Safe, lightweight, and cost-effective materials are required to practically store hydrogen for use in portable fuel cell applications. Compressed hydrogen and on-board hydrocarbon reforming present certain advantages, but their limitations must ultimately render them insufficient. Storage in hydrides and adsorption systems show promise in modeling and experimentation, but a practical medium remains unavailable. Since the earliest report of adsorption on single-walled carbon nanotubes (SWNT) in 1997, a number of controversial publications have claimed the hydrogen capacity of these materials to be between 0.1 to 10 wt. %. However, no study has yet demonstrated a plateau of adsorption with pressure that would verify the reported capacity. A volumetric adsorption measurement instrument was designed and constructed to resolve this controversy. The instrument is capable of degassing samples under high vacuum and offers unprecedented measurements of hydrogen storage up to a pressure of 300 atm and a broad range of temperatures. In addition, an electrical probe within the sample cell was designed to study the mechanism of adsorption in situ. The best hydrogen storage observed on bundles of purified SWNT was 1.6 wt. % at 264 atm and 200 K. At room temperature, a high-pressure plateau was found corresponding to an adsorption of 0.9 wt. % at a pressure of 300 atm, which equates to an adsorption to surface area ratio of 1.14 wt. %/l 000 m2/g. Contrary to the claim by the Caltech Group [Ye et al., 1999], resistance measurements of purified SWNT bundles revealed that bundles do not separate under high pressure. Instead, the bundles were found to compress under the action of external pressure, leading to an increase in conductivity with pressure. A simple geometrical model suggests that without this bundle separation the volume displaced by the sample may counteract the benefit gained by adsorption because of the increase in gas density at high pressure. The isosteric heat of adsorption on SWNT bundles was measured to be between 3.9 and 5.0 kJ/mol at low levels of adsorption, and the activation energy for adsorption determined by the Langmuir model was found to be 1.9 kJ/mol. These low energy parameters are indicative of weak physisorption. / Thesis / Master of Applied Science (MASc)

The discovery of nanotubes with unique mechanical, electrical, and thermal properties has led to their use in the development of the next generation of composite materials. However, their poor solubility and dispersion properties in any organic and aqueous solvents limits their potential applications. In order to improve their solubility, single-walled carbon nanotubes (SWNTs) were functionalized along their sidewalls with phenol groups using a 1,3-di^polar cycloaddition reaction. These phenols could be further derivatized with 2-bromoisobutyryl bromide, resulting in the attachment of atom transfer radical polymerization initiators to the sidewalls of the nanotubes. These initiators were found to be active in the polymerization of methyl methacrylate and t-butyl acrylate from the surface of the nanotubes. However, the polymerizations were not controlled, leading to the production of high molecular weight polymeric grafts with relatively large polydispersities. The resulting polymer carrying nanotubes were analyzed by IR, Raman spectroscopy, solid-state NMR, DSC, TEM, and AFM. The nanotubes functionalized with poly(methyl methacrylate) were found to be insoluble in organic solvents, such as THF and CH2CI2. However, the dispersion property of SWNTs in the polymer matrix was improved dramatically. Another monomer t-butyl acrylate (t-BuA) was also polymerized using the same macroinitiators. It was found that the SWNTs functionalized with t-BuA iii were soluble in a variety of organic solvents. The t-butyl groups of these appended polymers could also be removed to produce nanotubes functionalized with poly (acrylic acid), resulting in nanocomposites that are soluble in aqueous solutions. In addition, polystyrene (PS) which was prepared by stable free radical polymerization, was used to functionalize SWNTs through the radical coupling reaction. IR, NMR, TEM, and AFM confirmed that this polystyrene was covalently bonded to the SWNTs. It was also found that the resulting PS-SWNTs composites were quite soluble in organic solvents, such as THF and CH2C12. / Thesis / Master of Science (MSc)

