A study is presented on the synthesis and characterization of nanoporous AgPt and AgAu alloys after annealing and dealloying in 5% HClO4. Dealloying removes the less-noble atom from the alloy surface to produce nanoporous, highly-interconnected ligaments. Voltammetry of AgPt and AgAu shows the critical potential, Ec, at various potential scan rates. Potential hold current decay experiments on Ag-23Pt and Ag-23Au further show the intrinsic Ec to be 275 mV and 290 mV, respectively. Ec was governed by thermodynamic clustering in the alloys as opposed to dissolution-diffusion kinetic effects. EDX shows the starting 77Ag-23Pt material changes composition after dealloying to about 12Ag-88Pt. XRD indicates the presence of ordering in AgPt via a superlattice (100)-peak for a specific anneal treatment. EIS measurements done on as-annealed and dealloyed AgPt and AgAu samples show the onset of bulk porosity and show that capacitance increase is equal for both alloys at two different dealloying potentials.

If solar energy is to be a significant component of our energy supply, technologies are required which produce high efficiency solar cells using inexpensive materials and versatile manufacturing processes. Solution-processed materials have been used to create low cost, easily fabricated devices, but have suffered from low power conversion efficiencies. A lack of infrared energy capture limits their efficiency. In this work we develop solution-processed photovoltaic devices using lead sulphide quantum dots and high surface area porous oxide electrodes. The resultant devices have a spectral response from 400 to 1800 nm. In fabricating these devices we utilize crosslinking molecules. We explore the impact crosslinkers have on the mobility and morphology of quantum dot films using field effect transistors and transmission electron microscopy. We also explore a hybrid organic/inorganic route for controlling the net doping in quantum dot films. We investigate the chemical and compositional changes that lead sulphide quantum dots films undergo during crosslinker treatment and annealing. Using this information we optimize our charge separation efficiency and our open circuit voltage. The resulting devices have an infrared power conversion efficiency of 2%, four orders of magnitude higher than that in previously reported lead sulphide quantum dot devices.

If solar energy is to be a significant component of our energy supply, technologies are required which produce high efficiency solar cells using inexpensive materials and versatile manufacturing processes. Solution-processed materials have been used to create low cost, easily fabricated devices, but have suffered from low power conversion efficiencies. A lack of infrared energy capture limits their efficiency. In this work we develop solution-processed photovoltaic devices using lead sulphide quantum dots and high surface area porous oxide electrodes. The resultant devices have a spectral response from 400 to 1800 nm. In fabricating these devices we utilize crosslinking molecules. We explore the impact crosslinkers have on the mobility and morphology of quantum dot films using field effect transistors and transmission electron microscopy. We also explore a hybrid organic/inorganic route for controlling the net doping in quantum dot films. We investigate the chemical and compositional changes that lead sulphide quantum dots films undergo during crosslinker treatment and annealing. Using this information we optimize our charge separation efficiency and our open circuit voltage. The resulting devices have an infrared power conversion efficiency of 2%, four orders of magnitude higher than that in previously reported lead sulphide quantum dot devices.

