao, Yinguang

We introduce an experimental approach for structural characterization of catalysts for fuel cells combining synchrotron x-ray spectroscopy and total scattering. The approach allows probing catalysts inside operating fuel cells with atomic-level precision (~ 0.02 Å) and element specificity (~ 2–3 at%) in both time (~ 1 min) and space (~ μm) resolved manner. The approach is demonstrated on exemplary Pd-Sn and Pt-Ni-Cu nanoalloy catalysts for the oxygen reduction reaction (ORR) deposited on the cathode of an operating proton exchange membrane fuel cell. In operando x-ray data show that under operating conditions, the catalyst particles can undergo specific structural changes, rangingmore » from sub-Å atomic fluctuations and sharp nanophase transitions to a gradual strain relaxation and growth, which inflict significant losses in their ORR activity. Though triggered electrochemically, the changes are not driven solely by differences in the reduction potential and surface energy of the metallic species constituting the nanoalloys but also by the formation energy of competing nanophases, mismatch between the size of individual atomic species and their ability to interdiffuse fast in search of energetically favorable configurations. Given their complexity, the changes are difficult to predict and so the resulting ORR losses remain difficult to limit. We show that in operando knowledge of the structural evolution of nanoalloy catalysts helps create strategies for improving their activity and stability. In particular, we show that shaping Pd-Sn nanoalloys rich in Pd as cubes reduces the interdiffusion of atoms at their surface and so makes them better catalysts for ORR in fuel cells in comparison to other Pd-Sn nanoalloys. In addition, we demonstrate that the approach introduced here can provide knowledge of other major factors affecting the performance of fuel cells such as operating temperature and the overall catalyst utilization, in particular the evolution of elemental and mass distribution of catalyst particles over the cells’ cathode. Last but not least, we discuss how in operando x-ray spectroscopy and total x-ray scattering can bridge the knowledge gap between the widely used in situ SAXS, EXAFS and monocrystal surface XRD techniques for structural characterization of nanoalloy catalysts explored for energy related applications.« less

Nanoalloy catalysts inside fuel cells: An atomic-level perspective on the functionality by combined in operando x-ray spectroscopy and total scattering

DOE PAGES

Petkov, Valeri; Maswadeh, Yazan; Zhao, Yinguang; ...

2018-04-18

We introduce an experimental approach for structural characterization of catalysts for fuel cells combining synchrotron x-ray spectroscopy and total scattering. The approach allows probing catalysts inside operating fuel cells with atomic-level precision (~ 0.02 Å) and element specificity (~ 2–3 at%) in both time (~ 1 min) and space (~ μm) resolved manner. The approach is demonstrated on exemplary Pd-Sn and Pt-Ni-Cu nanoalloy catalysts for the oxygen reduction reaction (ORR) deposited on the cathode of an operating proton exchange membrane fuel cell. In operando x-ray data show that under operating conditions, the catalyst particles can undergo specific structural changes, rangingmore » from sub-Å atomic fluctuations and sharp nanophase transitions to a gradual strain relaxation and growth, which inflict significant losses in their ORR activity. Though triggered electrochemically, the changes are not driven solely by differences in the reduction potential and surface energy of the metallic species constituting the nanoalloys but also by the formation energy of competing nanophases, mismatch between the size of individual atomic species and their ability to interdiffuse fast in search of energetically favorable configurations. Given their complexity, the changes are difficult to predict and so the resulting ORR losses remain difficult to limit. We show that in operando knowledge of the structural evolution of nanoalloy catalysts helps create strategies for improving their activity and stability. In particular, we show that shaping Pd-Sn nanoalloys rich in Pd as cubes reduces the interdiffusion of atoms at their surface and so makes them better catalysts for ORR in fuel cells in comparison to other Pd-Sn nanoalloys. In addition, we demonstrate that the approach introduced here can provide knowledge of other major factors affecting the performance of fuel cells such as operating temperature and the overall catalyst utilization, in particular the evolution of elemental and mass distribution of catalyst particles over the cells’ cathode. Last but not least, we discuss how in operando x-ray spectroscopy and total x-ray scattering can bridge the knowledge gap between the widely used in situ SAXS, EXAFS and monocrystal surface XRD techniques for structural characterization of nanoalloy catalysts explored for energy related applications.« less

Water sprays in space retrieval operations. [for disabled spacecraft detumbling and despinning

NASA Technical Reports Server (NTRS)

Freesland, D. C.

1978-01-01

The water spray technique (WST) for nullifying the angular momentum of a disabled spacecraft is examined. Such a despinning operation is necessary before a disabled spacecraft can be retrieved by the Space Shuttle. The WST involving the use of liquid sprays appears to be less complex and costly than other techniques proposed to despin a disabled vehicle. A series of experiments have been conducted to determine physical properties of water sprays exhausting into a vacuum. A computer model is built which together with the experimental results yields satellite despin performance parameters. The selection and retrieval of an actual disabled spacecraft is considered to demonstrate an application of the WST.

Evaluation of mechanical properties of Aluminum-Copper cold sprayed and alloy 625 wire arc sprayed coatings

NASA Astrophysics Data System (ADS)

Bashirzadeh, Milad

This study examines microstructural-based mechanical properties of Al-Cu composite deposited by cold spraying and wire arc sprayed nickel-based alloy 625 coating using numerical modeling and experimental techniques. The microhardness and elastic modulus of samples were determined using the Knoop hardness technique. Hardness in both transverse and longitudinal directions on the sample cross-sections has been measured. An image-based finite element simulation algorithm was employed to determine the mechanical properties through an inverse analysis. In addition mechanical tests including, tensile, bending, and nano-indentation tests were performed on alloy 625 wire arc sprayed samples. Overall, results from the experimental tests are in relatively good agreement for deposited Al-Cu composites and alloy 625 coating. However, results obtained from numerical simulation are significantly higher in value than experimentally obtained results. Examination and comparison of the results are strong indications of the influence of microstructure characteristics on the mechanical properties of thermally spray deposited coatings.

Microscopic Examination of Cold Spray Cermet Sn+In2O3 Coatings for Sputtering Target Materials

PubMed Central

Baszczuk, A.; Rutkowska-Gorczyca, M.; Jasiorski, M.; Małachowska, A.; Posadowski, W.; Znamirowski, Z.

2017-01-01

Low-pressure cold spraying is a newly developed technology with high application potential. The aim of this study was to investigate potential application of this technique for producing a new type of transparent conductive oxide films target. Cold spraying technique allows the manufacture of target directly on the backing plate; therefore the proposed sputtering target has a form of Sn+In2O3 coating sprayed onto copper substrate. The microstructure and properties of the feedstock powder prepared using three various methods as well as the deposited ones by low-pressure cold spraying coatings were evaluated, compared, and analysed. Produced cermet Sn+In2O3 targets were employed in first magnetron sputtering process to deposit preliminary, thin, transparent conducting oxide films onto the glass substrates. The resistivity of obtained preliminary films was measured and allows believing that fabrication of TCO (transparent conducting oxide) films using targets produced by cold spraying is possible in the future, after optimization of the deposition conditions. PMID:29109810

Microscopic Examination of Cold Spray Cermet Sn+In2O3 Coatings for Sputtering Target Materials.

PubMed

Winnicki, M; Baszczuk, A; Rutkowska-Gorczyca, M; Jasiorski, M; Małachowska, A; Posadowski, W; Znamirowski, Z; Ambroziak, A

2017-01-01

Low-pressure cold spraying is a newly developed technology with high application potential. The aim of this study was to investigate potential application of this technique for producing a new type of transparent conductive oxide films target. Cold spraying technique allows the manufacture of target directly on the backing plate; therefore the proposed sputtering target has a form of Sn+In 2 O 3 coating sprayed onto copper substrate. The microstructure and properties of the feedstock powder prepared using three various methods as well as the deposited ones by low-pressure cold spraying coatings were evaluated, compared, and analysed. Produced cermet Sn+In 2 O 3 targets were employed in first magnetron sputtering process to deposit preliminary, thin, transparent conducting oxide films onto the glass substrates. The resistivity of obtained preliminary films was measured and allows believing that fabrication of TCO (transparent conducting oxide) films using targets produced by cold spraying is possible in the future, after optimization of the deposition conditions.

Iridium-Doped Ruthenium Oxide Catalyst for Oxygen Evolution

NASA Technical Reports Server (NTRS)

Valdez, Thomas I.; Narayan, Sri R.; Billings, Keith J.

2011-01-01

NASA requires a durable and efficient catalyst for the electrolysis of water in a polymer-electrolyte-membrane (PEM) cell. Ruthenium oxide in a slightly reduced form is known to be a very efficient catalyst for the anodic oxidation of water to oxygen, but it degrades rapidly, reducing efficiency. To combat this tendency of ruthenium oxide to change oxidation states, it is combined with iridium, which has a tendency to stabilize ruthenium oxide at oxygen evolution potentials. The novel oxygen evolution catalyst was fabricated under flowing argon in order to allow the iridium to preferentially react with oxygen from the ruthenium oxide, and not oxygen from the environment. Nanoparticulate iridium black and anhydrous ruthenium oxide are weighed out and mixed to 5 18 atomic percent. They are then heat treated at 300 C under flowing argon (in order to create an inert environment) for a minimum of 14 hours. This temperature was chosen because it is approximately the creep temperature of ruthenium oxide, and is below the sintering temperature of both materials. In general, the temperature should always be below the sintering temperature of both materials. The iridium- doped ruthenium oxide catalyst is then fabricated into a PEM-based membrane- electrode assembly (MEA), and then mounted into test cells. The result is an electrolyzer system that can sustain electrolysis at twice the current density, and at the same efficiency as commercial catalysts in the range of 100-200 mA/sq cm. At 200 mA/sq cm, this new system operates at an efficiency of 85 percent, which is 2 percent greater than commercially available catalysts. Testing has shown that this material is as stable as commercially available oxygen evolution catalysts. This means that this new catalyst can be used to regenerate fuel cell systems in space, and as a hydrogen generator on Earth.

Detailed assessment of diesel spray atomization models using visible and X-ray extinction measurements

DOE Office of Scientific and Technical Information (OSTI.GOV)

Magnotti, G. M.; Genzale, C. L.

The physical mechanisms characterizing the breakup of a diesel spray into droplets are still unknown. This gap in knowledge has largely been due to the challenges of directly imaging this process or quantitatively measuring the outcomes of spray breakup, such as droplet size. Recent x-ray measurements by Argonne National Laboratory, utilized in this work, provide needed information about the spatial evolution of droplet sizes in selected regions of the spray under a range of injection pressures (50–150 MPa) and ambient densities (7.6–22.8 kg/m3) relevant for diesel operating conditions. Ultra-small angle x-ray scattering (USAXS) measurements performed at the Advanced Photon Sourcemore » are presented, which quantify Sauter mean diameters (SMD) within optically thick regions of the spray that are inaccessible by conventional droplet sizing measurement techniques, namely in the near-nozzle region, along the spray centerline, and within the core of the spray. To quantify droplet sizes along the periphery of the spray, a complementary technique is proposed and introduced, which leverages the ratio of path-integrated x-ray and visible laser extinction (SAMR) measurements to quantify SMD. The SAMR and USAXS measurements are then utilized to evaluate current spray models used for engine computational fluid dynamic (CFD) simulations. We explore the ability of a carefully calibrated spray model, premised on aerodynamic wave growth theory, to capture the experimentally observed trends of SMD throughout the spray. The spray structure is best predicted with an aerodynamic primary and secondary breakup process that is represented with a slower time constant and larger formed droplet size than conventionally recommended for diesel spray models. Additionally, spray model predictions suggest that droplet collisions may not influence the resultant droplet size distribution along the spray centerline in downstream regions of the spray.« less

Non-Platinum Group Metal OER/ORR Catalysts for Alkaline Membrane Fuel Cells and Electrolyzers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Danilovic, Nemanja; Ayers, Katherine

Regenerative fuel cells (RFC) are energy storage devices that capture electrical energy in the form of hydrogen, with potential application for backup power and energy storage in remote locations, unmanned missions, and renewable energy capture. A unitized regenerative fuel cell (URFC) combines two separate electrochemical devices (fuel cell and electrolyzer) into one stack. The stack cost is driven by the platinum group metal (PGM) catalysts and the flow field components designed to withstand high potentials in acidic environments. Since the stack is the most expensive subcomponent of both the fuel cell and electrolyzer system, combining the two devices results inmore » substantial reduction in capital cost. However, in the past, combining the two stacks sacrificed device performance (operating cost) largely because the fuel cell had to operate with the thick electrolysis membranes in a URFC configuration, and due to water management issues in switching modes. Recent work in membrane-based electrolysis has resulted in more mechanically robust designs and materials that allow much thinner membranes, and work in flow cell design such as flow batteries has shown improved water transport through channel design and wet-proofing approaches. Therefore, the URFC concept is worth revisiting. At the same time, alkaline exchange membrane (AEM) devices are gathering attention due to the promise of PGM and valve metal elimination from the stack and a resulting strategic and capital cost benefit as compared with proton exchange membrane (PEM) systems. The result is a lower capital cost system that has half the precious metal group (PGM) catalysts, membrane and other stack component materials compared with discrete RFCs, although at the sacrifice of performance (operating cost). Proton has identified innovative AEM based RFC's to fulfill the role of low capital cost energy storage device owing to the use of non-precious metal containing electrodes, that enables certain markets where higher operating costs can be tolerated.« less

Hydrogen production by reforming of liquid hydrocarbons in a membrane reactor for portable power generation-Experimental studies

NASA Astrophysics Data System (ADS)

Damle, Ashok S.

One of the most promising technologies for lightweight, compact, portable power generation is proton exchange membrane (PEM) fuel cells. PEM fuel cells, however, require a source of pure hydrogen. Steam reforming of hydrocarbons in an integrated membrane reactor has potential to provide pure hydrogen in a compact system. Continuous separation of product hydrogen from the reforming gas mixture is expected to increase the yield of hydrogen significantly as predicted by model simulations. In the laboratory-scale experimental studies reported here steam reforming of liquid hydrocarbon fuels, butane, methanol and Clearlite ® was conducted to produce pure hydrogen in a single step membrane reformer using commercially available Pd-Ag foil membranes and reforming/WGS catalysts. All of the experimental results demonstrated increase in hydrocarbon conversion due to hydrogen separation when compared with the hydrocarbon conversion without any hydrogen separation. Increase in hydrogen recovery was also shown to result in corresponding increase in hydrocarbon conversion in these studies demonstrating the basic concept. The experiments also provided insight into the effect of individual variables such as pressure, temperature, gas space velocity, and steam to carbon ratio. Steam reforming of butane was found to be limited by reaction kinetics for the experimental conditions used: catalysts used, average gas space velocity, and the reactor characteristics of surface area to volume ratio. Steam reforming of methanol in the presence of only WGS catalyst on the other hand indicated that the membrane reactor performance was limited by membrane permeation, especially at lower temperatures and lower feed pressures due to slower reconstitution of CO and H 2 into methane thus maintaining high hydrogen partial pressures in the reacting gas mixture. The limited amount of data collected with steam reforming of Clearlite ® indicated very good match between theoretical predictions and experimental results indicating that the underlying assumption of the simple model of conversion of hydrocarbons to CO and H 2 followed by equilibrium reconstitution to methane appears to be reasonable one.