Since their discovery in 1991, carbon nanotubes, and especially single walled carbon nanotubes (SWNTs), have attracted significant attention due to their unique structural, mechanical, and electronic characteristics. Although many potential applications for carbon nanotubes have been suggested, several key obstacles currently preclude their practical commercial applications. One of these is their lack of solubility and processability. In order to address this issue, a number of covalent and non-covalent nanotube functionalization techniques have recently been reported in the literature. These methods allow for the manipulation of nanotube properties, such as their solubility, through the attachment of various chemical moieties. Although most of these methods involve covalent attachment of structures to either the ends or sidewalls of SWNTs, several examples of non- covalent functionalization have also been reported. Pyrene, with its flat and aromatic structure, has been shown to form strong pi-pi stacking interactions with the surface of SWNTs. With this in mind, we explored several methods towards SWNT solubilization with diblock copolymers through non-covalent polymer- nanotube interactions. Living free radical polymerizations (SFRP, ATRP) were employed to produce diblock copolymers with narrow polydispersity. Commercial and synthetic monomers with different functionalities could be utilized to produce polymers with varying properties. Specifically, we used polymers such as polystyrene, poly(methyl methacrylate), poly(t-butyl acrylate) and poly(acrylic acid) as one block of our diblock copolymers. The second block was composed of synthetic pyrene-functionalized monomers mixed with different amounts of monomers that match the composition of the first block. It was found that, upon mixing these diblock copolymers with insoluble nanotubes in various solvents, the nanotubes were partially solubilized through pi-pi stacking with the pyrene- containing blocks. / Thesis / Master of Science (MS)

Single-walled carbon nanotubes (SWNTs) are a new class of materials that have recently attracted a great deal of interest because of their unique structural, mechanical, and electronic properties. Also, SWNTs have a high potential for a number of technological applications, including molecular electronics, emissive devices, and photovoltaic devices. To fully utilize their unique properties, control of the solubility, processibility, and functionality of SWNTs is required. Therefore chemical functionalization of SWNTs using a variety of methods, in either covalent or noncovalent manner, has been developed to produce soluble nanotube composites coupled with various chemical moieties. To explore the possibility of making potential soluble nanotube-based materials for solar cells, SWNTs were functionalized with organic chromophore-labeled polymers via a radical coupling process. The organic chromophore was used to absorb light to produce photo-induced electrons, while the polymer chains were used for improving the solubility of SWNTs. These novel chromophore-labeled polymers were made by stable free radical polymerization (SFRP), either using a synthetic chromophore-functionalized styrenic monomer or by derivatizing well-defined polystyrenes. Specifically, the chromophores employed in this investigation were commercially available 7-hydroxycoumarin and coumarin-343. In order to carry out fluorescence studies of SWNT-coumarin composites systematically, various factors were probed by (1) altering polystyrene lengths between the SWNT and the coumarin; (2) changing the distribution of coumarins along the polymer chain, in the form of either a block or random copolymer; (3) placing single coumarins on the surface of SWNTs. All of these resulting polymer functionalized SWNTs were found to be soluble in certain organic solvents such as CHCl3. Different absorption behaviors have been observed for SWNTs functionalized with 7-hydroxycoumarin containing copolymers. Fluorescence was still observable for all of these composites, and the pi-pi interactions between coumarins and nanotubes were believed to be responsible for the broadening of emission bands of the resulting composites. / Thesis / Master of Science (MS)