Cette thèse présente une étude théorique du transport de chaleur dans les matériaux composites nano poreux et nano fils ainsi qu'une étude théorique des propriétés thermoélectriques de l'alliage Si0:8Ge0:2 confrontée à des mesures expérimentales réalisées pour une partie, dans le cadre de l'étude.La première étude démontre que les alliages poreux affichent des réductions de conductivité thermique à des dimensions de pores beaucoup plus grandes que les matériaux poreux non alliés de même porosité nominale. Si on considère une taille de pores de 1000nm, la conductivité thermique de l'alliage Si0:5Ge0:5 avec 0:1 de porosité est deux fois plus faible que la conductivité thermique d'un matériau non poreux, alors que les pores plus petits que 100 nm sont nécessaires pour obtenir la même réduction relative dans le Si ou Ge pur. Nos résultats indiquent que les alliages nano poreux devraient être avantageux devant les matériaux nano poreux non alliés, et ceux pour les applications nécessitant une faible conductivité thermique, tels que les nouveaux matériaux thermoélectriques.La deuxième étude théorique sur la conductance thermique de nano fils révèle l'effet de la structure sur le transport des phonons. Avec un modèle théorique qui considère la dépendance en fréquence du transport des phonons, nous sommes en mesure quantitativement de rendre compte des résultats expérimentaux sur des nano fils droits et coudés dans la gamme de température qui montre qu'un double coude sur un fil réduit sa conductance thermique de 40% à la température de 5K. Enfin, nous avons procédé à une approche théorique des propriétés thermoélectriques des alliages SiGe frittés, en les comparant aux mesures expérimentales nouvelles et antérieures, tout en évaluant leur potentiel d'amélioration. L'approche théorique a été validée par comparaison de la mobilité prévue et la conductivité thermique prévues, en faisant varier la quantité de Ge et les concentrations de dopage, dans une gamme de température comprise entre 300 et 1000K. Nos calculs suggèrent qu'une optimisation par rapport à l'état de l'art actuel est possible pour le matériau de type n et type p, conduisant potentiellement à une augmentation de 6% (5%) du ZT _a 1000K et 25% (4%) _a température ambiante. Même des améliorations plus grandes devraient être possibles si la probabilité de diffusion des phonons aux joints de grains pouvait être augmentée au-delà de sa valeur actuelle de 10%. / This dissertation presents a theoretical study of heat transport in nanoporous composites andin nanowire and also theoretical study of thermoelectric properties of the Si0:8Ge0:2 alloywith some experimental new and old measurements.The first study on the porous alloys show that its can display thermal conductivity reductionsat considerably larger pore sizes than nonalloyed porous materials of the same nominalporosity. The thermal conductivity of Si0:5Ge0:5 alloy with 0.1 porosity becomes half thenonporous value at 1000 nm pore sizes, whereas pores smaller than 100 nm are required toachieve the same relative reduction in pure Si or Ge. Using Monte Carlo simulations, we alsoshow that previous models had overestimated the thermal conductivity in the small pore limit.Our results imply that nanoporous alloys should be advantageous with respect to nanoporousnonalloys, for applications requiring a low thermal conductivity, such as novel thermoelectrics.The second theoretical study on the nanowire thermal conductance reveals the structureeffect on the phonon transport. With a theoretical model that considers the frequency dependenceof phonon transport, we are able to quantitatively account for the experimental resultsof straight and bent nanowires in the whole temperature range which shows that due to andouble bend on the straight thermal conductance reduced by 40% at temperature 5K.Finally, we theoretically investigate the thermoelectric properties of sintered SiGe alloys,compare them with new and previous experimental measurements, and determine their potentialfor further improvement. The theoretical approach is validated by extensive comparisonof predicted bulk mobility, thermopower, and thermal conductivity, for varying Ge and dopingconcentrations, in the 300 �� 1000K temperature range. The effect of grain boundariesis then included for Si0:8Ge0:2 sintered nanopowders , and used to predict optimized valuesof the thermoelectric figure of merit at different grain sizes. Our calculations suggest thatfurther optimization of current state of the art n-type (p-type) material would be possible,possibly leading to 6% (5%) ZT enhancement at 1000K and 25% (4%) at room temperature.Even larger enhancements should be possible if the phonon scattering probability of the grainboundaries could be increased beyond its present value of 10%.

Nanoporous gold is an exciting topic that has been highly researched due to its potential in applications including sensing, catalysts, gas storage, and heat exchangers, made possible by its high surface area to volume ratio and high porosity. However, these applications tend to require a specific morphology, which is often difficult to control. In this work, significant strides have been made in tuning the morphology of nanoporous gold by studying the effect of different fabrication parameters on the ligament diameter, pore diameter, and ligament length, three characteristics which are most discussed in previous studies concerning nanoporous gold. This material also, generally shows a brittle behavior despite it consisting of a normally ductile constituent element, limiting many commercial applications. There have been multiple simulated studies on the tensile mechanical properties and the fracture mode of this material, but limited experimental tensile testing research exists due to technical difficulty of conducting such experiments with small fragile samples. We examine the tensile mechanical behavior of nanoporous gold with ligament sizes ranging from 10 to 30 nm using in situ tensile testing under an environmental scanning electron microscope (ESEM). A specially designed tensile stage and sample holders are used to deform the sample inside the ESEM, allowing us to observing both the macro and microscopic structure changes. Our experimental results advance our understandings of how porous structure influence the mechanical properties of nanoporous gold, and they also serve to increase the accuracy of future simulation studies that will take this material a step towards commercial use by providing a thorough understanding of its structural mechanical limitations. / MS

