The Effect of Various Electrode Microstructure Parameters on the Effective Conductivity and Three-Phase Boundary Density of Infiltrated SOFC Electrodes

Solid oxide fuel cell (SOFC) technology has the potential to be a significant player in our future energy technology repertoire based on its ability to convert chemical energy into electrical energy. Infiltrated SOFCs, in particular, have demonstrated improved performance and at lower cost than traditional SOFCs. An infiltrated electrode comprises porous ceramic scaffolding (typically constructed from the oxygen ion conducting material) that is infiltrated with electron conducting and catalytic particles. Two important SOFC electrode properties are effective conductivity and three phase boundary density (TPB). Researchers study these electrode properties separately, and fail to recognize them as competing properties. This thesis aims to (1) develop a method to model the TPB density and use it to determine the effect of porosity, scaffolding particle size, and pore former size on TPB density as well as to (2) compare the effect of porosity, scaffolding particle size, and pore former size on TPB density and effective conductivity to determine a desired set of parameters for infiltrated SOFC electrode performance. A computational model was used to study the effect of microstructure parameters on the effective conductivity and TPB density of the infiltrated SOFC electrode. From this study, effective conductivity and TPB density are determined to be competing properties of SOFC electrodes. Increased porosity, scaffolding particle size, and pore former particle size increase the effective conductivity for a given infiltrate loading above percolation threshold. Increased scaffolding particle size and pore former size ratio, however, decreases the TPB density. The maximum TPB density is achievable between porosities of 45% and 60%. The effect of microstructure parameters are more prominent at low loading with scaffolding particle size being the most significant factor and pore former size ratio being the least significant factor.

Composition of bottom sediments, rocks, and ores from the Tropical Atlantic

Geological features of some areas of the Tropical Atlantic (stratigraphy, tectonic structure, lithology, distribution of ore components in bottom sediments, petrography of bedrocks, etc.) are under consideration in the book. Regularities of concentration of trace elements in iron-manganese nodules, features of these nodules in bottom sediments, distribution of phosphorite nodules and other phosphorites have been studied. Much attention is paid to rocks of the ocean crust. A wide range of mineralization represented by magnetite, chromite, chalcopyrite, pyrite, pentlandite, and other minerals has been found.

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

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

Sol–gel copper chromium delafossite thin films as stable oxide photocathodes for water splitting

Significant effort is being devoted to the study of photoactive electrode materials for artificial photosynthesis devices. In this context, photocathodes promoting water reduction, based on earth-abundant elements and possessing stability under illumination, should be developed. Here, the photoelectrochemical behavior of CuCrO2 sol–gel thin film electrodes prepared on conducting glass is presented. The material, whose direct band gap is 3.15 eV, apparently presents a remarkable stability in both alkaline and acidic media. In 0.1 M HClO4 the material is significantly photoactive, with IPCE values at 350 nm and 0.36 V vs. RHE of over 6% for proton reduction and 23% for oxygen reduction. This response was obtained in the absence of charge extraction layers or co-catalysts, suggesting substantial room for optimization. The photocurrent onset potential is equal to 1.06 V vs. RHE in both alkaline and acidic media, which guarantees the combination of the material with different photoanodes such as Fe2O3 or WO3, potentially yielding bias-free water splitting devices.

Synthesis and electrochemical properties of mesoporous nickel oxide

Mesoporous Ni(OH)(2) is synthesized using sodium dodecyl sulfate as a template and urea as a hydrolysis-controlling agent. Mesoporous NiO with a centralized pore-size distribution is obtained by calcining Ni(OH)(2) at different temperatures. The BET specific surface area reaches 477.7 m(2) g(-1) for NiO calcined at 250 degreesC. Structure characterizations indicate a good mesoporous structure for the nickel oxide samples. Cyclic voltammetry shows the NiO to have good capacitive behaviour due to its unique mesoporous structure when using a large amount of NiO to fabricate the electrode. Compared with NiO prepared by dip-coating and cathodic precipitation methods, mesoporous NiO with a controlled pore structure can be used in much larger amounts to fabricate electrodes and still maintain a high specific capacitance and good capacitive behaviour. (C) 2004 Elsevier B.V. All rights reserved.