Effect of whey protein isolate and β-cyclodextrin wall systems on stability of microencapsulated vanillin by spray-freeze drying method.

PubMed

Hundre, Swetank Y; Karthik, P; Anandharamakrishnan, C

2015-05-01

Vanillin flavour is highly volatile in nature and due to that application in food incorporation is limited; hence microencapsulation of vanillin is an ideal technique to increase its stability and functionality. In this study, vanillin was microencapsulated for the first time by non-thermal spray-freeze-drying (SFD) technique and its stability was compared with other conventional techniques such as spray drying (SD) and freeze-drying (FD). Different wall materials like β-cyclodextrin (β-cyd), whey protein isolate (WPI) and combinations of these wall materials (β-cyd + WPI) were used to encapsulate vanillin. SFD microencapsulated vanillin with WPI showed spherical shape with numerous fine pores on the surface, which in turn exhibited good rehydration ability. On the other hand, SD powder depicted spherical shape without pores and FD encapsulated powder yielded larger particle sizes with flaky structure. FTIR analysis confirmed that there was no interaction between vanillin and wall materials. Moreover, spray-freeze-dried vanillin + WPI sample exhibited better thermal stability than spray dried and freeze-dried microencapsulated samples. Copyright © 2014 Elsevier Ltd. All rights reserved.

Kinetics of the water/air phase transition of radon and its implication on detection of radon-in-water concentrations: practical assessment of different on-site radon extraction methods.

PubMed

Schubert, Michael; Paschke, Albrecht; Bednorz, Denise; Bürkin, Walter; Stieglitz, Thomas

2012-08-21

The on-site measurement of radon-in-water concentrations relies on extraction of radon from the water followed by its detection by means of a mobile radon-in-air monitor. Many applications of radon as a naturally occurring aquatic tracer require the collection of continuous radon concentration time series, thus necessitating the continuous extraction of radon either from a permanent water stream supplied by a water pump or directly from a water body or a groundwater monitoring well. Essentially, three different types of extraction units are available for this purpose: (i) a flow-through spray chamber, (ii) a flow-through membrane extraction module, and (iii) a submersible (usually coiled) membrane tube. In this paper we discuss the advantages and disadvantages of these three methodical approaches with particular focus on their individual response to instantaneously changing radon-in-water concentrations. After a concise introduction into theoretical aspects of water/air phase transition kinetics of radon, experimental results for the three types of extraction units are presented. Quantitative suggestions for optimizing the detection setup by increasing the water/air interface and by reducing the air volume circulating through the degassing unit and radon detector are made. It was shown that the flow-through spray chamber and flow-through membrane perform nearly similarly, whereas the submersible membrane tubing has a significantly larger delay in response to concentration changes. The flow-through spray chamber is most suitable in turbid waters and to applications where high flow rates of the water pump stream can be achieved (e.g., where the power supply is not constrained by field conditions). The flow-through membrane is most suited to radon extraction from clear water and in field conditions where the power supply to a water pump is limited, e.g., from batteries. Finally, the submersible membrane tube is most suitable if radon is to be extracted in situ without any water pumping, e.g., in groundwater wells with a low yield, or in long-term time series, in which short-term variations in the radon concentration are of no relevance.

A New Quantitative 3D Imaging Method for Characterizing Spray in the Near-field of Nozzle Exits

DTIC Science & Technology

2015-01-13

measurements were performed on a flat-panel tabletop cone - beam CT system in the Radiology Department at Stanford University. The X-ray generator (CPI...quantitative measurement technique to examine the dense near-field region of sprays using X-ray computed tomography (CT). An optimized “spray CT system” was...Office P.O. Box 12211 Research Triangle Park, NC 27709-2211 X-ray CT, Spray, Hollow Cone Spray, Near Field REPORT DOCUMENTATION PAGE 11. SPONSOR

Operando chemistry of catalyst surfaces during catalysis.

PubMed

Dou, Jian; Sun, Zaicheng; Opalade, Adedamola A; Wang, Nan; Fu, Wensheng; Tao, Franklin Feng

2017-04-03

Chemistry of a catalyst surface during catalysis is crucial for a fundamental understanding of mechanism of a catalytic reaction performed on the catalyst in the gas or liquid phase. Due to the pressure- or molecular density-dependent entropy contribution of gas or liquid phase of the reactants and the potential formation of a catalyst surface during catalysis different from that observed in an ex situ condition, the characterization of the surface of a catalyst under reaction conditions and during catalysis can be significant and even necessary for understanding the catalytic mechanism at a molecular level. Electron-based analytical techniques are challenging for studying catalyst nanoparticles in the gas or liquid phase although they are necessary techniques to employ. Instrumentation and further development of these electron-based techniques have now made in situ/operando studies of catalysts possible. New insights into the chemistry and structure of catalyst nanoparticles have been uncovered over the last decades. Herein, the origin of the differences between ex situ and in situ/operando studies of catalysts, and the technical challenges faced as well as the corresponding instrumentation and innovations utilized for characterizing catalysts under reaction conditions and during catalysis, are discussed. The restructuring of catalyst surfaces driven by the pressure of reactant(s) around a catalyst, restructuring in reactant(s) driven by reaction temperature and restructuring during catalysis are also reviewed herein. The remaining challenges and possible solutions are briefly discussed.

Recent developments in plasma spray processes for applications in energy technology

NASA Astrophysics Data System (ADS)

Mauer, G.; Jarligo, M. O.; Marcano, D.; Rezanka, S.; Zhou, D.; Vaßen, R.

2017-03-01

This work focuses on recent developments of plasma spray processes with respect to specific demands in energy technology. High Velocity Atmospheric Plasma Spraying (HV-APS) is a novel variant of plasma spraying devoted to materials which are prone to oxidation or decomposition. It is shown how this process can be used for metallic bondcoats in thermal barrier coating systems. Furthermore, Suspension Plasma Spraying (SPS) is a new method to process submicron-sized feedstock powders which are not sufficiently flowable to feed them in dry state. SPS is presently promoted by the development of novel torch concepts with axial feedstock injection. An example for a columnar structured double layer thermal barrier coating is given. Finally, Plasma Spray-Physical Vapor Deposition (PS-PVD) is a novel technology operating in controlled atmosphere at low pressure and high plasma power. At such condition, vaporization even of high-melting oxide ceramics is possible enabling the formation of columnar structured, strain tolerant coatings with low thermal conductivity. Applying different conditions, the deposition is still dominated by liquid splats. Such process is termed Low Pressure Plasma Spraying-Thin Film (LPPS-TF). Two examples of applications are gas-tight and highly ionic and electronic conductive electrolyte and membrane layers which were deposited on porous metallic substrates.

Comparative study on structural and optical properties of CdS films fabricated by three different low-cost techniques

NASA Astrophysics Data System (ADS)

Ravichandran, K.; Philominathan, P.

2009-03-01

Highly crystalline and transparent cadmium sulphide films were fabricated at relatively low temperature by employing an inexpensive, simplified spray technique using perfume atomizer (generally used for cosmetics). The structural, surface morphological and optical properties of the films were studied and compared with that prepared by conventional spray pyrolysis using air as carrier gas and chemical bath deposition. The films deposited by the simplified spray have preferred orientation along (1 0 1) plane. The lattice parameters were calculated as a = 4.138 Å and c = 6.718 Å which are well agreed with that obtained from the other two techniques and also with the standard data. The optical transmittance in the visible range and the optical band gap were found as 85% and 2.43 eV, respectively. The structural and optical properties of the films fabricated by the simplified spray are found to be desirable for opto-electronic applications.

Quantifying liquid boundary and vapor distributions in a fuel spray by rainbow schlieren deflectometry.

PubMed

Taber Wanstall, C; Agrawal, Ajay K; Bittle, Joshua A

2017-10-20

The rainbow schlieren deflectometry (RSD) technique is used to determine the liquid boundary and the fuel volume fraction distributions in the vapor region of a high-pressure fuel spray. Experiments were conducted in a constant pressure flow vessel, whereby a customized single-hole common-rail diesel injector is used to introduce n-heptane fuel into a coflow of low-speed ambient air at two different test conditions. Only the quasi-steady period of the fuel spray is considered, and multiple injections are performed to acquire statistically significant data at an image acquisition rate of 20 kHz. An algorithm to identify the liquid boundary using intensity recorded by the RSD images is presented. The results are compared against measurements obtained by the Mie scattering technique. Results demonstrate that the RSD can be a powerful optical diagnostics technique to simultaneously quantify both the vapor and liquid regions in the high-pressure fuel sprays.

Field Hydraulic and Air-Blast Sprayers for Row Crops.

ERIC Educational Resources Information Center

Cole, Herbert, Jr., Comp.

This agriculture extension service publication from Pennsylvania State University discusses techniques and equipment used in spraying field crops. In the discussion of field hydraulic sprayers, specific topics include types of sprayers, tanks, pumps, pressure regulators, hoses, boom spraying, directed spraying, and nozzle bodies. In the discussion…

An investigation of flow-limited field-injection electrostatic spraying (FFESS) and its applications to thin film deposition

NASA Astrophysics Data System (ADS)

Singh, Ravindra Pratap

Electrostatic spraying is the process of controlled disruption of a liquid surface due to excess surface charge density. The technique has found applications in a wide range of fields from agricultural sprays to fuel injectors to colloidal thrusters for space vehicle propulsion. Over the past 20 years, the technique has been intensely studied in material processing for synthesis of ceramic and metal powders, nanoparticles and thin films. The importance of the technique lies in its simple setup, high deposition efficiency, and ambient atmosphere operation. In conventional electrostatic spraying (CESS), one uses a conducting nozzle to charge the liquid, mostly by induction charging. CESS is therefore restricted to the single jet mode of spraying which occurs at low spray currents. It lacks stability and reproducibility in the high current, multiple jet regime, which can generate much finer sprays. In flow-limited field-injection electrostatic spraying (FFESS), one uses a field-injection electrode to stably and controllably inject higher currents into the liquid, a la Fowler-Nordheim, using an otherwise insulating nozzle. This way, it is possible to stably electrospray in the multiple jet mode. In addition to producing much finer sprays, the multi-jet mode atomizes liquids at higher rates, and spreads the spray over a wider region and more uniformly than single jet sprays, thus paving way for large-area uniform thin film deposition. A simple yet comprehensive theory is formulated to describe the multi jet formation. The theory, which is based on the energy minimization principle, takes into account, for the first time, the interactions between charged jets which leads to saturation in the number of jets at high spray currents. The possibility of using an array of nozzles to obtain uniform large-area high-throughput thin film deposition is also investigated. A large number of FFESS nozzles with alternating positive and negative polarities arranged in a periodic 2-dimensional array are found to produce uniform thin films over large areas. Deposition of TiO2 and silver thin films using multi jet FFESS is studied, demonstrating great control on film morphology and properties. TiO2 thin films deposited on high-intensity discharge arc lamps are found to improve the quality of its light output. Silver thin films of high purity and conductivity, and with good adhesion, could be deposited at relatively high deposition rates and high deposition efficiency as compared to CVD techniques.

Characterization of sprays

NASA Technical Reports Server (NTRS)

Chigier, N.; Mao, C.-P.

1984-01-01

It is pointed out that most practical power generation and propulsion systems involve the burning of different types of fuel sprays, taking into account aircraft propulsion, industrial furnaces, boilers, gas turbines, and diesel engines. There has been a lack of data which can serve as a basis for spray model development and validation. A major aim of the present investigation is to fill this gap. Experimental apparatus and techniques for studying the characteristics of fuel sprays are discussed, taking into account two-dimensional still photography, cinematography, holography, a laser diffraction particle sizer, and a laser anemometer. The considered instruments were used in a number of experiments, taking into account three different types of fuel spray. Attention is given to liquid fuel sprays, high pressure pulsed diesel sprays, and coal-water slurry sprays.

Piezoelectric Sol-Gel Composite Film Fabrication by Stencil Printing.

PubMed

Kaneko, Tsukasa; Iwata, Kazuki; Kobayashi, Makiko

2015-09-01

Piezoelectric films using sol-gel composites could be useful as ultrasonic transducers in various industrial fields. For sol-gel composite film fabrication, the spray coating technique has been used often because of its adaptability for various substrates. However, the spray technique requires multiple spray coating processes and heating processes and this is an issue of concern, especially for on-site fabrication in controlled areas. Stencil printing has been developed to solve this issue because this method can be used to fabricate thick sol-gel composite films with one coating process. In this study, PbTiO3 (PT)/Pb(Zr,Ti)O3 (PZT) films, PZT/PZT films, and Bi4Ti3O12 (BiT)/PZT films were fabricated by stencil printing, and PT/ PZT films were also fabricated using the spray technique. After fabrication, a thermal cycle test was performed for the samples to compare their ultrasonic performance. The sensitivity and signal-to-noise-ratio (SNR) of the ultrasonic response of PT/PZT fabricated by stencil printing were equivalent to those of PT/PZT fabricated by the spray technique, and better than those of other samples between room temperature and 300°C. Therefore, PT/PZT films fabricated by stencil printing could be a good candidate for nondestructive testing (NDT) ultrasonic transducers from room temperature to 300°C.