Single-w ailed carbon nanotubes (SWNTs) were oxidatively shortened and functionalized with ruthenium-based olefin metathesis catalysts. These catalyst-functionalized nanotubes were shown to be effective in the ring-opening metathesis polymerization of norbornene, resulting in rapid polymerization from the catalyst sites on the nanotube. It was found that high polymer molecular weights could be reached, and the molecular weight increased linearly with polymerization time. The resulting polynorbomene-functionalized nanotubes were found to exhibit solubility in organic solvents, while the starting materials and catalyst-functionalized nanotubes were completely insoluble. The polymerized materials were characterized by NMR, IR, DSC, AFM and TEM. Polystyrene and poly[(t-butyl acrylate)-b-styrene] with well-defined molecular weights and polydispersities were prepared by nitroxide-mediated free-radical polymerization. The homo- and block-copolymers were used to functionalize shortened single-walled carbon nanotubes (SWNTs) through a radical coupling reaction involving polymer-centered radicals generated at 125°C via loss of the stable free-radical nitroxide capping agent. The resulting polymer-SWNT composites were fully characterized and were found to be highly soluble in a variety of organic solvents. This solubility could also be altered through chemical modification of the appended polymers. The t-butyl groups of appended PtBA-b-PS could be removed to produce poly[(acrylic acid)-b-styrene]- functionalized carbon nanotubes. The resulting composite was found to form aggregates in a mixture of chloroform/methanol (v/v: 1/1), as determined by dynamic light scattering (DLS). / Thesis / Master of Science (MS)

The overall research theme of this dissertation was the study of nanoparticle/polymer composites. Two types of nanoparticles were utilized: Single-Walled Carbon Nanotubes and quantum dots. Chapter 1 of this thesis comprises an extensive literature review on Carbon Nanotubes, which presents theoretical aspects relevant to the structure and properties of CNTs, methods of purifying and solubilizing CNTs in aqueous and organic solvents and selected applications. This literature review is followed by the study and comparison of the optical limiting performances of different Single-Walled Carbon Nanotubes/conjugated polymer dispersions (Chapter 2). The results obtained are discussed in terms of dispersion of the SWNTs in the polymer solutions and resulting SWNT bundle diameters. Chapter 3 presents the spontaneous assembly of dendrimer patterns induced by SWNTs. Finally, chapter 4 presents a new method for fabricating quantum dot/polymer composites, which uses the extraction of positively charged quantum dot into a hydrophobic liquid. The resulting solution is used as a compatible polymerization medium for poly(methylmethacrylate ) networks enabling the formation of transparent and fluorescent composites. / Ph. D.

Single walled carbon nanotubes (SWNTs) are considered potential biomedical materials because of their flexible structure, hollow interior for fluidic transport, propensity for functionalization of the exterior walls, and biocompatibility. Research into exploiting these properties has focused on SWNTs as building blocks for novel drug-delivery systems, dosage forms, and biomedical substrates. However, the use of the internal nanochannels as conduits for trans-membrane drug delivery has not been explored. This research was initially designed to explore the latter.<p> It is postulated that due to their mechanical strength and the presence of an internal conduit, SWNTs can be used for nanofluidic transport. Using a magnetic field, the magnetically responsive SWNT are driven into intact stratum corneum, creating nanochannels, for trans-membrane drug delivery. Initial studies showed however that a bottleneck is the aggregation of SWNTs on the surface of stratum corneum. To achieve trans-membrane nanofluidic delivery, the SWNTs have to be well dispersed in an appropriate pharmaceutical medium, and the SWNT have to be of high purity. Similarly, the presence of impurities in SWNTs, and the dispersion state of these materials in pharmaceutical solvents may give an insight into the discrepancies in toxicity that is reported.<p> The purity of five commercially available SWNTs (AP-SWNT and P2-SWNT, from Carbon Solutions Inc, HMS-SWNT from Helix Materials, and NA-SWNT from Nanostructured and Amorphous Materials Inc. and CT-SWNT from ChepTubes Inc.) were analyzed by raman and electron dispersive x-ray spectroscopy (EDS) spectroscopy. Secondly, the dispersion states of SWNTs in various pharmaceutical solvents were evaluated by ultraviolet (UV) spectroscopy, scanning electron microscopy (SEM), dynamic light scattering (DLS), zeta potential, and Raman spectroscopy to identify potential agents for exfoliation of SWNTs in selected pharmaceutical solution.