Electrochemical characteristics of ordered mesoporous carbon used as electrode material in Li-ion battery

Ordered mesoporous carbon CMK-5 was comprehensively tested for the first time as electrode materials in lithium ion battery. The surface morphology, pore structure and crystal structure were investigated by Scanning Electronic Microscopy (SEM), N-2 adsorption technique and X-ray diffraction (XRD) respectively. Electrochemical properties of CMK-5 were studied by galvanostatic cycling and cyclic voltammetry, and compared with conventional anode material graphite. Results showed that the reversible capacity of CMK-5 was 525 mAh/g at the third charge-discharge cycle and that CMK-5 was more compatible for quick charge-discharge cycling because of its special mesoporous structure. Of special interest was that the CMK-5 gave no peak on its positive sweep of the cyclic voltammetry, which was different from all the other known anode materials. Besides, X-ray photoelectron spectroscopy (XPS) and XRD were also applied to investigate the charge-discharge characteristics of CMK-5.

Synthesis and characterization of mesoporous nickel oxide and its application to electrochemical capacitor

Mesoporous Ni(OH)(2) was synthesized using cationic surfactant as template and urea as hydrolysis-controlling agent. Mesoporous NiO with centralized pore size distribution was obtained by calcining Ni(OH)(2) at different temperatures. The BET specific surface area reaches 477.7 m(2).g(-1) for NiO calcined at 523 K. Structure characterizations indicate the polycrystalline pore wall of mesoporous nickel oxide. The pore-formation mechanism is also deduced to be quasi-reverse micelle mechanism. Cyclic voltammetry shows the good capacitive behavior of these NiO samples due to its unique mesoporous structure when using large amount of NiO to fabricate electrode. Compared with NiO prepared by dip-coating and cathodic precipitation methods, this mesoporous NiO with controlled pore structure can be used in much larger amount to fabricate the electrode and still maintains high specific capacitance and good capacitive behavior.

Interlamellar modification of smectite clays

Clay minerals, both natural and synthetic, have a wide range of applications. Smectite clays are not true insulators, their slight conductivity has been utilized by the paper industry in the development of mildly conducting paper. In particular, the synthetic hectorite clay, laponite, is employed to produce paper which is used in automated drawing offices where electro graphic printing is common. The primary objective of this thesis was to modify smectite clays, particularly laponite, to achieve enhanced conductivity. The primary objective was more readily achieved if the subsidiary objective of understanding the mechanism of conductivity was defined. The cyclic voltammograms of some cobalt complexes were studied in free solution and as clay modified electrodes to investigate the origin of electroactivity in clay modified electrodes. The electroactivity of clay modified electrodes prepared using our method can be attributed to ion pairs sorbed to the surface of the electrode, in excess of the cationic exchange capacity. However, some new observations were made concerning the co-ordination chemistry of the tri-2-pyridylamine complexes used which needed clarification. The a.c. conductivity of pressed discs of laponite RD was studied over the frequency range 12Hz- 100kHz using three electrode systems namely silver-loaded epoxy resin (paste), stainless-steel and aluminium. The a. c. conductivity of laponite consists of two components, reactive (minor) and ionic (major) which can be observed almost independently by utilizing the different electrode systems. When the temperature is increased the conductivity of laponite increases and the activation energy for conductivity can be calculated. Measurement of the conductivity of thin films of laponite RD in two crystal planes shows a degree of anisotropy in the a.c. conductivity. Powder X-ray diffraction and 119Sn Mossbauer spectroscopy studies have shown that attempts to intercalate some phenyltin compounds into laponite RD under ambient conditions result in the formation of tin(IV) oxide pillars. 119Sn Mossbauer data indicate that the order of effectiveness of conversion to pillars is in the order: Ph3SnCl > (Ph3Sn)2O, Ph2SnCl2 The organic product of the pillaring process was identified by 13C m.a.s.n.m.r. spectroscopy as trapped in the pillared lattice. This pillaring reaction is much more rapid when carried out in Teflon containers in a simple domestic microwave oven. These pillared clays are novel materials since the pillaring is achieved via neutral precursors rather than sacrificial reaction of the exchangeable cation. The pillaring reaction depends on electrophilic attack on the aryl tin bond by Brønsted acid sites within the clay. Two methods of interlamellar modification were identified which lead to enhanced conductivity of laponite, namely ion exchange and tin(IV) oxide pillaring. A monoionic potassium exchanged laponite shows a four fold increase in a.c. conductivity compared to sodium exchanged laponite RD. The increased conductivity is due to the appearence of an ionic component. The conductivity is independent of relative humidity and increases with temperature. Tin(IV) oxide pillared laponite RD samples show a significant increase in conductivity. Samples prepared from Ph2SnCl2 show an increase in excess of an order of magnitude. The conductivity of tin(IV) oxide pillared laponite samples is dominated by an ionic component.