DOE Office of Scientific and Technical Information (OSTI.GOV)

None

During this time period, at WVU, we tried several methods to eliminate problems related to condensation of heavier products when reduced Mo-Ni-K/C materials were used as catalysts. We then resumed our kinetic study on the reduced Mo-Ni-K/C catalysts. We have also obtained same preliminary results in our attempts to analyze quantitatively the temperature-programmed reduction (TPR) spectra for C-supported Mo-based catalysts. We have completed the kinetic study for the sulfided Co-K-MoS /C catalyst. We have compared the results of methanol synthesis 2 using the membrane reactor with those using a simple plug-flow reactor. At UCC, the complete characterization of selected catalystsmore » has been completed. The results suggest that catalyst pretreatment under different reducing conditions yield different surface compositions and thus different catalytic reactivities.« less

Development of a Stochastically-driven, Forward Predictive Performance Model for PEMFCs

NASA Astrophysics Data System (ADS)

Harvey, David Benjamin Paul

A one-dimensional multi-scale coupled, transient, and mechanistic performance model for a PEMFC membrane electrode assembly has been developed. The model explicitly includes each of the 5 layers within a membrane electrode assembly and solves for the transport of charge, heat, mass, species, dissolved water, and liquid water. Key features of the model include the use of a multi-step implementation of the HOR reaction on the anode, agglomerate catalyst sub-models for both the anode and cathode catalyst layers, a unique approach that links the composition of the catalyst layer to key properties within the agglomerate model and the implementation of a stochastic input-based approach for component material properties. The model employs a new methodology for validation using statistically varying input parameters and statistically-based experimental performance data; this model represents the first stochastic input driven unit cell performance model. The stochastic input driven performance model was used to identify optimal ionomer content within the cathode catalyst layer, demonstrate the role of material variation in potential low performing MEA materials, provide explanation for the performance of low-Pt loaded MEAs, and investigate the validity of transient-sweep experimental diagnostic methods.

New insights into non-precious metal catalyst layer designs for proton exchange membrane fuel cells: Improving performance and stability

NASA Astrophysics Data System (ADS)

Banham, Dustin; Kishimoto, Takeaki; Sato, Tetsutaro; Kobayashi, Yoshikazu; Narizuka, Kumi; Ozaki, Jun-ichi; Zhou, Yingjie; Marquez, Emil; Bai, Kyoung; Ye, Siyu

2017-03-01

The activity of non-precious metal catalysts (NPMCs) has now reached a stage at which they can be considered as possible alternatives to Pt for some proton exchange membrane fuel cell (PEMFC) applications. However, despite significant efforts over the past 50 years on catalyst development, only limited studies have been performed on NPMC-based cathode catalyst layer (CCL) designs. In this work, an extensive ionomer study is performed to investigate the impact of ionomer equivalent weight on performance, which has uncovered two crucial findings. Firstly, it is demonstrated that beyond a critical CCL conductance, no further improvement in performance is observed. The procedure used to determine this critical conductance can be used by other researchers in this field to aid in their design of high performing NPMC-based CCLs. Secondly, it is shown that the stability of NPMC-based CCLs can be improved through the use of low equivalent weight ionomers. This represents a completely unexplored pathway for further stability improvements, and also provides new insights into the possible degradation mechanisms occurring in NPMC-based CCLs. These findings have broad implications on all future NPMC-based CCL designs.

Comparison of the decomposition characteristics of aromatic VOCs using an electron beam hybrid system

NASA Astrophysics Data System (ADS)

Son, Youn-Suk; Kim, Ki-Joon; Kim, Ji-Yong; Kim, Jo-Chun

2010-12-01

We applied a hybrid technique to assess the decomposition characteristics of ethylbenzene and toluene that annexed the catalyst technique with existing electron beam (EB) technology. The removal efficiency of ethylbenzene in the EB-catalyst hybrid turned out to be 30% greater than that of EB-only treatment. We concluded that ethylbenzene was decomposed more easily than toluene by EB irradiation. We compared the independent effects of the EB-catalyst hybrid and catalyst-only methods, and observed that the efficiency of the EB-catalyst hybrid demonstrated approximately 6% improvement for decomposing toluene and 20% improvement for decomposing ethylbenzene. The G-values for ethylbenzene increased with initial concentration and reactor type: for example, the G-values by reactor type at 2800 ppmC were 7.5-10.9 (EB-only) and 12.9-25.7 (EB-catalyst hybrid). We also observed a significant decrease in by-products as well as in the removal efficiencies associated with the EB-catalyst hybrid technique.

Mixing of an Airblast-atomized Fuel Spray Injected into a Crossflow of Air

NASA Technical Reports Server (NTRS)

Leong, May Y.; McDonell, Vincent G.; Samuelsen, G. Scott

2000-01-01

The injection of a spray of fuel droplets into a crossflow of air provides a means of rapidly mixing liquid fuel and air for combustion applications. Injecting the liquid as a spray reduces the mixing length needed to accommodate liquid breakup, while the transverse injection of the spray into the air stream takes advantage of the dynamic mixing induced by the jet-crossflow interaction. The structure of the spray, formed from a model plain-jet airblast atomizer, is investigated in order to determine and understand the factors leading to its dispersion. To attain this goal, the problem is divided into the following tasks which involve: (1) developing planar imaging techniques that visualize fuel and air distributions in the spray, (2) characterizing the airblast spray without a crossflow, and (3) characterizing the airblast spray upon injection into a crossflow. Geometric and operating conditions are varied in order to affect the atomization, penetration, and dispersion of the spray into the crossflow. The airblast spray is first characterized, using imaging techniques, as it issues into a quiescent environment. The spray breakup modes are classified in a liquid Reynolds number versus airblast Weber number regime chart. This work focuses on sprays formed by the "prompt" atomization mode, which induces a well-atomized and well-dispersed spray, and which also produces a two-lobed liquid distribution corresponding to the atomizing air passageways in the injector. The characterization of the spray jet injected into the crossflow reveals the different processes that control its dispersion. Correlations that describe the inner and outer boundaries of the spray jet are developed, using the definition of a two-phase momentum-flux ratio. Cross-sections of the liquid spray depict elliptically-shaped distributions, with the exception of the finely-atomized sprays which show kidney-shaped distributions reminiscent of those obtained in gaseous jet in crossflow systems. A droplet trajectory analysis overpredicts the liquid mass penetration, and indicates a need for a more rigorous model to account for the three-dimensional mixing field induced by the jet-crossflow interaction. Nonetheless, the general procedures and criteria that are outlined can be used to efficiently assess and compare the quality of sprays formed under different conditions.

Metal-catalyst-free carbohydrazide fuel cells with three-dimensional graphene anodes.

PubMed

Qi, Ji; Benipal, Neeva; Wang, Hui; Chadderdon, David J; Jiang, Yibo; Wei, Wei; Hu, Yun Hang; Li, Wenzhen

2015-04-13

As a potential solution to concerns on sustainable energy, the wide spread commercialization of fuel cell has long been hindered by limited reserves and relatively high costs of metal catalysts. 3D graphene, a carbon-only catalyst prepared by reduction of carbon monoxide with lithium oxide, is found to electrochemically catalyze carbohydrazide oxidation reaction efficiently. A prototype of a completely metal-catalyst-free anion exchange membrane fuel cell (AEMFC) with a 3D graphene anode catalyst and an N-doped CNT (N-CNT) cathode catalyst generate a peak power density of 24.9 mW cm(-2) . The average number of electrons electrochemically extracted from one carbohydrazide molecule is 4.9, indicating the existence of CN bond activation, which is a key factor contributing to high fuel utilization efficiency. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Spray drying formulation of amorphous solid dispersions.

PubMed

Singh, Abhishek; Van den Mooter, Guy

2016-05-01

Spray drying is a well-established manufacturing technique which can be used to formulate amorphous solid dispersions (ASDs) which is an effective strategy to deliver poorly water soluble drugs (PWSDs). However, the inherently complex nature of the spray drying process coupled with specific characteristics of ASDs makes it an interesting area to explore. Numerous diverse factors interact in an inter-dependent manner to determine the final product properties. This review discusses the basic background of ASDs, various formulation and process variables influencing the critical quality attributes (CQAs) of the ASDs and aspects of downstream processing. Also various aspects of spray drying such as instrumentation, thermodynamics, drying kinetics, particle formation process and scale-up challenges are included. Recent advances in the spray-based drying techniques are mentioned along with some future avenues where major research thrust is needed. Copyright © 2015 Elsevier B.V. All rights reserved.

Detailed investigation of a vaporising fuel spray. Part 1: Experimental investigation of time averaged spray

NASA Technical Reports Server (NTRS)

Yule, A. J.; Seng, C. A.; Boulderstone, R.; Ungut, A.; Felton, P. G.; Chigier, N. A.

1980-01-01

A laser tomographic light scattering technique provides rapid and accurate high resolution measurements of droplet sizes, concentrations, and vaporization. Measurements using a computer interfaced thermocouple are presented and it is found that the potential exists for separating gas and liquid temperature measurements and diagnosing local spray density by in situ analysis of the response characteristics of the thermocouple. The thermocouple technique provides a convenient means for measuring mean gas velocity in both hot and cold two phase flows. The experimental spray is axisymmetric and has carefully controlled initial and boundary conditions. The flow is designed to give relatively insignificant transfer of momentum and mass from spray to air flow. The effects of (1) size-dependent droplet dispersion by the turbulence, (2) the initial spatial segregation of droplet sizes during atomization, and (3) the interaction between droplets and coherent large eddies are diagnosed.

Metallization of bacterial cellulose for electrical and electronic device manufacture

DOEpatents

Evans, Barbara R.; O'Neill, Hugh M.; Jansen, Valerie Malyvanh; Woodward, Jonathan

2006-01-17

The employment of metallized bacterial cellulose in the construction of fuel cells and other electronic devices is disclosed. The fuel cell includes an electrolyte membrane comprising a membrane support structure comprising bacterial cellulose, an anode disposed on one side of the electrolyte membrane, and a cathode disposed on an opposite side of the electrolyte membrane. At least one of the anode and the cathode comprises an electrode support structure comprising bacterial cellulose, and a catalyst disposed in or on the electrode support structure.

Highly efficient transition metal and nitrogen co-doped carbide-derived carbon electrocatalysts for anion exchange membrane fuel cells

NASA Astrophysics Data System (ADS)

Ratso, Sander; Kruusenberg, Ivar; Käärik, Maike; Kook, Mati; Puust, Laurits; Saar, Rando; Leis, Jaan; Tammeveski, Kaido

2018-01-01

The search for an efficient electrocatalyst for oxygen reduction reaction (ORR) to replace platinum in fuel cell cathode materials is one of the hottest topics in electrocatalysis. Among the many non-noble metal catalysts, metal/nitrogen/carbon composites made by pyrolysis of cheap materials are the most promising with control over the porosity and final structure of the catalyst a crucial point. In this work we show a method of producing a highly active ORR catalyst in alkaline media with a controllable porous structure using titanium carbide derived carbon as a base structure and dicyandiamide along with FeCl3 or CoCl2 as the dopants. The resulting transition metal-nitrogen co-doped carbide derived carbon (M/N/CDC) catalyst is highly efficient for ORR electrocatalysis with the activity in 0.1 M KOH approaching that of commercial 46.1 wt.% Pt/C. The catalyst materials are also investigated by scanning electron microscopy, Raman spectroscopy and X-ray photoelectron spectroscopy to characterise the changes in morphology and composition causing the raise in electrochemical activity. MEA performance of M/N/CDC cathode materials in H2/O2 alkaline membrane fuel cell is tested with the highest power density reached being 80 mW cm-2 compared to 90 mW cm-2 for Pt/C.

PtCo Cathode Catalyst Morphological and Compositional Changes after PEM Fuel Cell Accelerated Stress Testing

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sneed, Brian T.; Cullen, David A.; Mukundan, R.

Development of Pt catalysts alloyed with transition metals has led to a new class of state-of-the-art electrocatalysts for oxygen reduction at the cathode of proton exchange membrane fuel cells; however, the durability of Pt-based alloy catalysts is challenged by poor structural and chemical stability. There is a need for better understanding of the morphological and compositional changes that occur to the catalyst under fuel cell operation. In this work, we report in-depth characterization results of a Pt-Co electrocatalyst incorporated in the cathode of membrane electrode assemblies, which were evaluated before and after accelerated stress tests designed specifically to enhance catalystmore » degradation. Electron microscopy, spectroscopy, and 3D electron tomography analyses of the Pt-Co nanoparticle structures suggest that the small- and intermediate-sized Pt-Co particles, which are typically Pt-rich in the fresh condition, undergo minimal morphological changes, whereas intermediate- and larger-sized Pt-Co nanoparticles that exhibit a porous “spongy” morphology and initially have a higher Co content, transform into hollowed-out shells, which is driven by continuous leaching of Co from the Pt-Co catalysts. We further show how these primary Pt-Co nanoparticle morphologies group toward a lower Co, larger size portion of the size vs. composition distribution, and provide details of their nanoscale morphological features.« less

Polybenzimidazole (PBI) functionalized nanographene as highly stable catalyst support for polymer Electrolyte membrane fuel cells (PEMFCs)

DOE PAGES

Xin, Le; Yang, Fan; Qiu, Yang; ...

2016-08-25

Nanoscale graphenes were used as cathode catalyst supports in proton exchange membrane fuel cells (PEMFCs). Surface-initiated polymerization that covalently bonds polybenzimidazole (PBI) polymer on the surface of graphene supports enables the uniform distribution of the Pt nanoparticles, as well as allows the sealing of the unterminated carbon bonds usually present on the edge of graphene from the chemical reduction of graphene oxide. The nanographene effectively shortens the length of channels and pores for O 2 diffusion/water dissipation and significantly increases the primary pore volume. Further addition of p-phenyl sulfonic functional graphitic carbon particles as spacers, increases the specific volume ofmore » the secondary pores and greatly improves O 2 mass transport within the catalyst layers. The developed composite cathode catalyst of Pt/PBI-nanographene (50 wt%) + SO 3H-graphitic carbon black demonstrates a higher beginning of life (BOL) PEMFC performance as compared to both Pt/PBI-nanographene (50 wt%) and Pt/PBI-graphene (50 wt%) + SO 3H-graphitic carbon black (GCB). Accelerated stress tests show excellent support durability compared to that of traditional Pt/Vulcan XC72 catalysts, when subjected to 10,000 cycles from 1.0 V to 1.5 V. As a result, this study suggests the promise of using PBI-nanographene + SO 3H-GCB hybrid supports in fuel cells to achieve the 2020 DOE targets for transportation applications.« less

3D Analysis of Fuel Cell Electrocatalyst Degradation on Alternate Carbon Supports.

PubMed

Sneed, Brian T; Cullen, David A; Reeves, Kimberly S; Dyck, Ondrej E; Langlois, David A; Mukundan, Rangachary; Borup, Rodney L; More, Karren L

2017-09-06

Understanding the mechanisms associated with Pt/C electrocatalyst degradation in proton exchange membrane fuel cell (PEMFC) cathodes is critical for the future development of higher-performing materials; however, there is a lack of information regarding Pt coarsening under PEMFC operating conditions within the cathode catalyst layer. We report a direct and quantitative 3D study of Pt dispersions on carbon supports (high surface area carbon (HSAC), Vulcan XC-72, and graphitized carbon) with varied surface areas, graphitic character, and Pt loadings ranging from 5 to 40 wt %. This is accomplished both before and after catalyst-cycling accelerated stress tests (ASTs) through observations of the cathode catalyst layer of membrane electrode assemblies. Electron tomography results show Pt nanoparticle agglomeration occurs predominantly at junctions and edges of aggregated graphitized carbon particles, leading to poor Pt dispersion in the as-prepared catalysts and increased coalescence during ASTs. Tomographic reconstructions of Pt/HSAC show much better initial Pt dispersions, less agglomeration, and less coarsening during ASTs in the cathode. However, a large loss of the electrochemically active surface area (ECSA) is still observed and is attributed to accelerated Pt dissolution and nanoparticle coalescence. Furthermore, a strong correlation between Pt particle/agglomerate size and measured ECSA is established and is proposed as a more useful metric than average crystallite size in predicting degradation behavior across different catalyst systems.

