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Injecting CO2 into unconventional reservoirs to enhance oil recovery has been widely studied due to its potential to improve the profitability of these reservoirs. CO2 Huff-n-Puff is emerging as a promising method, but exploiting its full potential is challenging due to difficulties in optimizing its operations. The latter arises from the limited understanding of CO2 and oil transport in unconventional reservoirs. This dissertation used molecular dynamics simulations to study the storage and transport of oil and CO2 in unconventional reservoirs in single nanopores. The first study examined the modulation of oil flow in calcite pores by CO2. It is discovered that CO2 molecules adsorb strongly on calcite walls and can change decane permeability through 8 nm-wide pores by up to 30%. They impede decane flow at moderate adsorption density but enhance flow as adsorption approaches saturation. The second study investigated the CO2 transport in 4 nm-wide calcite pores during the soaking phase of Huff-n-Puff operations. CO2 entering the pore can become adsorbed on pore walls and diffuse on them or diffuse as free CO2 molecules. The accumulation of CO2 follows a diffusion behavior with an effective diffusivity ~50% smaller than bulk CO2. Two dimensionless groups are proposed to gauge the importance of surface adsorption and diffusion in CO2 storage and transport in nanopores. The third study examined the extraction of decane initially sealed in a 4 nm-wide calcite pore through exchange with CO2 and CH4 in a reservoir. The CO2-decane exchange is significantly driven by the evolution of adsorbed oil and gas initially, but a transition to dominance by free oil and gas occurs later; for CH4-decane exchange, the opposite occurs. The net gas accumulation and decane extraction follow the diffusive law, but their effective diffusivities do not always align well with the self-diffusion coefficients of CO2, CH4, and decane in the nanopore. The three studies identified the essential roles of gas/oil adsorption in their net transport in nanopores and, thus, unconventional reservoirs. Delineating these roles and formulating dimensionless groups to gauge their importance help develop better models for enhanced oil recovery from unconventional reservoirs by CO2 injection. / Doctor of Philosophy / Unconventional reservoirs are hydrocarbon-bearing formations with ultralow permeabilities, and they have emerged as a critical source of liquid petroleum production in the United States over the past decade. However, because oil is trapped in nanoscale pores in these reservoirs, the oil recovery rate is low. Therefore, many methods have been developed to enhance the oil recovery from unconventional reservoirs. One of the popular methods is to inject gas into reservoirs to enhance oil recovery. Improving this method's efficacy requires a fundamental understanding of the thermodynamic and transport phenomena underlying its operation is needed. This dissertation used molecular dynamics simulations to study the storage and transport of oil and CO2 in unconventional reservoirs at the single nanopore scale. Three series of studies have been performed to elucidate how CO2 modulates the flow of oil inside nanopores, how CO2 enters a nanopore filled with oil, and how oil is extracted from the nanopore by the ingression of CO2. These studies showed that when CO2 molecules adsorb strongly on a nanopore's walls, they can either enhance or impede the permeation of oil through the pore. The ingression of CO2 into an oil-filled nanopore and the concurrent oil extraction can be described by the same equation for the conduction of heat in one-dimensional objects. The CO2 ingression and oil extraction rates are heavily affected by the adsorption of CO2 and oil on the nanopore's walls. These results highlight the important effects of surface adsorption on the storage and transport of gas and oil in nanopores and, thus, unconventional oil reservoirs. Incorporating these effects into oil recovery models will improve their predictive power, and thus help model-guided optimization of oil recovery.