Enhanced zinc oxide and graphene nanostructures for electronics and sensing applications

Zinc oxide and graphene nanostructures are important technological materials because of their unique properties and potential applications in future generation of electronic and sensing devices. This dissertation investigates a brief account of the strategies to grow zinc oxide nanostructures (thin film and nanowire) and graphene, and their applications as enhanced field effect transistors, chemical sensors and transparent flexible electrodes. Nanostructured zinc oxide (ZnO) and low-gallium doped zinc oxide (GZO) thin films were synthesized by a magnetron sputtering process. Zinc oxide nanowires (ZNWs) were grown by a chemical vapor deposition method. Field effect transistors (FETs) of ZnO and GZO thin films and ZNWs were fabricated by standard photo and electron beam lithography processes. Electrical characteristics of these devices were investigated by nondestructive surface cleaning, ultraviolet irradiation treatment at high temperature and under vacuum. GZO thin film transistors showed a mobility of ∼5.7 cm2/V·s at low operation voltage of <5 V and a low turn-on voltage of ∼0.5 V with a sub threshold swing of ∼85 mV/decade. Bottom gated FET fabricated from ZNWs exhibit a very high on-to-off ratio (∼106) and mobility (∼28 cm2/V·s). A bottom gated FET showed large hysteresis of ∼5.0 to 8.0 V which was significantly reduced to ∼1.0 V by the surface treatment process. The results demonstrate charge transport in ZnO nanostructures strongly depends on its surface environmental conditions and can be explained by formation of depletion layer at the surface by various surface states. A nitric oxide (NO) gas sensor using single ZNW, functionalized with Cr nanoparticles was developed. The sensor exhibited average sensitivity of ∼46% and a minimum detection limit of ∼1.5 ppm for NO gas. The sensor also is selective towards NO gas as demonstrated by a cross sensitivity test with N2, CO and CO2 gases. Graphene film on copper foil was synthesized by chemical vapor deposition method. A hot press lamination process was developed for transferring graphene film to flexible polymer substrate. The graphene/polymer film exhibited a high quality, flexible transparent conductive structure with unique electrical-mechanical properties; ∼88.80% light transmittance and ∼1.1742Ω/sq k sheet resistance. The application of a graphene/polymer film as a flexible and transparent electrode for field emission displays was demonstrated.

Effects of Natural Organic Matter on the Dissolution Kinetics and Bioavailability of Metal Oxide Nanoparticles

The rapid development of nanotechnology and wider applications of engineered nanomaterials (ENMs) in the last few decades have generated concerns regarding their environmental and health risks. After release into the environment, ENMs undergo aggregation, transformation, and, for metal-based nanomaterials, dissolution processes, which together determine their fate, bioavailability and toxicity to living organisms in the ecosystems. The rates of these processes are dependent on nanomaterial characteristics as well as complex environmental factors, including natural organic matter (NOM). As a ubiquitous component of aquatic systems, NOM plays a key role in the aggregation, dissolution and transformation of metal-based nanomaterials and colloids in aquatic environments.

The goal of this dissertation work is to investigate how NOM fractions with different chemical and molecular properties affect the dissolution kinetics of metal oxide ENMs, such as zinc oxide (ZnO) and copper oxide (CuO) nanoparticles (NPs), and consequently their bioavailability to aquatic vertebrate, with Gulf killifish (Fundulus grandis) embryos as model organisms.

ZnO NPs are known to dissolve at relatively fast rates, and the rate of dissolution is influenced by water chemistry, including the presence of Zn-chelating ligands. A challenge, however, remains in quantifying the dissolution of ZnO NPs, particularly for time scales that are short enough to determine rates. This dissertation assessed the application of anodic stripping voltammetry (ASV) with a hanging mercury drop electrode to directly measure the concentration of dissolved Zn in ZnO NP suspensions, without separation of the ZnO NPs from the aqueous phase. Dissolved zinc concentration measured by ASV ([Zn]ASV) was compared with that measured by inductively coupled plasma mass spectrometry (ICP-MS) after ultracentrifugation ([Zn]ICP-MS), for four types of ZnO NPs with different coatings and primary particle diameters. For small ZnO NPs (4-5 nm), [Zn]ASV was 20% higher than [Zn]ICP-MS, suggesting that these small NPs contributed to the voltammetric measurement. For larger ZnO NPs (approximately 20 nm), [Zn]ASV was (79±19)% of [Zn]ICP-MS, despite the high concentrations of ZnO NPs in suspension, suggesting that ASV can be used to accurately measure the dissolution kinetics of ZnO NPs of this primary particle size.