3D Analysis of Fuel Cell Electrocatalyst Degradation on Alternate Carbon Supports

DOE PAGES

Sneed, Brian T.; Cullen, David A.; Reeves, Kimberly S.; ...

2017-08-15

Understanding the mechanisms associated with Pt/C electrocatalyst degradation in proton exchange membrane fuel cell (PEMFC) cathodes is critical for the future development of higher-performing materials; however, there is a lack of information regarding Pt coarsening under PEMFC operating conditions within the cathode catalyst layer. We report a direct and quantitative 3D study of Pt dispersions on carbon supports (high surface area carbon (HSAC), Vulcan XC-72, and graphitized carbon) with varied surface areas, graphitic character, and Pt loadings ranging from 5 to 40 wt %. This is accomplished both before and after catalyst-cycling accelerated stress tests (ASTs) through observations of themore » cathode catalyst layer of membrane electrode assemblies. Electron tomography results show Pt nanoparticle agglomeration occurs predominantly at junctions and edges of aggregated graphitized carbon particles, leading to poor Pt dispersion in the as-prepared catalysts and increased coalescence during ASTs. Tomographic reconstructions of Pt/HSAC show much better initial Pt dispersions, less agglomeration, and less coarsening during ASTs in the cathode. However, a large loss of the electrochemically active surface area (ECSA) is still observed and is attributed to accelerated Pt dissolution and nanoparticle coalescence. Moreover, a strong correlation between Pt particle/agglomerate size and measured ECSA is established and is proposed as a more useful metric than average crystallite size in predicting degradation behavior across different catalyst systems.« less

PtCo Cathode Catalyst Morphological and Compositional Changes after PEM Fuel Cell Accelerated Stress Testing

DOE PAGES

Sneed, Brian T.; Cullen, David A.; Mukundan, R.; ...

2018-03-01

Development of Pt catalysts alloyed with transition metals has led to a new class of state-of-the-art electrocatalysts for oxygen reduction at the cathode of proton exchange membrane fuel cells; however, the durability of Pt-based alloy catalysts is challenged by poor structural and chemical stability. There is a need for better understanding of the morphological and compositional changes that occur to the catalyst under fuel cell operation. In this work, we report in-depth characterization results of a Pt-Co electrocatalyst incorporated in the cathode of membrane electrode assemblies, which were evaluated before and after accelerated stress tests designed specifically to enhance catalystmore » degradation. Electron microscopy, spectroscopy, and 3D electron tomography analyses of the Pt-Co nanoparticle structures suggest that the small- and intermediate-sized Pt-Co particles, which are typically Pt-rich in the fresh condition, undergo minimal morphological changes, whereas intermediate- and larger-sized Pt-Co nanoparticles that exhibit a porous “spongy” morphology and initially have a higher Co content, transform into hollowed-out shells, which is driven by continuous leaching of Co from the Pt-Co catalysts. We further show how these primary Pt-Co nanoparticle morphologies group toward a lower Co, larger size portion of the size vs. composition distribution, and provide details of their nanoscale morphological features.« less

3D Analysis of Fuel Cell Electrocatalyst Degradation on Alternate Carbon Supports

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sneed, Brian T.; Cullen, David A.; Reeves, Kimberly S.

Understanding the mechanisms associated with Pt/C electrocatalyst degradation in proton exchange membrane fuel cell (PEMFC) cathodes is critical for the future development of higher-performing materials; however, there is a lack of information regarding Pt coarsening under PEMFC operating conditions within the cathode catalyst layer. We report a direct and quantitative 3D study of Pt dispersions on carbon supports (high surface area carbon (HSAC), Vulcan XC-72, and graphitized carbon) with varied surface areas, graphitic character, and Pt loadings ranging from 5 to 40 wt %. This is accomplished both before and after catalyst-cycling accelerated stress tests (ASTs) through observations of themore » cathode catalyst layer of membrane electrode assemblies. Electron tomography results show Pt nanoparticle agglomeration occurs predominantly at junctions and edges of aggregated graphitized carbon particles, leading to poor Pt dispersion in the as-prepared catalysts and increased coalescence during ASTs. Tomographic reconstructions of Pt/HSAC show much better initial Pt dispersions, less agglomeration, and less coarsening during ASTs in the cathode. However, a large loss of the electrochemically active surface area (ECSA) is still observed and is attributed to accelerated Pt dissolution and nanoparticle coalescence. Moreover, a strong correlation between Pt particle/agglomerate size and measured ECSA is established and is proposed as a more useful metric than average crystallite size in predicting degradation behavior across different catalyst systems.« less

Synchronized droplet size measurements for Coal-Water-Slurry (CWS) diesel sprays of an electronically-controlled fuel injection system

NASA Astrophysics Data System (ADS)

Kihm, K. D.; Terracina, D. P.; Payne, S. E.; Caton, J. A.

Experiments were completed to study intermittent coal-water slurry (CWS) fuel sprays injected from an electronically-controlled accumulator injector system. A laser diffraction particle analyzing (LDPA) technique was used to measure the spray diameters (Sauter mean diameter, SMD) assuming the Rosin-Rammler two parameter model. In order to ensure an accurate synchronization of the measurement with the intermittent sprays, a new synchronization technique was developed using the light extinction signal as a triggering source for the data taking initiation. This technique allowed measurement of SMD's near the spray tip where the light extinction was low and the data were free from the multiscattering bias. Coal-water slurry fuel with 50% coal loading in mass containing 5 (mu)m mass median diameter coal particulates was considered. Injection pressures ranging from 28 to 110 MPa, two different nozzle orifice diameters, 0.2 ad 0.4 mm, and four axial measurement locations from 60 to 120 mm from the nozzle orifice were studied. Measurements were made for pressurized (2.0 MPa in gauge) and for ambient chamber conditions. The spray SMD showed an increase with the distance of the axial measurement location and with the ambient gas density, and showed a decrease with increasing injection pressure. A correlation of the Sauter mean diameter with the injection conditions was determined. The results were also compared with previous SMD correlations that were available only for diesel fuel sprays.

Cold spray nozzle design

DOEpatents

Haynes, Jeffrey D [Stuart, FL; Sanders, Stuart A [Palm Beach Gardens, FL

2009-06-09

A nozzle for use in a cold spray technique is described. The nozzle has a passageway for spraying a powder material, the passageway having a converging section and a diverging section, and at least the diverging section being formed from polybenzimidazole. In one embodiment of the nozzle, the converging section is also formed from polybenzimidazole.

Fuel cell catalyst layers containing short-side-chain perfluorosulfonic acid ionomers

NASA Astrophysics Data System (ADS)

Peron, Jennifer; Edwards, Dave; Haldane, Mark; Luo, Xiaoyan; Zhang, Yongming; Holdcroft, Steven; Shi, Zhiqing

Porous catalyst layers (CLs) containing short-side-chain (SSC) perfluorosulfonic acid (PFSA) ionomers of different ion exchange capacity (IEC: 1.3, 1.4 and 1.5 meq g -1) were deposited onto Nafion 211 to form catalyst-coated membranes. The porosity of SSC-PFSA-based CLs is larger than Nafion-CL analogues. CLs incorporating SSC ionomer extend the current density of fuel cell polarization curves at elevated temperature and lower relative humidity compared to those based on long-side chain PFSA (e.g., Nafion)-based CLs. Fuel cell polarization performance was greatly improved at 110 °C and 30% relative humidity (RH) when SSC PFSI was incorporated into the catalyst layer.

From bio-mineralisation to fuel cells: biomanufacture of Pt and Pd nanocrystals for fuel cell electrode catalyst.

PubMed

Yong, P; Paterson-Beedle, M; Mikheenko, I P; Macaskie, L E

2007-04-01

Biosynthesis of nano-scale platinum and palladium was achieved via enzymatically-mediated deposition of metal ions from solution. The bio-accumulated Pt(0) and Pd(0) crystals were dried, applied onto carbon paper and tested as anodes in a polymer electrolyte membrane (PEM) fuel cell for power production. Up to 100% and 81% of the maximum power generation was achieved by the bio-Pt and bio-Pd catalysts, respectively, compared to commercial fuel cell grade Pt catalyst. Hence, biomineralisation could pave the way for economical production of fuel cell catalysts since previous studies have shown that precious metals can be biorecovered from wastes into catalytically active bionanomaterials.

A versatile in situ spectroscopic cell for fluorescence/transmission EXAFS and X-ray diffraction of heterogeneous catalysts in gas and liquid phase.

PubMed

Hannemann, Stefan; Casapu, Maria; Grunwaldt, Jan Dierk; Haider, Peter; Trüssel, Philippe; Baiker, Alfons; Welter, Edmund

2007-07-01

A new spectroscopic cell suitable for the analysis of heterogeneous catalysts by fluorescence EXAFS (extended X-ray absorption fine structure), transmission EXAFS and X-ray diffraction during in situ treatments and during catalysis is described. Both gas-phase and liquid-phase reactions can be investigated combined with on-line product analysis performed either by mass spectrometry or infrared spectroscopy. The set-up allows measurements from liquid-nitrogen temperature to 973 K. The catalysts are loaded preferentially as powders, but also as self-supporting wafers. The reaction cell was tested in various case studies demonstrating its flexibility and its wide applicability from model studies at liquid-nitrogen temperature to operando studies under realistic reaction conditions. Examples include structural studies during (i) the reduction of alumina-supported noble metal particles prepared by flame-spray pyrolysis and analysis of alloying in bimetallic noble metal particles (0.1%Pt-0.1%Pd/Al(2)O(3), 0.1%Pt-0.1%Ru/Al(2)O(3), 0.1%Pt-0.1%Rh/Al(2)O(3), 0.1%Au-0.1%Pd/Al(2)O(3)), (ii) reactivation of aged 0.8%Pt-16%BaO-CeO(2) NO(x) storage-reduction catalysts including the NO(x) storage/reduction cycle, and (iii) alcohol oxidation over gold catalysts (0.6%Au-20%CuO-CeO(2)).

Engineering a new class of thermal spray nano-based microstructures from agglomerated nanostructured particles, suspensions and solutions: an invited review

NASA Astrophysics Data System (ADS)

Fauchais, P.; Montavon, G.; Lima, R. S.; Marple, B. R.

2011-03-01

From the pioneering works of McPherson in 1973 who identified nanometre-sized features in thermal spray conventional alumina coatings (using sprayed particles in the tens of micrometres size range) to the most recent and most advanced work aimed at manufacturing nanostructured coatings from nanometre-sized feedstock particles, the thermal spray community has been involved with nanometre-sized features and feedstock for more than 30 years. Both the development of feedstock (especially through cryo-milling, and processes able to manufacture coatings structured at the sub-micrometre or nanometre sizes, such as micrometre-sized agglomerates made of nanometre-sized particles for feedstock) and the emergence of thermal spray processes such as suspension and liquid precursor thermal spray techniques have been driven by the need to manufacture coatings with enhanced properties. These techniques result in two different types of coatings: on the one hand, those with a so-called bimodal structure having nanometre-sized zones embedded within micrometre ones, for which the spray process is similar to that of conventional coatings and on the other hand, sub-micrometre or nanostructured coatings achieved by suspension or solution spraying. Compared with suspension spraying, solution precursor spraying uses molecularly mixed precursors as liquids, avoiding a separate processing route for the preparation of powders and enabling the synthesis of a wide range of oxide powders and coatings. Such coatings are intended for use in various applications ranging from improved thermal barrier layers and wear-resistant surfaces to thin solid electrolytes for solid oxide fuel cell systems, among other numerous applications. Meanwhile these processes are more complex to operate since they are more sensitive to parameter variations compared with conventional thermal spray processes. Progress in this area has resulted from the unique combination of modelling activities, the evolution of diagnostic tools and strategies, and experimental advances that have enabled the development of a wide range of coating structures exhibiting in numerous cases unique properties. Several examples are detailed. In this paper the following aspects are presented successively (i) the two spray techniques used for manufacturing such coatings: thermal plasma and HVOF, (ii) sensors developed for in-flight diagnostics of micrometre-sized particles and the interaction of a liquid and hot gas flow, (iii) three spray processes: conventional spraying using micrometre-sized agglomerates of nanometre-sized particles, suspension spraying and solution spraying and (iv) the emerging issues resulting from the specific structures of these materials, particularly the characterization of these coatings and (v) the potential industrial applications. Further advances require the scientific and industrial communities to undertake new research and development activities to address, understand and control the complex mechanisms occurring, in particular, thermal flow—liquid drops or stream interactions when considering suspension and liquid precursor thermal spray techniques. Work is still needed to develop new measurement devices to diagnose in-flight droplets or particles below 2 µm average diameter and to validate that the assumptions made for liquid-hot gas interactions. Efforts are also required to further develop some of the characterization protocols suitable to address the specificities of such nanostructured coatings, as some existing 'conventional' protocols usually implemented on thermal spray coatings are not suitable anymore, in particular to address the void network architectures from which numerous coatings properties are derived.

Highly Active and Stable Pt–Pd Alloy Catalysts Synthesized by Room‐Temperature Electron Reduction for Oxygen Reduction Reaction

PubMed Central

Wang, Wei; Wang, Zongyuan; Wang, Jiajun; Zhong, Chuan‐Jian

2017-01-01

Carbon‐supported platinum (Pt) and palladium (Pd) alloy catalyst has become a promising alternative electrocatalyst for oxygen reduction reaction (ORR) in proton exchange membrane fuel cells. In this work, the synthesis of highly active and stable carbon‐supported Pt–Pd alloy catalysts is reported with a room‐temperature electron reduction method. The alloy nanoparticles thus prepared show a particle size around 2.6 nm and a core–shell structure with Pt as the shell. With this structure, the breaking of O–O bands and desorption of OH are both promoted in electrocatalysis of ORR. In comparison with the commercial Pt/C catalyst prepared by conventional method, the mass activity of the Pt–Pd/C catalyst for ORR is shown to increase by a factor of ≈4. After 10 000‐cycle durability test, the Pt–Pd/C catalyst is shown to retain 96.5% of the mass activity, which is much more stable than that of the commercial Pt/C catalyst. PMID:28435780

Fluidizable particulate materials and methods of making same

DOEpatents

Gupta, Raghubir P.