<p> SWNTs were dispersed in various solvents (water, propylene glycol [PG], dimethylsulfoxide [DMSO], and ethanol) as well as in 0.1% w/v aqueous solutions of anionic, cationic and neutral surfactants at a SWNT concentration of 0.1 mg/mL. SWNT suspensions described as dispersed yielded an evenly coloured suspension with no visible precipitate. The most stable dispersions were obtained with the gemini surfactants, which were confirmed by SEM observation of exfoliated SWNTs. Zeta (î) potential measurements of the fully dispersed SWNTs showed typical values of greater than +30 mV, while non-dispersed samples were less than +20 mV. SEM images of the dispersed solution showed the presence of exfoliated SWNTs compared to the aggregated SWNT clusters observed in non-dispersed systems. Raman spectra of dispersed SWNTs showed G-band peak shifts (to higher wavelengths), confirming the presence of exfoliated SWNTs.<p> Even though the purity of SWNT did not correlate with amount of SWNT in dispersion, exfoliation of bundled SWNTs was accompanied by an increase in UV absorbance of the dispersion, with maximum exfoliation determined by a relatively stable UV absorbance.<p> As pharmaceutical excipients, we have demonstrated that gemini surfactants are suitable dispersing agents for SWNTs, and shown that the dispersion of SWNT for gemini surfactants (12-3-12) is achieved below the critical micelle concentration. The dispersion of SWNT bundles into individual strands is the first crucial step towards their use in biological systems as drug carriers.

Single walled carbon nanotubes (SWNTs) are considered potential biomedical materials because of their flexible structure, hollow interior for fluidic transport, propensity for functionalization of the exterior walls, and biocompatibility. Research into exploiting these properties has focused on SWNTs as building blocks for novel drug-delivery systems, dosage forms, and biomedical substrates. However, the use of the internal nanochannels as conduits for trans-membrane drug delivery has not been explored. This research was initially designed to explore the latter.<p> It is postulated that due to their mechanical strength and the presence of an internal conduit, SWNTs can be used for nanofluidic transport. Using a magnetic field, the magnetically responsive SWNT are driven into intact stratum corneum, creating nanochannels, for trans-membrane drug delivery. Initial studies showed however that a bottleneck is the aggregation of SWNTs on the surface of stratum corneum. To achieve trans-membrane nanofluidic delivery, the SWNTs have to be well dispersed in an appropriate pharmaceutical medium, and the SWNT have to be of high purity. Similarly, the presence of impurities in SWNTs, and the dispersion state of these materials in pharmaceutical solvents may give an insight into the discrepancies in toxicity that is reported.<p> The purity of five commercially available SWNTs (AP-SWNT and P2-SWNT, from Carbon Solutions Inc, HMS-SWNT from Helix Materials, and NA-SWNT from Nanostructured and Amorphous Materials Inc. and CT-SWNT from ChepTubes Inc.) were analyzed by raman and electron dispersive x-ray spectroscopy (EDS) spectroscopy. Secondly, the dispersion states of SWNTs in various pharmaceutical solvents were evaluated by ultraviolet (UV) spectroscopy, scanning electron microscopy (SEM), dynamic light scattering (DLS), zeta potential, and Raman spectroscopy to identify potential agents for exfoliation of SWNTs in selected pharmaceutical solution.<p> SWNTs were dispersed in various solvents (water, propylene glycol [PG], dimethylsulfoxide [DMSO], and ethanol) as well as in 0.1% w/v aqueous solutions of anionic, cationic and neutral surfactants at a SWNT concentration of 0.1 mg/mL. SWNT suspensions described as dispersed yielded an evenly coloured suspension with no visible precipitate. The most stable dispersions were obtained with the gemini surfactants, which were confirmed by SEM observation of exfoliated SWNTs. Zeta (î) potential measurements of the fully dispersed SWNTs showed typical values of greater than +30 mV, while non-dispersed samples were less than +20 mV. SEM images of the dispersed solution showed the presence of exfoliated SWNTs compared to the aggregated SWNT clusters observed in non-dispersed systems. Raman spectra of dispersed SWNTs showed G-band peak shifts (to higher wavelengths), confirming the presence of exfoliated SWNTs.<p> Even though the purity of SWNT did not correlate with amount of SWNT in dispersion, exfoliation of bundled SWNTs was accompanied by an increase in UV absorbance of the dispersion, with maximum exfoliation determined by a relatively stable UV absorbance.<p> As pharmaceutical excipients, we have demonstrated that gemini surfactants are suitable dispersing agents for SWNTs, and shown that the dispersion of SWNT for gemini surfactants (12-3-12) is achieved below the critical micelle concentration. The dispersion of SWNT bundles into individual strands is the first crucial step towards their use in biological systems as drug carriers.