Using the ASV technique to directly measure dissolved zinc concentration, we examined the effects of 16 different NOM isolates on the dissolution kinetics of ZnO NPs in buffered potassium chloride solution. The observed dissolution rate constants (kobs) and dissolved zinc concentrations at equilibrium increased linearly with NOM concentration (from 0 to 40 mg-C L-1) for Suwannee River humic acid (SRHA), Suwannee River fulvic acid and Pony Lake fulvic acid. When dissolution rates were compared for the 16 NOM isolates, kobs was positively correlated with certain properties of NOM, including specific ultraviolet absorbance (SUVA), aromatic and carbonyl carbon contents, and molecular weight. Dissolution rate constants were negatively correlated to hydrogen/carbon ratio and aliphatic carbon content. The observed correlations indicate that aromatic carbon content is a key factor in determining the rate of NOM-promoted dissolution of ZnO NPs. NOM isolates with higher SUVA were also more effective at enhancing the colloidal stability of the NPs; however, the NOM-promoted dissolution was likely due to enhanced interactions between surface metal ions and NOM rather than smaller aggregate size.

Based on the above results, we designed experiments to quantitatively link the dissolution kinetics and bioavailability of CuO NPs to Gulf killifish embryos under the influence of NOM. The CuO NPs dissolved to varying degrees and at different rates in diluted 5‰ artificial seawater buffered to different pH (6.3-7.5), with or without selected NOM isolates at various concentrations (0.1-10 mg-C L-1). NOM isolates with higher SUVA and aromatic carbon content (such as SRHA) were more effective at promoting the dissolution of CuO NPs, as with ZnO NPs, especially at higher NOM concentrations. On the other hand, the presence of NOM decreased the bioavailability of dissolved Cu ions, with the uptake rate constant negatively correlated to dissolved organic carbon concentration ([DOC]) multiplied by SUVA, a combined parameter indicative of aromatic carbon concentration in the media. When the embryos were exposed to CuO NP suspension, changes in their Cu content were due to the uptake of both dissolved Cu ions and nanoparticulate CuO. The uptake rate constant of nanoparticulate CuO was also negatively correlated to [DOC]×SUVA, in a fashion roughly proportional to changes in dissolved Cu uptake rate constant. Thus, the ratio of uptake rate constants from dissolved Cu and nanoparticulate CuO (ranging from 12 to 22, on average 17±4) were insensitive to NOM type or concentration. Instead, the relative contributions of these two Cu forms were largely determined by the percentage of CuO NP that was dissolved.

Overall, this dissertation elucidated the important role that dissolved NOM plays in affecting the environmental fate and bioavailability of soluble metal-based nanomaterials. This dissertation work identified aromatic carbon content and its indicator SUVA as key NOM properties that influence the dissolution, aggregation and biouptake kinetics of metal oxide NPs and highlighted dissolution rate as a useful functional assay for assessing the relative contributions of dissolved and nanoparticulate forms to metal bioavailability. Findings of this dissertation work will be helpful for predicting the environmental risks of engineered nanomaterials.

Ordered mesoporous titanium oxide for thin film microbatteries with enhanced lithium storage

A 3D mesoporous TiO2 material with well-developed mesostructure is prepared in the form of a binder-free thin (100 nm) film and studied as potential candidate for the negative electrode in lithium microbatteries. By appropriate thermal treatments, the selected crystal structure (anatase, rutile, or amorphous), and micro-/mesostructure of the materials was obtained. The effects of voltage window and prelithiation treatment improved first cycle reversibility up to 86% and capacity retention of 90% over 100 cycles. After a prolonged intercalation of lithium ions in ordered mesoporous TiO2 appeared small particles assigned to Li2Ti2O4 with cubic structure as observed from ex-situ TEM micrographs. This study highlights the flexibility of the potential window to which the electrode can operate. Maximum capacity values over 100 cycles of 470 μA h cm−2 μm−1 and 177 μA h cm−2 μm−1 are obtained for voltage ranges of 0.1–2.6 V and 1.0–2.6 V, respectively. The observed values are between 6 and 2 times higher than those obtained for films with 600 nm (80 μA h cm−2 μm−1) and 900 nm (92 μA h cm−2 μm−1) lengths. This indicates that 100 nm thin TiO2 films with high accessibility show finite-length type diffusion which is interesting for this particular application.