1999-01-01

The invention provides fluidizable, substantially spherical particulate material of improved attrition resistance having an average particle size from about 100 to about 400 microns useful as sorbents, catalysts, catalytic supports, specialty ceramics or the like. The particles are prepared by spray drying a slurry comprising inorganic starting materials and an organic binder. Exemplary inorganic starting materials include mixtures of zinc oxide with titanium dioxide, or with iron oxide, alumina or the like. Exemplary organic binders include polyvinyl alcohol, hydroxypropylemethyl cellulose, polyvinyl acetate and the like. The spray dried particles are heat treated at a first temperature wherein organic binder material is removed to thereby provide a porous structure to the particles, and thereafter the particles are calcined at a higher temperature to cause reaction of the inorganic starting materials and to thereby form the final inorganic particulate material.

Experimental Polyvinyl Chloride (PVC) Roofing: Field Test Results.

DTIC Science & Technology

1987-02-01

construction. These were the single-ply membranes of the ethylene-propylene-diene monomer ( EPDM ) and polyvinyl chloride (PVC) types, and the sprayed-in-place...polyurethane foam (PUF) with an elastomeric coating. EPDM and PUF roofs were constructed in 19802 and the PVC roofs were completed during summer 1983...faced isocyanu- rate foam board in two layers . Roofing systems were installed loose-laid and ballasted. Specific membrane materials were Plymouth

Activity inhibition and its mitigation in high temperature proton exchange membrane fuel cells: The role of phosphoric acid, ammonium trifluoromethanesulfonate, and polyvinylidene difluoride

NASA Astrophysics Data System (ADS)

Holst-Olesen, Kaspar; Nesselberger, Markus; Perchthaler, Markus; Hacker, Viktor; Arenz, Matthias

2014-12-01

In the presented work we systematically study the influence of phosphoric acid, ammonium trifluoromethanesulfonate (ATFMS), and polyvinylidene difluoride (PVDF) on the oxygen reduction reaction (ORR) activity of carbon supported, Pt based catalysts. The influence of phosphoric acid is investigated in a mixed solution of perchloric acid with small amounts of phosphoric acid added. Thin-film rotating disk electrode (TF-RDE) measurements show that such a mixed electrolyte is advantageous as the oxygen reduction reaction (ORR) is inhibited without influencing the oxygen solubility in the electrolyte. In contrast to previous reports it is seen when investigating additives that ATFMS acts as a catalyst poison; whereas the results provide evidence of a better performance in case of the PVDF incorporated catalysts as compared to reference samples without PVDF. The technological relevance of the PVDF improvements and its stability over prolonged time was validated by membrane electrode assembly (MEA) tests.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gottesfeld, Shimshon; Dekel, Dario R.; Page, Miles

The anion exchange membrane fuel cell (AEMFC) is an attractive alternative to acidic proton exchange membrane fuel cells, which to date have required platinum-based catalysts, as well as acid-tolerant stack hardware. The AEMFC could use non-platinum-group metal catalysts and less expensive metal hardware thanks to the high pH of the electrolyte. Over the last decade, substantial progress has been made in improving the performance and durability of the AEMFC through the development of new materials and the optimization of system design and operation conditions. Here in this perspective article, we describe the current status of AEMFCs as having reached beginningmore » of life performance very close to that of PEMFCs when using ultra-low loadings of Pt, while advancing towards operation on non-platinum-group metal catalysts alone. In the latter sections, we identify the remaining technical challenges, which require further research and development, focusing on the materials and operational factors that critically impact AEMFC performance and/or durability. Finally, these perspectives may provide useful insights for the development of next-generation of AEMFCs.« less

Erythrocyte-like hollow carbon capsules and their application in proton exchange membrane fuel cells.

PubMed

Kim, Jung Ho; Yu, Jong-Sung

2010-12-14

Hierarchical nanostructured erythrocyte-like hollow carbon (EHC) with a hollow hemispherical macroporous core of ca. 230 nm in diameter and 30-40 nm thick mesoporous shell was synthesized and explored as a cathode catalyst support in a proton exchange membrane fuel cell (PEMFC). The morphology control of EHC was successfully achieved using solid core/mesoporous shell (SCMS) silica template and different styrene/furfuryl alcohol mixture compositions by a nanocasting method. The EHC-supported Pt (20 wt%) cathodes prepared have demonstrated markedly enhanced catalytic activity towards oxygen reduction reactions (ORRs) and greatly improved PEMFC polarization performance compared to carbon black Vulcan XC-72 (VC)-supported ones, probably due to the superb structural characteristics of the EHC such as uniform size, well-developed porosity, large specific surface area and pore volume. In particular, Pt/EHC cathodes exhibited ca. 30-60% higher ORR activity than a commercial Johnson Matthey Pt catalyst at a low catalyst loading of 0.2 mg Pt cm(-2).

Synthesis and characterization of high performing Fe-N-C catalyst for oxygen reduction reaction (ORR) in Alkaline Exchange Membrane Fuel Cells

NASA Astrophysics Data System (ADS)

Hossen, Md Mosaddek; Artyushkova, Kateryna; Atanassov, Plamen; Serov, Alexey

2018-01-01

In this article, three different Fe-N-C oxygen reduction reaction (ORR) catalysts derived from different organic molecules i.e. Fe-NMG, Fe-NMP, Fe-MBZ have been synthesized, characterized by physical-chemical methods and studied in the reaction of oxygen reduction (ORR). It is found that Fe-NMG shows higher ORR performance than Fe-NMP and Fe-MBZ, by both rotating ring disk electrode (RRDE) and fuel cell tests. From characterization and surface analysis, it can be explained that the presence of higher amount of surface oxides and pyridinic nitrogen is the main reason for better performance towards ORR in alkaline media. To achieve the highest performance in alkaline exchange membrane fuel cell (AEMFC), the optimization of catalyst layer composition using various concentrations of ionomer (Tokuyama, AS4) was performed. At the optimum cathode layer configuration utilizing Fe-NMG produces the peak power density of 218 mWcm-2, which is one of the highest values presented in the open literature.

Synthesizing 2D MoS2 Nanofins on carbon nanospheres as catalyst support for Proton Exchange Membrane Fuel Cells.

PubMed

Hu, Yan; Chua, Daniel H C

2016-06-15

Highly dense 2D MoS2 fin-like nanostructures on carbon nanospheres were fabricated and formed the main catalyst support structure in the oxygen reduction reaction (ORR) for polymer electrolyte membrane (PEM) fuel cells. These nanofins were observed growing perpendicular to the carbon nanosphere surface in random orientations and high resolution transmission electron microscope confirmed 2D layers. The PEM fuel cell test showed enhanced electrochemical activity with good stability, generating over 8.5 W.mgPt(-1) as compared to standard carbon black of 7.4 W.mgPt(-1) under normal operating conditions. Electrochemical Impedance Spectroscopy confirmed that the performance improvement is highly due to the excellent water management of the MoS2 lamellar network, which facilitates water retention at low current density and flood prevention at high current density. Reliability test further demonstrated that these nanofins are highly stable in the electrochemical reaction and is an excellent ORR catalyst support.

Synthesizing 2D MoS2 Nanofins on carbon nanospheres as catalyst support for Proton Exchange Membrane Fuel Cells

PubMed Central

Hu, Yan; Chua, Daniel H. C.

2016-01-01

Highly dense 2D MoS2 fin-like nanostructures on carbon nanospheres were fabricated and formed the main catalyst support structure in the oxygen reduction reaction (ORR) for polymer electrolyte membrane (PEM) fuel cells. These nanofins were observed growing perpendicular to the carbon nanosphere surface in random orientations and high resolution transmission electron microscope confirmed 2D layers. The PEM fuel cell test showed enhanced electrochemical activity with good stability, generating over 8.5 W.mgPt−1 as compared to standard carbon black of 7.4 W.mgPt−1 under normal operating conditions. Electrochemical Impedance Spectroscopy confirmed that the performance improvement is highly due to the excellent water management of the MoS2 lamellar network, which facilitates water retention at low current density and flood prevention at high current density. Reliability test further demonstrated that these nanofins are highly stable in the electrochemical reaction and is an excellent ORR catalyst support. PMID:27302135

Electrochemical investigation of stainless steel corrosion in a proton exchange membrane electrolyzer cell

DOE PAGES

Mo, Jingke; Steen, Stuart M.; Zhang, Feng-Yuan; ...

2015-08-05

The lack of a fundamental understanding of the corrosion mechanisms in the electrochemical environments of proton exchange membrane (PEM) electrolyzer and/or fuel cells (ECs/FCs) has seriously hindered the improvement of performance and efficiency of PEM ECs/FCs. In this study, a stainless steel mesh was purposely used as an anode gas diffusion layer that was intentionally operated with high positive potentials under harsh oxidative environments in a PEMEC to study the corrosion mechanism of metal migration. A significant amount of iron and nickel cations were determined to transport through the anode catalyst layer, the PEM and the cathode catalyst layer duringmore » the PEMEC operation. The formation/deposition of iron oxide and nickel oxide on the carbon paper gas diffusion layer at the cathode side is first revealed by both scanning electron microscope and X-ray diffraction. The results indicate the corrosion elements of iron and nickel are transported from anode to cathode through the catalyst-coated membrane, and deposited on carbon fibers as oxides. This phenomenon could also open a new corrosion-based processing approach to potentially fabricate multifunctional oxide structures on carbon fiber devices. This study has demonstrated a new accelerated test method for investigating the corrosion and durability of metallic materials as well.« less

Electrochemical investigation of stainless steel corrosion in a proton exchange membrane electrolyzer cell

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mo, Jingke; Steen, Stuart M.; Zhang, Feng-Yuan

The lack of a fundamental understanding of the corrosion mechanisms in the electrochemical environments of proton exchange membrane (PEM) electrolyzer and/or fuel cells (ECs/FCs) has seriously hindered the improvement of performance and efficiency of PEM ECs/FCs. In this study, a stainless steel mesh was purposely used as an anode gas diffusion layer that was intentionally operated with high positive potentials under harsh oxidative environments in a PEMEC to study the corrosion mechanism of metal migration. A significant amount of iron and nickel cations were determined to transport through the anode catalyst layer, the PEM and the cathode catalyst layer duringmore » the PEMEC operation. The formation/deposition of iron oxide and nickel oxide on the carbon paper gas diffusion layer at the cathode side is first revealed by both scanning electron microscope and X-ray diffraction. The results indicate the corrosion elements of iron and nickel are transported from anode to cathode through the catalyst-coated membrane, and deposited on carbon fibers as oxides. This phenomenon could also open a new corrosion-based processing approach to potentially fabricate multifunctional oxide structures on carbon fiber devices. This study has demonstrated a new accelerated test method for investigating the corrosion and durability of metallic materials as well.« less

Microscale X-ray tomographic investigation of the interfacial morphology between the catalyst and micro porous layers in proton exchange membrane fuel cells

NASA Astrophysics Data System (ADS)

Prass, Sebastian; Hasanpour, Sadegh; Sow, Pradeep Kumar; Phillion, André B.; Mérida, Walter

2016-07-01

The interfacial morphology between the catalyst layer (CL) and micro porous layer (MPL) influences the performance of proton exchange membrane fuel cells (PEMFCs). Here we report a direct method to investigate the CL-MPL interfacial morphology of stacked and compressed gas diffusion layer (GDL with MPL)-catalyst coated membrane (CCM) assemblies. The area, origin and dimensions of interfacial gaps are studied with high-resolution X-ray micro computed tomography (X-μCT). The projected gap area (fraction of the CL-MPL interface separated by gaps) is higher for GDL-CCM assemblies with large differences in the surface roughness between CL and MPL but reduces with increasing compression and similarity in roughness. Relatively large continuous gaps are found in proximity to cracks in the MPL. These are hypothesized to form due to the presence of large pores on the surface of the GDL. Smaller gaps are induced by the surface roughness features throughout the CL-MPL interface. By modification of the pore sizes on the GDL surface serving as substrate for the MPL, the number and dimension of MPL crack induced gaps can be manipulated. Moreover, adjusting the CL and MPL surface roughness parameters to achieve similar orders of roughness can improve the surface mating characteristics of these two components.

Combination of photocatalytic and membrane distillation hybrid processes for reactive dyes treatment.

PubMed

Yatmaz, H Cengiz; Dizge, Nadir; Kurt, Merve Sezen

2017-11-01

In this study, the degradation of azo dye solutions (Reactive Red 180 and Reactive Orange 16) of textile industry wastewater was investigated for using innovative hybrid process of photocatalytic and membrane distillation (MD) processes. Photocatalytic oxidation was conducted with semiconductor catalysts (ZnO and TiO2) and their mixture under UVA and UVC irradiation. More effective results were obtained under UVA at the initial stages of the reactions for both dye solutions. ZnO and TiO2 catalysts have given similar efficient results, but results with ZnO were better at initial stages. For the next stage, hybrid design of MD and photocatalytic processes was performed sequentially. Initially, the photocatalytic process was conducted for at least 1 h at initial values of 100 mg/L RR-180 dye solutions and 1 g/L ZnO catalyst loading under UVA irradiation and then treated solution was run through the distillation module at different temperatures (30°C and 40°C) and flow rates (210, 425, and 665 mL/min). Three types of membranes (polypropylene, polytetrafluoroethylene, and polyvinylidene fluoride) with different pore sizes (0.45 and 0.22 μm) were used in the module. Increasing temperature on the side of treated solution and decreasing the temperature on the other side has increased the distillate efficiency.

High Temperature Polymers for use in Fuel Cells

NASA Technical Reports Server (NTRS)

Peplowski, Katherine M.