Nanoporous materials have attracted tremendous interest, investment and effort in research and development due to their potential applications in various areas such as membranes, catalysis, sensors, delivery, and micro devices. Controlling a nanoporous material’s microstructure is of great interest due to the strong influence on efficiency and performance. For particles, microstructure refers to particle size, shape, surface morphology, and composition. When discussing thin films, microstructure includes film thickness, crystal orientation and grain boundaries. In this respect, we focus to develop novel methods for the synthesis and characterization of nanoporous materials and their films, which are capable of controlling the microstructure of material. This dissertation is composed of two main sections and each explores the fabrication of a different nanoporous material: 1) A simple fabrication method for producing oriented MFI zeolite membranes with controlled thickness, orientation, and grain boundary; 2) A microfluidic synthesis of ordered mesoporous silica particles with controllable size, shape, surface morphology, and composition. The first section of this dissertation demonstrates a simple and commercially viable method termed the micro-tiles-and-mortar method to make continuous b-oriented MFI membranes with controlled membrane microstructure. This simple method allows for control of the thickness of the membrane by using plate-like seed crystals with different thicknesses along the b-axis (0.5 μm to 2.0 μm), as well as to manipulate the density and structure of grain boundaries. Microstructural effects of silicalite-1 membranes on the gas separation are investigated by measuring the permeation and separation for xylene isomers. In the second section of this dissertation, a new synthesis method for the ordered mesoporous silica particles with controllable microstructure is demonstrated. This novel method combines a microfluidic emulsification technique and nonaqueous inorganic synthesis with a diffusion-induced self-assembly (DISA). The systematic control of the particle microstructure such as size, shape, and surface morphology is shown by adjusting microfluidic conditions.

Nanoporous (NP) metals are a unique class of materials that are characterized by extremely high surface-to-volume ratios and possess such desirable properties of metals as high electrical conductivity, catalytic activity, and mechanical strength. At the same time, understanding of their physical properties is often lacking, especially for hierarchical NP metals where individual struts and joints that make up open cell 3D network are nanocrystalline. The aim of this work is to employ a dedicated experimental campaign to understand the structure property relation of nanostructured nanoporous metals. Towards this goal, NP Pt and NP Cu have been synthesized for a range of strut sizes and their mechanical properties have been investigated via ex-situ and in-situ nanoindentation experiments. Both NP Pt and NP Cu exhibit relatively high hardness in the range of 0.2 to 1.3 GPa. The relative role of material effects arising from small dimensions of the struts/joints and the geometrical features of NP metals are discussed. Selected applications of the systems synthesized during this work in electrochemistry and catalysis are demonstrated. In the examined applications the NP metals exhibited catalytic activity comparable to or significantly exceeding the best available alternative systems, while offering superior stability.

Nanostructured noble metals exhibit novel physical, mechanical and chemical behavior, and hold promise for applications such as gas sensing and electron emission. A strong emphasis was placed on the processing and characterization of these materials, in the form of nanoporous or nanocrystalline thin films. Palladium-based and osmium-ruthenium alloys were investigated in this dissertation research and will be presented as follows: (1) Preparation and Characterization of Nanoporous Metal Thin Films (2) Characterization of Osmium-Ruthenium Coatings Nanoporous palladium (np-Pd) thin films were prepared by dealloying co-sputtered palladium-nickel precursor alloys. Nanoporous structures were created with 3-D interconnected ligaments and open pores. Size of ligaments and pores was ~5 nm, achieved with a novel processing method developed in this study. Hydrogen cycling tests performed with np-Pd films demonstrated a significant improvement in sensitivity to hydrogen and response time for sensing. Effects of alloying element (Ni), film thickness, local stress and pore/ligament size on hydrogen cycling behavior were investigated in detail. Additionally, nanoporous gold and gold-palladium thin films were studied to clarify the evolution of microstructure during dealloying, including the formation of nanoporous structure and effects of substrate curvature on dealloying behavior. The results from this project have yielded a new understanding of dealloying as well as an ideal coating material for hydrogen sensing. Nanocrystalline osmium-ruthenium (Os-Ru) thin films were deposited on porous tungsten substrates with varied sputtering parameters. These parameters were mapped to microstructure, film texture and film composition in samples that were comparable to commercial devices. Using this map, Os-Ru films can be produced with higher stability during annealing and/or high-temperature operation. These results should lead to Os-Ru top coatings that increase the lifetime and emission performance of dispenser cathodes.