In order to find/design porous materials that could be used in practical applications involving adsorption, it is important to investigate the basic properties (i.e. isosteric heat, specific surface area, binding energy, pore size, pore volume, etc.) of each material. With this aim in mind we have looked at three different types of materials: single-walled carbon nanotubes (prepared by the HiPco and laser methods), single-walled nanohorns (dahlia-like and bud-like) and metal-organic frameworks (Cu-BTC and RPM-1). For these substrates we have measured volumetric adsorption isotherms using several gases such as neon, argon, tetrafluoromethane (CF4), xenon, and methane (not all gases for all substrates). Experimental adsorption isotherms were measured using methane, argon, xenon, and neon gases on unpurified single-walled carbon nanotubes prepared by the HiPco method. The main idea behind these experiments was to investigate, using different size gas molecules, the sites available for adsorption on this type of porous material. We found that surface area occupied by these adsorbates on the sample is the same, regardless of their size. This means that all the gases have access to the same group of adsorption sites. Since the biggest adsorbate in this experiment was Xe, and since it is unlikely that it could penetrate the interstitial channels in the nanotube bundles, we conclude that none of the gases, including the smallest one - Ne, are able to adsorb in the interstitial channels in bundles of single-walled carbon nanotubes. For the case of argon on laser produced single-walled carbon nanotubes we measured 21 adsorption isotherms using argon gas temperatures between 40 and 153 K that were used to determine the isosteric heat of adsorption for this system. Our experimental results were compared to the ones from computer simulations performed by J. K. Johnson (from the University of Pittsburgh) for the same gas on heterogeneous and homogenous bundles. It was observed that the isosteric heat data matches better with data computed for heterogeneous nanotube bundles. This indicates that at the lowest pressure and coverages argon might be adsorbing in the defect-induced interstitial channels. We studied Cu3(Benzene-1,3,5-tricarboxylate)2(H2O)3 (abbreviated as Cu-BTC) metal-organic framework with argon to determine the sites available for adsorption on this material. Volumetric adsorption isotherms were measured at temperatures between 66 and 143 K. We found two substeps in the isotherm data, indicating that there are two types of pores present in the material: tetrahedrally-shaped side pockets and the main channels. Our experimental results were compared with data from simulations conducted using the Grand Canonical Monte Carlo method. We determined that the theoretical results match reasonably well with ours if the coverage is scaled down by a factor of 1.6. We explored the potential of two different metal-organic framework materials (Cu-BTC and RPM-1) for gas separation application. We used argon and tetrafluoromethane (CF4) gases to check if this can be achieved through kinetic and steric mechanisms. We found that Cu-BTC has excellent potential in gas separation using a steric mechanism, since argon easily adsorbs into the small pores present in the sample, while CF4 is excluded from them. Adsorption properties of RPM-1 showed that it could be employed in gas separation using a kinetic mechanism - argon gas adsorbs and reaches equilibrium in the pores of the sample more than the order of magnitude faster than CF4. Closed-ended dahlia-like nanohorns were studied with neon and tetrafluoromethane gases. In the first layer of neon and tetrafluoromethane adsorbed on dahlia-like nanohorns we found two substeps. These results were compared with results of computer simulations performed by Prof. M. Calbi. We determined, after comparison with the simulation isotherms, that the lower pressure substeps correspond to adsorption of Ne and CF4 in the narrowest parts of interstitial channels of the aggregates. Surface area calculated from neon isotherms was found to be higher than the one obtained using CF4, meaning that the smaller Ne molecule has the access to the parts of the interstitial channels that are not accessible for the bigger CF4 molecule. Features that appeared in neon adsorption isotherms on bud-like nanohorn aggregates were quite different from the ones on dahlia-like aggregates. We measured neon adsorption isotherms on this type of sample at temperatures between 22 and 49 K. In the monolayer regime we observed one single substep whose origin we can not definitely identify, because the structure of the bud-like nanohorns is not well-known. The binding energy value that was calculated from the isotherm data was lower than the value for neon adsorbed in the grooves of nanotube bundles but higher than for neon on graphite.