2004-01-01

NASA Glenn Research Center (GRC) is currently working on polymers for fuel cell and lithium battery applications. The desire for more efficient, higher power density, and a lower environmental impact power sources has led to interest in proton exchanges membrane fuels cells (PEMFC) and lithium batteries. A PEMFC has many advantages as a power source. The fuel cell uses oxygen and hydrogen as reactants. The resulting products are electricity, heat, and water. The PEMFC consists of electrodes with a catalyst, and an electrolyte. The electrolyte is an ion-conducting polymer that transports protons from the anode to the cathode. Typically, a PEMFC is operated at a temperature of about 80 C. There is intense interest in developing a fuel cell membrane that can operate at higher temperatures in the range of 80 C- 120 C. Operating the he1 cell at higher temperatures increases the kinetics of the fuel cell reaction as well as decreasing the susceptibility of the catalyst to be poisoned by impurities. Currently, Nafion made by Dupont is the most widely used polymer membrane in PEMFC. Nafion does not function well above 80 C due to a significant decrease in the conductivity of the membrane from a loss of hydration. In addition to the loss of conductivity at high temperatures, the long term stability and relatively high cost of Nafion have stimulated many researches to find a substitute for Nafion. Lithium ion batteries are popular for use in portable electronic devices, such as laptop computers and mobile phones. The high power density of lithium batteries makes them ideal for the high power demand of today s advanced electronics. NASA is developing a solid polymer electrolyte that can be used for lithium batteries. Solid polymer electrolytes have many advantages over the current gel or liquid based systems that are used currently. Among these advantages are the potential for increased power density and design flexibility. Automobiles, computers, and cell phones require highly efficient power density for lowering emissions and meeting increasing consumer demands. Many of the solutions can be provided by proton exchange membrane fuel cells and lithium batteries. NASA Glenn Research Center has recognized this need, and is presently engaged in a solution. The goals for the summer include mastering synthesis techniques, understanding the reactions occurring during the synthesis, and characterizing the resulting polymer membranes using NMR, DSC, and TGA for the PEMFC and lithium batteries.

The Pharmacokinetics of Atomized Lidocaine Administered via the Trachea: A Randomized Trial.

PubMed

Takaenoki, Yumiko; Masui, Kenichi; Oda, Yutaka; Kazama, Tomiei

2016-07-01

Under emergent conditions, endotracheal drug administration may be an effective method of delivering emergency drugs. A common technique is to administer these drugs using a nonatomized spray. Atomized drug delivery may be an attractive alternative to nonatomized delivery because atomized particles are small, cover a large surface area, and may better adhere to endotracheal membrane resulting in more effective drug absorption. In this study, we compared the pharmacokinetic profile of lidocaine administered into the trachea using an atomized or a nonatomized technique. Twenty patients were anesthetized using propofol and remifentanil. Ten minutes after rocuronium was administered, patients received 4% lidocaine (2 mg/kg) intratracheally over 2 seconds before tracheal intubation. Ten patients received atomized lidocaine using a mucosal atomization device, and the other 10 patients received nonatomized lidocaine using a traditional spray tube. Arterial lidocaine plasma concentrations were measured before; at 1, 3, 5, 7, 10, 15, 20, 30, 45, and 60 minutes; and then every 60 minutes after the administration of lidocaine until the end of the operation. We developed a pharmacokinetic model to examine whether bioavailability or absorption rate was different between atomized versus nonatomized lidocaine administration. The total body clearance was fixed at a published value to determine the bioavailability. Peak plasma concentrations were larger using the mucosal atomization device (median [range]: 1.9 [1.4-3.2] μg/mL) than the spray tube (1.1 [0.6-2.0] μg/mL; P = 0.0021). Our pharmacokinetic model estimated a difference of bioavailability between the atomized and the nonatomized lidocaine (0.801 and 0.559 respectively, P = 0.0005), whereas our model estimated no difference in the absorption rate constant (0.00688/min). Our results suggest that when using atomized delivery of lidocaine, less drug is required to achieve a near equivalent plasma lidocaine concentration. Atomized drug administration may be a more efficient method for endotracheal drug administration.

Materials Challenges for Automotive PEM Fuel Cells

NASA Astrophysics Data System (ADS)

Gasteiger, Hubert

2004-03-01

Over the past few years, significant R efforts aimed at meeting the challenging cost and performance targets required for the use of Polymer Electrolyte Membrane (PEM) fuel cells in automotive applications. Besides engineering advances in bipolar plate materials and design, the optimization of membrane-electrode assemblies (MEAs) was an important enabler in reducing the cost and performance gaps towards commercial viability for the automotive market. On the one hand, platinum loadings were reduced from several mgPt/cm2MEA [1] to values of 0.5-0.6 mgPt/cm2MEA in current applications and loadings as low as 0.25 mgPt/cm2MEA have been demonstrated on the research level [2]. On the other hand, implementation of thin membranes (20-30 micrometer) [3, 4] as well as improvements in diffusion medium materials, essentially doubled the achievable power density of MEAs to ca. 0.9 W/cm2MEA (at 0.65 V) [5], thereby not only reducing the size of a PEMFC fuel cell system, but also reducing its overall materials cost (controlled to a large extent by membrane and Pt-catalyst cost). While this demonstrated a clear path towards automotive applications, a renewed focus of R efforts is now required to develop materials and fundamental materials understanding to assure long-term durability of PEM fuel cells. This presentation therefore will discuss the state-of-the-art knowledge of catalyst, catalyst-support, and membrane degradation mechanisms. In the area of Pt-catalysts, experience with phosphoric acid fuel cells (PAFCs) has shown that platinum sintering leads to long-term performance losses [6]. While this is less critical at the lower PEMFC operating temperatures (<100C) compared to PAFCs (>200C), very little is known about the dependence of Pt-sintering on temperature, cell voltage, and catalyst type (i.e., Pt versus Pt-alloys) and will be discussed here. Similarly, carbon-support corrosion can contribute significantly to voltage degradation in PAFCs [7], and even in the PEMFC environment more corrosion-resistant support materials (e.g., graphitized carbons) are desirable. While thin polymer electrolyte membranes (20-30 micrometer) enable high power density operation, the requirements on their chemical and mechanical stability are significantly more demanding compared to the thick membranes (100-200 micrometer) used in the past [1]. While the currently used perfluoro-sulfonicacid (PFSA) membranes are chemically very stable, they are known to degrade in the fuel cell environment [4] via peroxyl-radical attack, strongly enhanced in the presence of iron [8]. While the exact degradation mechanism is actively investigated, its understanding is clearly required to improve the chemical stability of PFSA's. Similarly, very little is known about the mechanical properties of polymer electrolyte membranes and critical issues will be discussed. References: 1. Strasser, K.; ``H2/O2 PEM Fuel Cell Module for an Air-Independent Propulsion System in a Submarine''; in: Handbook of Fuel Cells Fundamentals, Technology and Applications; Vielstich, W.; Lamm, A.; Gasteiger, H. A. (Eds.); John Wiley & Sons (Chichester, UK): volume 4, chapter 88, 2003, pp. 1201-1214. 2. Gasteiger, H. A.; Panels, J. E.; Yan, S. G.; J. Power Sources in press. 3. Gasteiger, H. A.; Gu, W.; Makharia, R.; Mathias, M. F.; Sompalli, S.; ``Beginning-of-Life MEA Performance: Efficiency Loss Contributions''; in: Handbook of Fuel Cells Fundamentals, Technology and Applications; Vielstich, W.; Lamm, A.; Gasteiger, H. A. (Eds.); John Wiley & Sons (Chichester, UK): volume 3, chapter 46, 2003, pp. 593-610. 4. Cleghorn, S.; Kolde, J.; Liu, W.; ``Catalyst-Coated Composite Membranes''; in: Handbook of Fuel Cells - Fundamentals, Technology and Applications; Vielstich, W.; Lamm, A.; Gasteiger, H. A. (Eds.); John Wiley & Sons (Chichester, UK): volume 3, chapter 44, 2003, pp. 566-575. 5. Mathias, M. F.; Gasteiger, H. A.; Fundamental Research and Development Challenges in Polymer Electrolyte Fuel Cell Technology; in Proceedings of the Proton Conducting Membrane Fuel Cells III Symposium; The Electrochemical Society: 2002, in press. 6. Landsman, D. A.; Luczak, F. J.; ``Catalyst Studies and Coating Technologies''; in: Handbook of Fuel Cells Fundamentals, Technology and Applications; Vielstich, W.; Lamm, A.; Gasteiger, H. A. (Eds.); John Wiley & Sons (Chichester, UK): volume 4, chapter 60, 2003, pp. 811-831. 7. Kinoshita, K.; Carbon: Electrochemical and Physicochemical Properites; John Wiley & Sons (New York, USA): 1988. 8. LaConti, A. B.; Hamdan, M.; McDonald, R. C.; ``Mechanisms of Chemical Degradation''; in: Handbook of Fuel Cells Fundamentals, Technology and Applications; Vielstich, W.; Lamm, A.; Gasteiger, H. A. (Eds.); John Wiley & Sons (Chichester, UK): volume 3, chapter 49, 2003, pp. 647-662.

Influence of solution deposition rate on properties of V2O5 thin films deposited by spray pyrolysis technique

NASA Astrophysics Data System (ADS)

Abd-Alghafour, N. M.; Ahmed, Naser M.; Hassan, Zai; Mohammad, Sabah M.

2016-07-01

Vanadium oxide (V2O5) thin films were deposited on glass substrates by using a cost-efficient spray pyrolysis technique. The films were grown at 350° through thermal decomposition of VCl3 in deionized water with different solution spray rates. The high resolution X-ray diffraction results revealed the formation of nanocrystalline films having orthorhombic structures with preferential orientation along (101) direction. The spray rate influenced the surface morphology and crystallite size of the films. The crystallite size was found to increase whereas the micro-strain was decreased by increasing the spray deposition rates. The increase in crystallite size and decrease in the macrostrain resulted in an improvement in the films' crystallinity. The UV-Visible spectroscopy analysis indicated that the average transmittance of all films lies in the range 75-80 %. The band gap of V2O5 film was decreased from 2.65 to 2.46 eV with increase of the spray deposition rate from 5 ml/min to 10 ml/min. first, second, and third level headings (first level heading).

Differentially pumped spray deposition as a rapid screening tool for organic and perovskite solar cells.

PubMed

Jung, Yen-Sook; Hwang, Kyeongil; Scholes, Fiona H; Watkins, Scott E; Kim, Dong-Yu; Vak, Doojin

2016-02-08

We report a spray deposition technique as a screening tool for solution processed solar cells. A dual-feed spray nozzle is introduced to deposit donor and acceptor materials separately and to form blended films on substrates in situ. Using a differential pump system with a motorised spray nozzle, the effect of film thickness, solution flow rates and the blend ratio of donor and acceptor materials on device performance can be found in a single experiment. Using this method, polymer solar cells based on poly(3-hexylthiophene) (P3HT):(6,6)-phenyl C61 butyric acid methyl ester (PC61BM) are fabricated with numerous combinations of thicknesses and blend ratios. Results obtained from this technique show that the optimum ratio of materials is consistent with previously reported values confirming this technique is a very useful and effective screening method. This high throughput screening method is also used in a single-feed configuration. In the single-feed mode, methylammonium iodide solution is deposited on lead iodide films to create a photoactive layer of perovskite solar cells. Devices featuring a perovskite layer fabricated by this spray process demonstrated a power conversion efficiencies of up to 7.9%.

Differentially pumped spray deposition as a rapid screening tool for organic and perovskite solar cells

PubMed Central

Jung, Yen-Sook; Hwang, Kyeongil; Scholes, Fiona H.; Watkins, Scott E.; Kim, Dong-Yu; Vak, Doojin

2016-01-01

We report a spray deposition technique as a screening tool for solution processed solar cells. A dual-feed spray nozzle is introduced to deposit donor and acceptor materials separately and to form blended films on substrates in situ. Using a differential pump system with a motorised spray nozzle, the effect of film thickness, solution flow rates and the blend ratio of donor and acceptor materials on device performance can be found in a single experiment. Using this method, polymer solar cells based on poly(3-hexylthiophene) (P3HT):(6,6)-phenyl C61 butyric acid methyl ester (PC61BM) are fabricated with numerous combinations of thicknesses and blend ratios. Results obtained from this technique show that the optimum ratio of materials is consistent with previously reported values confirming this technique is a very useful and effective screening method. This high throughput screening method is also used in a single-feed configuration. In the single-feed mode, methylammonium iodide solution is deposited on lead iodide films to create a photoactive layer of perovskite solar cells. Devices featuring a perovskite layer fabricated by this spray process demonstrated a power conversion efficiencies of up to 7.9%. PMID:26853266

Evaluation of dip and spray coating techniques in corrosion inhibition of AA2024 alloy using a silicon/zirconium sol-gel film as coating

NASA Astrophysics Data System (ADS)

Garcia, R. B. R.; Silva, F. S.; Kawachi, E. Y.

2017-02-01

For corrosion protection of aluminum alloy AA2024 -T3 a silicon/zirconium films were obtained via sol-gel process, prepared from tetraethoxysilane and zirconium acetate, in acid medium with a 5 wt% of nonionic surfactant in order to replace the pre-treatment based on chromium conversion coatings. A homogeneous film was obtained and deposited, at low viscosity condition of the sol (˜10cP), by dip and spray coating techniques. The films morphology was evaluated by Scanning Electron Microscopy (SEM), and to know more about the used deposition methodology, the deposited mass and the film thickness were measured. The corrosion protection efficiency of deposited films was evaluated by potentiodynamic polarization. The film deposition by both dip and spray coatings were effective for the deposition of a homogeneous film layer, and the results showed the thickness is directly related with the deposited mass, and the film deposited by spray technique presented the lower value. Potentiodynamic polarization indicated that the film deposited by spray coating apparently has a better inert ceramic film due the polarization resistance increased around 57% against 27 and 14% of dip coating samples (4 and 1 layer, respectively).

Wear and Adhesive Failure of Al2O3 Powder Coating Sprayed onto AISI H13 Tool Steel Substrate

NASA Astrophysics Data System (ADS)

Amanov, Auezhan; Pyun, Young-Sik

2016-07-01

In this study, an alumina (Al2O3) ceramic powder was sprayed onto an AISI H13 hot-work tool steel substrate that was subjected to sanding and ultrasonic nanocrystalline surface modification (UNSM) treatment processes. The significance of the UNSM technique on the adhesive failure of the Al2O3 coating and on the hardness of the substrate was investigated. The adhesive failure of the coating sprayed onto sanded and UNSM-treated substrates was investigated by a micro-scratch tester at an incremental load. It was found, based on the obtained results, that the coating sprayed onto the UNSM-treated substrate exhibited a better resistance to adhesive failure in comparison with that of the coating sprayed onto the sanded substrate. Dry friction and wear property of the coatings sprayed onto the sanded and UNSM-treated substrates were assessed by means of a ball-on-disk tribometer against an AISI 52100 steel ball. It was demonstrated that the UNSM technique controllably improved the adhesive failure of the Al2O3 coating, where the critical load was improved by about 31%. Thus, it is expected that the application of the UNSM technique to an AISI H13 tool steel substrate prior to coating may delay the adhesive failure and improve the sticking between the coating and the substrate thanks to the modified and hardened surface.

Pt monolayer shell on nitrided alloy core — A path to highly stable oxygen reduction catalyst

DOE PAGES

Hu, Jue; Kuttiyiel, Kurian A.; Sasaki, Kotaro; ...