Abstract NEW SYNTHETIC STRATEGIES FOR IMPROVED GAS SEPARATION BY NANOPOROUS ORGANIC POLYMERS Suha S. Altarawneh, Ph.D. The emission of carbon dioxide (CO2) from fossil fuel combustion is a major cause of climate change. Therefore, the efficient separation of CO2 from mixtures of gases such as flue gas and impure sources of CH4 (e.g. natural gas and landfill gas) is an essential step in meeting the ever increasing demands on natural gas and creating a cleaner environment. Carbon capture and storage technology (CCS) is one of the methods employed for gas separation using chemisorption and/or physisorption processes. Several materials such as porous polymers and amine solutions have been used as gas adsorbents. However, the amount of energy required for the adsorbent regeneration is one of the main concerns that needs to be addressed. In this regard, porous organic polymers (POPs) with defined porosity and preferential binding affinity for CO2 over N2 and CH4 are some of the most attractive materials that could fulfill the above requirement and are also applicable for use in gas storage and separation. Suitable POPs that can be used for gas storage applications need to have high porosity and mechanical stability under high pressure conditions (~100 bar). Alternatively, the most effective POPs in gas separation are those that have preferential binding affinity for CO2 over other gases present at low pressure settings. In all cases, the chemical nature of POPs and their textural properties are key parameters, however, the modest surface area of most POPs limits their efficiency. With the above considerations in mind, the aim of our research is to develop benzimidazole–linked polymers (BILPs) that have variable porosity levels and chemical functionality to enhance gas separation (CO2/CH4, CO2/N2). We have established new synthetic routes that utilize polycondensation reactions between aryl-aldehydes and aryl-o-diamine building units to construct new BILPs with improved gas separation properties. Our strategy targeted structural and textural modifications of BILPs. We used longer linkers (building units) to improve porosity; however, the flexible linkers offered only low porosity due to network interpenetration. To overcome this challenge, a more controlled network growth rate was assessed by adjusting imine-bond formation rates through different acid loading. The acid, HCl, was used to catalyze imine-bond formation. The new resulting acid-catalyzed BILPs have shown an improved porosity up to 92% compared to the non-catalyzed BILPs. We also used the “rational ligand design” approach to introduce new functionalities into BILPs (-OR) to alter the hydrophobic nature of their pores. In this regard, we have illustrated the applicability of this strategy to BILPs containing flexible aryl-o-diamine linkers. The bulky alkoxy groups were incorporated into the aryl-aldehyde building unit prior to polymerization. The resulting polymers have proven that the presence of the bulky pendant alkoxy-chains plays a significant role during the polymerization process which allows for increased control over network formation, and in turn, porosity. Sorption measurements, selectivity, and heats of adsorption data have confirmed the positive impact of the alkoxy-groups and shown that varying the pendant groups is a promising method for designing highly porous BILPs. In addition to pore functionalization with alkoxy-chains, we used pi-conjugated and N-rich building units to prepare new BILPs that have semiconducting properties in addition to their porous nature. This class of BILPs has shown that the extended-conjugated system improved BILPs electronic properties. The other studies performed in this research, involved the use of DFT theory to investigate CO2/BILPs interaction sites and binding affinities. The computational outcomes of DFT have shown that (C-H) bond of the aryl system is a possible site for CO2 interaction beside the free-N side and hydrogen bonding. All new polymers were characterized by spectral and analytical characterization methods and their sorption data were collected to evaluate their capability as candidates for gas separation applications.

Porous organic polymers (POPs) received great attention in recent years because of their novel properties such as permanent porosity, adjustable chemical nature, and remarkable thermal and chemical stability. These attractive features make POPs very promising candidates for use in gas separation and storage applications. In particular, CO2 capture and separation from gas mixtures by POPs have been intensively investigated in recent years because of the greenhouse nature of CO2, which is considered a leading cause for global warming. CO2 chemical absorption by amine solutions from the flue gas of coal-fired power plants suffers from several challenges such as high-energy consumption in desorption, chemical instability, volatility, and corrosive nature, limiting the widespread use of this technology. To mitigate these limitations, new adsorbents with improved CO2 capturing properties need to be designed, synthesized, and tested. Alternatively, the use of cleaner fuels such as methane can reduce CO2 release or completely eliminates it in the case of hydrogen. However, the on-board storage of methane and hydrogen for automotive applications remains a great challenge. With these considerations in mind, our research goals in this dissertation focus on the systematic design and synthesis of N-rich POPs and their use in small gas (H2 and CH4) storage as well as selective CO2 capture from gas mixtures. In particular, we have studied the effect of integrating pyrene and triazine building units into benzimidazole-linked polymers (BILPs) and covalent organic frameworks (COFs) on gas storage and separation. We have found that pyrene-based BILPs exhibit remarkable selective CO2 capturing capacities under industrial settings (VAS, PSA). However the methane and hydrogen storage capacities of BILPs were found to be only modest especially at high pressure due to their moderate surface area and pore volume. We addressed these limitations by the synthesis of a highly porous imine-linked COF (ILCOF-1), which has very high surface area and improved hydrogen and methane uptakes when compared to BILPs. We have demonstrated that the use of pyrene in BILPs and COFs can direct frameworks growth through - stacking and improve porosity and pore volume whereas the use of triazine is instrumental in improving the binding affinity of the frameworks towards CO2.