Carbon nanomaterials have attracted significant attention in the past decades for their unique properties and potential applications in many areas. This dissertation addresses the preparation, functionalization and potential biomedical applications of various carbonaceous nanomaterials. Trimetallic nitride template endohedral metallofullerenes (TNT-EMFs, M₃N@C₈₀, M = Gd, Lu, etc.) are some of the most promising materials for biomedical applications. Water-soluble Gd₃N@C₈₀ was prepared by the functionalization with poly(ethylene glycol) (PEG) and hydroxyl groups (Gd₃N@C₈₀[DiPEG(OH)ₓ]). The length of the PEG chain was tuned by changing the molecular weight of the PEG from 350 to 5000. The 1H magnetic resonance relaxivities of the materials were studied at 0.35 T, 2.4 T and 9.4 T. Their relaxivities were found to increase as the molecular weight of the PEG decreased, which is attributed to the increasing aggregate size. The aggregate sizes were confirmed by dynamic light scattering. In vivo study suggested that Gd3N@C₈₀[DiPEG(OH)x] was a good candidate for magnetic resonance imaging (MRI) contrast agents. Another facile method was also developed to functinalize Gd₃N@C₈₀ with both carboxyl and hydroxyl groups by reaction with succinic acyl peroxide and sodium hydroxide thereafter. The product was determined to be Gd₃N@C₈₀(OH)~₂₆(CH₂CH₂COOM)~₁₆ (M = Na, H) by X-ray photoelectron spectrometry. The Gd₃N@C₈₀(OH)~₂₆(CH₂CH₂COOM)~₁₆ also exhibited high relaxivity, and aggregates in water. The research on both pegylated and carboxylated Gd₃N@C₈₀ suggests that aggregation and rotational correlation time plays an important role in relaxation, and the relaxivities and aggregation of the water-soluble metallofullerenes can be tuned by varying the molecular weight of the functionality. TNT-EMFs can be encapsulated inside single-walled carbon nanotubes (SWNTs) to form "peapod" structures by heating the mixture of TNT-EMFs and SWNTs in a vacuum. The peapods were characterized by Raman spectrometry and transmission electron microscopy (TEM). The peapods were then functionalized with hydroxyl groups by a high speed vibration milling (HSVM) method in the presence of KOH. The functionalized Gd-doped peapods exhibited high relaxivites and had an additional advantage of "double carbon wall" protection of the toxic Gd atoms from possible leaking. The HSVM method was modified by using succinic acyl peroxide. The modified HSVM method could functionalize multi-walled carbon nanotubes (MWNT) and single-walled carbon nanohorns (SWNHs) with carboxyl groups. In the presence of N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride (EDC), carboxylate MWNTs and SWNHs could be conjugated with CdSe/ZnS quantum dots (QDs). TNT-EMFs were also encapsulated inside SWNHs to form SWNH peapods. SWNH peapods were functionalized by the modified HSVM method and then were conjugated with CdSe/ZnS QDs. The peapods were characterized by TEM. In vitro and in vivo studies indicated that SWNH peapods could serve as a multimodal diagnostic agent: MRI contrast agent (Gd₃N@C₈₀ encapsulated), radio-active therapeutic agent (Lu₃N@C₈₀ encapsulated) and optical imaging agent (QDs). / Ph. D.