2015-07-22

The inadequate activity and stability of Pt as a cathode catalyst under the severe operation conditions are the critical problems facing the application of the proton exchange membrane fuel cell (PEMFC). Here we report on a novel route to synthesize highly active and stable oxygen reduction catalysts by depositing Pt monolayer on a nitrided alloy core. The prepared Pt MLPdNiN/C catalyst retains 89% of the initial electrochemical surface area after 50,000 cycles between potentials 0.6 and 1.0 V. By correlating electron energy-loss spectroscopy and X-ray absorption spectroscopy analyses with electrochemical measurements, we found that the significant improvement of stability ofmore » the Pt MLPdNiN/C catalyst is caused by nitrogen doping while reducing the total precious metal loading.« less

TiO2 and Al2O3 promoted Pt/C nanocomposites as low temperature fuel cell catalysts for electro oxidation of methanol in acidic media

NASA Astrophysics Data System (ADS)

Naeem, Rabia; Ahmed, Riaz; Shahid Ansari, Muhammad

2014-06-01

Carbon corrosion and platinum dissolution are the two major catalyst layer degradation problems in polymer electrolyte membrane fuel cells (PEMFC). Ceramic addition can reduce the corrosion of carbon and increase the stability of catalysts. Pt/TiO2, Pt/TiO2-C, Pt/Al2O3 and Pt/Al2O3-C catalysts were synthesized and characterized. Electrochemical surface area of Pt/TiO2-C and Pt/Al2O3-C nanocomposite catalysts was much higher than the Pt/TiO2 and Pt/Al2O3 catalysts. Peak current, specific activity and mass activity of the catalysts was also determined by cyclic voltammetry and were much higher for the carbon nanocomposites. Exchange current densities were determined from Tafel plots. Heterogeneous rates of reaction of electro oxidation of methanol were determined for all the catalysts and were substantially higher for titania catalysts as compared to alumina added catalysts. Mass activity of Pt/TiO2-C was much higher than mass activity of Pt/Al2O3-C. Stability studies showed that addition of ceramics have increased the catalytic activity and durability of the catalysts considerably.

Fe2P as a novel efficient catalyst promoter in Pd/C system for formic acid electro-oxidation in fuel cells reaction

NASA Astrophysics Data System (ADS)

Wang, Fulong; Xue, Huaiguo; Tian, Zhiqun; Xing, Wei; Feng, Ligang

2018-01-01

Developing catalyst promoter for Pd/C catalyst is significant for the catalytic ability improvement in energy transfer related electrochemical reactions. Herein, we demonstrate Fe2P as an efficient catalyst promoter in Pd/C catalyst system for formic acid electro-oxidation in fuel cells reactions. Adding Fe2P in the Pd/C catalyst system greatly increases the performances for formic acid oxidation by 3-4 times; the CO stripping technique displays two kinds of active sites formation in the Pd-Fe2P/C catalyst system coming from the interaction of Pd, Fe2P and Pd oxide species and both are more efficient for formic acid and CO-species electrooxidation. The smaller charge transfer resistance and Tafel slope for formic acid oxidation indicate the improvements in kinetics by Fe2P in the Pd-Fe2P/C system. The nanostructured hybrid units of Pd, Fe2P and carbon are evidently visible in the high resolution microscopy images and XPS technique confirmes the electronic effect in the catalyst system. The promotion effect of Fe2P in the catalyst system arising from the structure, composition and electronic effect changes is discussed with the help from multiple physical and electrochemical techniques. It is concluded that Fe2P as a significant catalyst promoter will have potential application in energy transfer related electrochemical reactions.

Antimisting kerosene atomization and flammability

NASA Technical Reports Server (NTRS)

Fleeter, R.; Petersen, R. A.; Toaz, R. D.; Jakub, A.; Sarohia, V.

1982-01-01

Various parameters found to affect the flammability of antimisting kerosene (Jet A + polymer additive) are investigated. Digital image processing was integrated into a technique for measurement of fuel spray characteristics. This technique was developed to avoid many of the error sources inherent to other spray assessment techniques and was applied to the study of engine fuel nozzle atomization performance with Jet A and antimisting fuel. Aircraft accident fuel spill and ignition dynamics were modeled in a steady state simulator allowing flammability to be measured as a function of airspeed, fuel flow rate, fuel jet Reynolds number and polymer concentration. The digital imaging technique was employed to measure spray characteristics in this simulation and these results were related to flammability test results. Scaling relationships were investigated through correlation of experimental results with characteristic dimensions spanning more than two orders of magnitude.

Catalytic membrane reactor for water and wastewater treatment

NASA Astrophysics Data System (ADS)

Heng, Samuel

A double membrane reactor was fabricated and assessed for continuous treatment of water containing organic contaminants by ozonation. This innovative reactor consisted of a zeolite membrane prepared on the inner surface of a porous a-alumina support, which served as water selective extractor and active contactor, and a porous stainless membrane which was the ozone gas diffuser. The coupling of membrane separation and chemical oxidation was found to be highly beneficial to both processes. The total organic carbon (TOC) removal rate at the retentate was enhanced by up to 2.2 times, as compared to membrane ozonation. Simultaneously, clean water (< 2 mg C.L-1 ) was consistently produced on the permeate side, using a feed solution containing up to 1000 mg C.L-1, while the retentate was concentrated and treated. Most significantly, the addition of an adsorbing material, as a bed or a coated layer, onto the pores of the membrane support, was shown to further enhance TOC degradation, permeated TOC concentration, permeate flux, and moreover, ozone yield. The achievements of this project included: (1) The development of a novel low-temperature zeolite membrane activation method that generates consistently high quality membranes (i.e. high reproducibility and fewer defects). (2) The demonstration that gamma-alumina and gamma-alumina supported catalysts do not have significant activity and that the TOC removal enhancement usually observed during catalytic ozonation was due primarily to the contribution of adsorption and metal leaching. Thermogravimetric analysis (TGA) and elemental analysis (EA) of the spent catalyst showed that, during catalytic ozonation, oxygenated by-products of increased adsorbability were concentrated onto the gamma-alumina contactor, and were subsequently degraded. (3) The development of a method for coating high surface area gamma-alumina layers onto the grains of zeolite membrane support used as the active membrane contactor.

In-membrane micro fuel cell

DOEpatents

Omosebi, Ayokunle; Besser, Ronald

2016-09-06

An in-membrane micro fuel cell comprises an electrically-insulating membrane that is permissive to the flow of cations, such as protons, and a pair of electrodes deposited on channels formed in the membrane. The channels are arranged as conduits for fluids, and define a membrane ridge between the channels. The electrodes are porous and include catalysts for promoting the liberation of a proton and an electron from a chemical species and/or or the recombination of a proton and an electron with a chemical specie. The fuel cell may be provided a biosensor, an electrochemical sensor, a microfluidic device, or other microscale devices fabricated in the fuel cell membrane.

Fabrication of a nanosize-Pt-embedded membrane electrode assembly to enhance the utilization of Pt in proton exchange membrane fuel cells.

PubMed

Choe, Junseok; Kim, Doyoung; Shim, Jinyong; Lee, Inhae; Tak, Yongsug

2011-08-01

A procedure to locate the Pt nanostructure inside the hydrophilic channel of a Nafion membrane was developed in order to enhance Pt utilization in PEMFCs. Nanosize Pt-embedded MEA was constructed by Cu electroless plating and subsequent Pt electrodeposition inside the hydrophilic channels of the Nafion membrane. The metallic Pt nanostructure fabricated inside the membrane was employed as an oxygen reduction catalyst for a PEMFC and facilitated effective use of the hydrophilic channels inside the membrane. Compared to the conventional MEA, a Pt-embedded MEA with only 68% Pt loading showed better PEMFC performance.

Experimental investigation on the characteristics of supersonic fuel spray and configurations of induced shock waves.

PubMed

Wang, Yong; Yu, Yu-Song; Li, Guo-Xiu; Jia, Tao-Ming

2017-01-05

The macro characteristics and configurations of induced shock waves of the supersonic sprays are investigated by experimental methods. Visualization study of spray shape is carried out with the high-speed camera. The macro characteristics including spray tip penetration, velocity of spray tip and spray angle are analyzed. The configurations of shock waves are investigated by Schlieren technique. For supersonic sprays, the concept of spray front angle is presented. Effects of Mach number of spray on the spray front angle are investigated. The results show that the shape of spray tip is similar to blunt body when fuel spray is at transonic region. If spray entered the supersonic region, the oblique shock waves are induced instead of normal shock wave. With the velocity of spray increasing, the spray front angle and shock wave angle are increased. The tip region of the supersonic fuel spray is commonly formed a cone. Mean droplet diameter of fuel spray is measured using Malvern's Spraytec. Then the mean droplet diameter results are compared with three popular empirical models (Hiroyasu's, Varde's and Merrigton's model). It is found that the Merrigton's model shows a relative good correlation between models and experimental results. Finally, exponent of injection velocity in the Merrigton's model is fitted with experimental results.

Experimental investigation on the characteristics of supersonic fuel spray and configurations of induced shock waves

PubMed Central

Wang, Yong; Yu, Yu-song; Li, Guo-xiu; Jia, Tao-ming

2017-01-01

The macro characteristics and configurations of induced shock waves of the supersonic sprays are investigated by experimental methods. Visualization study of spray shape is carried out with the high-speed camera. The macro characteristics including spray tip penetration, velocity of spray tip and spray angle are analyzed. The configurations of shock waves are investigated by Schlieren technique. For supersonic sprays, the concept of spray front angle is presented. Effects of Mach number of spray on the spray front angle are investigated. The results show that the shape of spray tip is similar to blunt body when fuel spray is at transonic region. If spray entered the supersonic region, the oblique shock waves are induced instead of normal shock wave. With the velocity of spray increasing, the spray front angle and shock wave angle are increased. The tip region of the supersonic fuel spray is commonly formed a cone. Mean droplet diameter of fuel spray is measured using Malvern’s Spraytec. Then the mean droplet diameter results are compared with three popular empirical models (Hiroyasu’s, Varde’s and Merrigton’s model). It is found that the Merrigton’s model shows a relative good correlation between models and experimental results. Finally, exponent of injection velocity in the Merrigton’s model is fitted with experimental results. PMID:28054555

Quantifying liquid boundary and vapor distributions in a fuel spray by rainbow schlieren deflectometry

DOE Office of Scientific and Technical Information (OSTI.GOV)

Taber Wanstall, C.; Agrawal, Ajay K.; Bittle, Joshua A.

The rainbow schlieren deflectometry (RSD) technique is used to determine the liquid boundary and the fuel volume fraction distributions in the vapor region of a high-pressure fuel spray. Experiments were conducted in a constant pressure flow vessel, whereby a customized single-hole common-rail diesel injector is used to introduce n-heptane fuel into a coflow of low-speed ambient air at two different test conditions. Only the quasi-steady period of the fuel spray is considered, and multiple injections are performed to acquire statistically significant data at an image acquisition rate of 20 kHz. An algorithm to identify the liquid boundary using intensity recordedmore » by the RSD images is presented. The results are compared against measurements obtained by the Mie scattering technique. Our results demonstrate that the RSD can be a powerful optical diagnostics technique to simultaneously quantify both the vapor and liquid regions in the high-pressure fuel sprays.« less

A Novel Hybrid Axial-Radial Atmospheric Plasma Spraying Technique for the Fabrication of Solid Oxide Fuel Cell Anodes Containing Cu, Co, Ni, and Samaria-Doped Ceria

NASA Astrophysics Data System (ADS)

Cuglietta, Mark; Kuhn, Joel; Kesler, Olivera

2013-06-01

Composite coatings containing Cu, Co, Ni, and samaria-doped ceria (SDC) have been fabricated using a novel hybrid atmospheric plasma spraying technique, in which a multi-component aqueous suspension of CuO, Co3O4, and NiO was injected axially simultaneously with SDC injected radially in a dry powder form. Coatings were characterized for their microstructure, permeability, porosity, and composition over a range of plasma spray conditions. Deposition efficiency of the metal oxides and SDC was also estimated. Depending on the conditions, coatings displayed either layering or high levels of mixing between the SDC and metal phases. The deposition efficiencies of both feedstock types were strongly dependent on the nozzle diameter. Plasma-sprayed metal-supported solid oxide fuel cells utilizing anodes fabricated with this technique demonstrated power densities at 0.7 V as high as 366 and 113 mW/cm2 in humidified hydrogen and methane, respectively, at 800 °C.

Quantifying liquid boundary and vapor distributions in a fuel spray by rainbow schlieren deflectometry

DOE PAGES

Taber Wanstall, C.; Agrawal, Ajay K.; Bittle, Joshua A.

2017-01-01

The rainbow schlieren deflectometry (RSD) technique is used to determine the liquid boundary and the fuel volume fraction distributions in the vapor region of a high-pressure fuel spray. Experiments were conducted in a constant pressure flow vessel, whereby a customized single-hole common-rail diesel injector is used to introduce n-heptane fuel into a coflow of low-speed ambient air at two different test conditions. Only the quasi-steady period of the fuel spray is considered, and multiple injections are performed to acquire statistically significant data at an image acquisition rate of 20 kHz. An algorithm to identify the liquid boundary using intensity recordedmore » by the RSD images is presented. The results are compared against measurements obtained by the Mie scattering technique. Our results demonstrate that the RSD can be a powerful optical diagnostics technique to simultaneously quantify both the vapor and liquid regions in the high-pressure fuel sprays.« less

Quantitative X-ray measurements of high-pressure fuel sprays from a production heavy duty diesel injector

NASA Astrophysics Data System (ADS)

Ramírez, A. I.; Som, S.; Aggarwal, Suresh K.; Kastengren, A. L.; El-Hannouny, E. M.; Longman, D. E.; Powell, C. F.

2009-07-01

A quantitative and time-resolved X-ray radiography technique has been used for detailed measurements of high-pressure fuel sprays in the near-nozzle region of a diesel engine injector. The technique provides high spatial and temporal resolution, especially in the relatively dense core region. A single spray plume from a hydraulically actuated electronically controlled unit injector model 315B injector with a 6-hole nozzle was isolated and studied at engine-like densities for two different injection pressures. Optical spray imaging was also employed to evaluate the effectiveness of the shield used to isolate a single spray plume. The steady state fuel distributions for both injection pressures are similar and show a dense spray region along the axis of the spray, with the on-axis spray density decreasing as the spray progresses downstream. The higher injection pressure case exhibits a larger cone angle and spray broadening at the exit of the nozzle. For some time periods, the near-nozzle penetration speed is lower for the high injection pressure case than the low injection pressure case, which is unexpected, but can be attributed to the needle and flow dynamics inside the injector causing slower pressure build-up for the former case. Rate of injection testing was performed to further understand near-nozzle behavior. Mass distribution data were obtained and used to find mass-averaged velocity of the spray. Comparisons of the radiography data with that from a common rail single-hole light duty injectors under similar injection conditions show several significant differences. The current data show a larger cone angle and lower penetration speed than that from the light-duty injector. Moreover, these data display a Gaussian mass distribution across the spray near the injector, whereas in previous light-duty injector measurements, the mass distribution had steeper sides and a flatter peak. Measurements are also used to examine the spray models in the STAR-CD software.

Advanced membrane electrode assemblies for fuel cells

DOEpatents

Kim, Yu Seung; Pivovar, Bryan S.

2012-07-24

A method of preparing advanced membrane electrode assemblies (MEA) for use in fuel cells. A base polymer is selected for a base membrane. An electrode composition is selected to optimize properties exhibited by the membrane electrode assembly based on the selection of the base polymer. A property-tuning coating layer composition is selected based on compatibility with the base polymer and the electrode composition. A solvent is selected based on the interaction of the solvent with the base polymer and the property-tuning coating layer composition. The MEA is assembled by preparing the base membrane and then applying the property-tuning coating layer to form a composite membrane. Finally, a catalyst is applied to the composite membrane.

Advanced membrane electrode assemblies for fuel cells

DOEpatents

Kim, Yu Seung; Pivovar, Bryan S

2014-02-25

A method of preparing advanced membrane electrode assemblies (MEA) for use in fuel cells. A base polymer is selected for a base membrane. An electrode composition is selected to optimize properties exhibited by the membrane electrode assembly based on the selection of the base polymer. A property-tuning coating layer composition is selected based on compatibility with the base polymer and the electrode composition. A solvent is selected based on the interaction of the solvent with the base polymer and the property-tuning coating layer composition. The MEA is assembled by preparing the base membrane and then applying the property-tuning coating layer to form a composite membrane. Finally, a catalyst is applied to the composite membrane.

Facile and scalable fabrication of polymer-ceramic composite electrolyte with high ceramic loadings

NASA Astrophysics Data System (ADS)

Pandian, Amaresh Samuthira; Chen, X. Chelsea; Chen, Jihua; Lokitz, Bradley S.; Ruther, Rose E.; Yang, Guang; Lou, Kun; Nanda, Jagjit; Delnick, Frank M.; Dudney, Nancy J.

2018-06-01

Solid state electrolytes are a promising alternative to flammable liquid electrolytes for high-energy lithium battery applications. In this work polymer-ceramic composite electrolyte membrane with high ceramic loading (greater than 60 vol%) is fabricated using a model polymer electrolyte poly(ethylene oxide) + lithium trifluoromethane sulfonate and a lithium-conducting ceramic powder. The effects of processing methods, choice of plasticizer and varying composition on ionic conductivity of the composite electrolyte are thoroughly investigated. The physical, structural and thermal properties of the composites are exhaustively characterized. We demonstrate that aqueous spray coating followed by hot pressing is a scalable and inexpensive technique to obtain composite membranes that are amazingly dense and uniform. The ionic conductivity of composites fabricated using this protocol is at least one order of magnitude higher than those made by dry milling and solution casting. The introduction of tetraethylene glycol dimethyl ether further increases the ionic conductivity. The composite electrolyte's interfacial compatibility with metallic lithium and good cyclability is verified by constructing lithium symmetrical cells. A remarkable Li+ transference number of 0.79 is discovered for the composite electrolyte.

Application of Rapid Prototyping and Wire Arc Spray to the Fabrication of Injection Mold Tools (MSFC Center Director's Discretionary Fund)

NASA Technical Reports Server (NTRS)

Cooper, K. G.

2000-01-01

Rapid prototyping (RP) is a layer-by-layer-based additive manufacturing process for constructing three-dimensional representations of a computer design from a wax, plastic, or similar material. Wire arc spray (WAS) is a metal spray forming technique, which deposits thin layers of metal onto a substrate or pattern. Marshall Space Flight Center currently has both capabilities in-house, and this project proposed merging the two processes into an innovative manufacturing technique, in which intermediate injection molding tool halves were to be fabricated with RP and WAS metal forming.

Resistance of Concrete Masonry Walls With Membrane Catcher Systems Subjected to Blast Loading

DTIC Science & Technology

2010-12-01

fiber reinforcement) sprayed-on polymers. The early versions of this approach were a polyurea -based coating similar to that used for truck bed liners...displacement. Figure 5 illustrates a resistance function using a polyurea membrane retrofit, and Figure 6 shows the complete resistance function. The...resistance function is truncated for these conditions: Figure 5. Resistance function — 3 mm thick polyurea retrofit DIsplacement (mm) P re s s u re

Hydrophilic TiO2 porous spheres anchored on hydrophobic polypropylene membrane for wettability induced high photodegrading activities.

PubMed

Niu, Fang; Zhang, Le-Sheng; Chen, Chao-Qiu; Li, Wei; Li, Lin; Song, Wei-Guo; Jiang, Lei

2010-08-01

TiO(2) porous nanospheres on polypropylene (PP) films (TiO(2)/PP composite) are produced at ambient temperature. Particle/pore size match up is the key anchoring point to overcome the low affinity between hydrophilic materials and hydrophobic materials. With the hydrophilic TiO(2) catalyst evenly dispersed on a hydrophobic surface, the aqueous solution will selectively skip the substrate and wet the catalysts. Such a wettability-induced smart system maximizes the degrading activity of the TiO(2) catalyst. In photodegrading reactions, the resulting TiO(2)/PP composite film exhibits a 10 times higher activity in flow-type setup than the same TiO(2) catalyst in a traditional batch-type setup.

Durability Improvement of Pt/RGO Catalysts for PEMFC by Low-Temperature Self-Catalyzed Reduction.

PubMed

Sun, Kang Gyu; Chung, Jin Suk; Hur, Seung Hyun

2015-12-01

Pt/C catalyst used for polymer electrolyte membrane fuel cells (PEMFCs) displays excellent initial performance, but it does not last long because of the lack of durability. In this study, a Pt/reduced graphene oxide (RGO) catalyst was synthesized by the polyol method using ethylene glycol (EG) as the reducing agent, and then low-temperature hydrogen bubbling (LTHB) treatment was introduced to enhance the durability of the Pt/RGO catalyst. The cyclic voltammetry (CV), oxygen reduction reaction (ORR) analysis, and transmittance electron microscopy (TEM) results suggested that the loss of the oxygen functional groups, because of the hydrogen spillover and self-catalyzed dehydration reaction during LTHB, reduced the carbon corrosion and Pt agglomeration and thus enhanced the durability of the electrocatalyst.

Mechanical and transport properties of layer-by-layer electrospun composite proton exchange membranes for fuel cell applications.

PubMed

Mannarino, Matthew M; Liu, David S; Hammond, Paula T; Rutledge, Gregory C

2013-08-28

Composite membranes composed of highly conductive and selective layer-by-layer (LbL) films and electrospun fiber mats were fabricated and characterized for mechanical strength and electrochemical selectivity. The LbL component consists of a proton-conducting, methanol-blocking poly(diallyl dimethyl ammonium chloride)/sulfonated poly(2,6-dimethyl-1,4-phenylene oxide) (PDAC/sPPO) thin film. The electrospun fiber component consists of poly(trimethyl hexamethylene terephthalamide) (PA 6(3)T) fibers in a nonwoven mat of 60-90% porosity. The bare mats were annealed to improve their mechanical properties, which improvements are shown to be retained in the composite membranes. Spray LbL assembly was used as a means for the rapid formation of proton-conducting films that fill the void space throughout the porous electrospun matrix and create a fuel-blocking layer. Coated mats as thin as 15 μm were fabricated, and viable composite membranes with methanol permeabilities 20 times lower than Nafion and through-plane proton selectivity five and a half times greater than Nafion are demonstrated. The mechanical properties of the spray coated electrospun mats are shown to be superior to the LbL-only system and possess intrinsically greater dimensional stability and lower mechanical hysteresis than Nafion under hydrated conditions. The composite proton exchange membranes fabricated here were tested in an operational direct methanol fuel cell. The results show the potential for higher open circuit voltages (OCV) and comparable cell resistances when compared to fuel cells based on Nafion.

Catalyst patterning for nanowire devices

NASA Technical Reports Server (NTRS)

Li, Jun (Inventor); Cassell, Alan M. (Inventor); Han, Jie (Inventor)

2004-01-01

Nanowire devices may be provided that are based on carbon nanotubes or single-crystal semiconductor nanowires. The nanowire devices may be formed on a substrate. Catalyst sites may be formed on the substrate. The catalyst sites may be formed using lithography, thin metal layers that form individual catalyst sites when heated, collapsible porous catalyst-filled microscopic spheres, microscopic spheres that serve as masks for catalyst deposition, electrochemical deposition techniques, and catalyst inks. Nanowires may be grown from the catalyst sites.

Polymer membrane based electrolytic cell and process for the direct generation of hydrogen peroxide in liquid streams

NASA Technical Reports Server (NTRS)

White, James H. (Inventor); Schwartz, Michael (Inventor); Sammells, Anthony F. (Inventor)

1997-01-01

An electrolytic cell for generating hydrogen peroxide is provided including a cathode containing a catalyst for the reduction of oxygen, and an anode containing a catalyst for the oxidation of water. A polymer membrane, semipermeable to either protons or hydroxide ions is also included and has a first face interfacing to the cathode and a second face interfacing to the anode so that when a stream of water containing dissolved oxygen or oxygen bubbles is passed over the cathode and a stream of water is passed over the anode, and an electric current is passed between the anode and the cathode, hydrogen peroxide is generated at the cathode and oxygen is generated at the anode.

Investigation of Expedient Ground Surfacing with a Glass Fiber-Resin Mixture by a Spray-Deposition Technique,

DTIC Science & Technology

PAVEMENTS, *REINFORCED PLASTICS), LANDING FIELDS, SPRAYS, GLASS TEXTILES, LAMINATED PLASTICS, TEST METHODS, FOUNDATIONS(STRUCTURES), SANDWICH CONSTRUCTION, SOILS, FEASIBILITY STUDIES, LOAD DISTRIBUTION

[A microbiological investigation of the effectiveness of Micro Megas E-spray].

PubMed

Kardel, K; Hegna, I K; Kardel, M

1976-06-01

The disinfecting effect of Micro Megas E-spray was tested using a microbiological technique which also included a practical test. Contra-angels and straight handpieces which were sprayed after being used for treatment on patients, and then dried and incubated in a liquid medium, showed a marked growth of microorganisms. The spray had a weak and barely significant growth inhibiting effect on contaminated, simulated instrument surfaces. using Pseudomonas aeruginosa, Escherichia coli and Staphylococcus aureus as test bacteria. It is concluded that the spray is not suitable for distinfection of contra-angels and straight handpieces.

Direct morphological comparison of vacuum plasma sprayed and detonation gun sprayed hydroxyapatite coatings for orthopaedic applications.

PubMed

Gledhill, H C; Turner, I G; Doyle, C

1999-02-01

Hydroxyapatite coatings on titanium substrates were produced using two thermal spray techniques vacuum plasma spraying and detonation gun spraying. X-ray diffraction was used to compare crystallinity and residual stresses in the coatings. Porosity was measured using optical microscopy in conjunction with an image analysis system. Scanning electron microscopy and surface roughness measurements were used to characterise the surface morphologies of the coatings. The vacuum plasma sprayed coatings were found to have a lower residual stress, a higher crystallinity and a higher level of porosity than the detonation gun coatings. It is concluded that consideration needs to be given to the significance of such variations within the clinical context.

Deactivation of Pt/VC proton exchange membrane fuel cell cathodes by SO2, H2S and COS

NASA Astrophysics Data System (ADS)

Gould, Benjamin D.; Baturina, Olga A.; Swider-Lyons, Karen E.

Sulfur contaminants in air pose a threat to the successful operation of proton exchange membrane fuel cells (PEMFCs) via poisoning of the Pt-based cathodes. The deactivation behavior of commercial Pt on Vulcan carbon (Pt/VC) membrane electrode assemblies (MEAs) is determined when exposed to 1 ppm (dry) of SO 2, H 2S, or COS in air for 3, 12, and 24 h while held at a constant potential of 0.6 V. All the three sulfur compounds cause the same deactivation behavior in the fuel cell cathodes, and the polarization curves of the poisoned MEAs have the same decrease in performance. Sulfur coverages after multiple exposure times (3, 12, and 24 h) are determined by cyclic voltammetry (CV). As the exposure time to sulfur contaminants increases from 12 to 24 h, the sulfur coverage of the platinum saturates at 0.45. The sulfur is removed from the cathodes and their activity is partially restored both by cyclic voltammetry, as shown by others, and by successive polarization curves. Complete recovery of fuel cell performance is not achieved with either technique, suggesting that sulfur species permanently affect the surface of the catalyst.

Detecting Heap-Spraying Code Injection Attacks in Malicious Web Pages Using Runtime Execution

NASA Astrophysics Data System (ADS)

Choi, Younghan; Kim, Hyoungchun; Lee, Donghoon

The growing use of web services is increasing web browser attacks exponentially. Most attacks use a technique called heap spraying because of its high success rate. Heap spraying executes a malicious code without indicating the exact address of the code by copying it into many heap objects. For this reason, the attack has a high potential to succeed if only the vulnerability is exploited. Thus, attackers have recently begun using this technique because it is easy to use JavaScript to allocate the heap memory area. This paper proposes a novel technique that detects heap spraying attacks by executing a heap object in a real environment, irrespective of the version and patch status of the web browser. This runtime execution is used to detect various forms of heap spraying attacks, such as encoding and polymorphism. Heap objects are executed after being filtered on the basis of patterns of heap spraying attacks in order to reduce the overhead of the runtime execution. Patterns of heap spraying attacks are based on analysis of how an web browser accesses benign web sites. The heap objects are executed forcibly by changing the instruction register into the address of them after being loaded into memory. Thus, we can execute the malicious code without having to consider the version and patch status of the browser. An object is considered to contain a malicious code if the execution reaches a call instruction and then the instruction accesses the API of system libraries, such as kernel32.dll and ws_32.dll. To change registers and monitor execution flow, we used a debugger engine. A prototype, named HERAD(HEap spRAying Detector), is implemented and evaluated. In experiments, HERAD detects various forms of exploit code that an emulation cannot detect, and some heap spraying attacks that NOZZLE cannot detect. Although it has an execution overhead, HERAD produces a low number of false alarms. The processing time of several minutes is negligible because our research focuses on detecting heap spraying. This research can be applied to existing systems that collect malicious codes, such as Honeypot.