The atmosphere is a heterogeneous system which is rich in potential chemistry. The processes taking place within this system as well as at the interface of its constituents are of immense importance in understanding how the atmosphere in turn can impact the well-being of all living on the surface of earth. Thus, the heterogeneous chemistry of atmospheric aerosols has since long been subjected to extensive scientific investigation, in view of broadening our understanding of this imperative system. In this study, the heterogeneous interactions of water vapor and gaseous HNO3 on goethite (a-FeOOH), a prominent component of mineral dust aerosol is investigated with quartz crystal microbalance (QCM) measurements and attenuated total reflectance - Fourier transform IR (ATR-FTIR) spectroscopy. Laboratory synthesized goethite samples of varying size (microrods of specific surface area 34 m2/g and nanorods of specific surface area 121 m2/g) were used in order to identify the size dependent interaction of goethite with H2O and HNO3. The study revealed that the exposure of goethite to gas phase H2O and HNO3 results in the uptake of these gases via surface adsorption. Additionally, this novel combined approach of QCM and ATR-FTIR spectroscopy allowed for quantification of the amount of uptake while the spectroscopic data provided information on the speciation of adsorbed products. Thus, with the QCM and spectroscopic data in hand, a precise interpretation of the reactivity as well as its size dependence was sought. In a general sense, the reactivity of a substance is believed to increase with decreasing particle size. The results of this investigation show that in the case of H2O, both microrods and nanorods take up water while the total amount of adsorbed water, when normalized to surface area, is similar for both particle sizes. However, for HNO3, the saturation coverage of total and irreversibly bound HNO3 on microrods was observed to be higher than that on nanorods. With supplementary analysis, this anomalous size effect was attributed to structural features such as the involvement of surface hydroxyl groups in determining the reactivity, which would be subjected to change as a function of particle size. Furthermore, an investigation of the behavior of HNO3 reacted goethite in aqueous media and the uptake of H2O and HNO3 at their mutual presence was carried out such as to better understand the effects of atmospheric processing upon dispersal within the hydrosphere. Further analysis is warranted before arriving at a general conclusion on the size-dependent reactivity of goethite. However, we may argue that goethite containing aerosols may indicate the same pattern of reactivity within the atmosphere as that observed here. Thus, the inference of this investigation proves to be significant in broadening our understanding of this atmosphere as well as the entire biosphere as a whole.

Nanoparticles have gained growing attention of the scientific community over the past few decades due to their high potential to be used in diverse industrial applications. Nanoparticles often possess superior characteristics, such as catalytic activity, photochemical activity, and mechanical strength, compared to their bulk counterparts, making them more desirable in different industrial applications. During the past few decades, the use of the nanoparticles in various industries has been increased. With increasing usage release of nanoparticles into the environment has also increased. There is a growing concern about the nanoparticle toxicity and numerous studies have shown the toxic effects of different nanoparticles on various plants, animals, and microorganisms in the environment. Toxicity of nanoparticles is often attributed to their morphology and their ability to undergo different transformations in the environment. These transformations include aggregation, dissolution, and surface adsorption. Natural organic matter (NOM) are the most abundant natural ligands in the environment which include Humic acid and Fulvic acid. These high molecular weight organic molecules have complex structures and contain many different functional groups such as carboxylic acid groups, hydroxyl, amino and phenolic groups that can interact with the nanoparticle surface. The nature and the intensity of the interaction are dependent on several factors including the size and the surface functionality of nanoparticles and pH of the medium. The smaller the nanoparticle, the higher the adsorption of NOM due to the high surface to volume ratio of smaller particles. Functional groups on the surface dictate the surface charge of the nanoparticles in water depending on the acidity. The higher the acidity, higher the adsorption of NOM due to increased electrostatic attractions between positively charged nanoparticles and the negatively charged NOM molecules. Adsorbed NOM on nanoparticles affect the other transformations such as aggregation and dissolution and can in turn alter the reactivity and toxicity of the nanoparticles. Therefore, effect of NOM is an important factor that should be considered in environmental toxicity related studies of nanoparticles.

A candidate hydrogen storing material should have high storage capacity and fast dehydrogenation kinetics. On this basis, magnesium hydride (MgH2) is an outstanding compound with 7.66 wt % storage capacity, despite its slow dehydriding kinetics and high desorption temperature. Therefore in this study, bulk and surface alloys of Mg with improved hydrogen desorption characteristics were investigated. In this respect, formation energies of alloyed bulk MgH2 as well as the adsorption energies on alloyed magnesium (Mg) and MgH2 surface structures were calculated by total energy pseudopotential methods. Furthermore, the effect of substitutionally placed dopants on the dissociation of hydrogen molecule (H2) at the surface of Mg was studied via Molecular Dynamics (MD). The results displayed that 31 out of 32 selected dopants contributed to the decrease in formation energy of MgH2 within a range of ~ 37 kJ/mol-H2 where only Sr did not exhibit any such effect. The most favorable elements in this respect came out to be / P, K, Tl, Si, Sn, Ag, Pb, Au, Na, v Mo, Ge and In. Afterwards, a systematical study within adsorption characteristics of hydrogen on alloyed Mg surfaces (via dynamic calculations) as well as calculations regarding adsorption energies of the impurity elements were performed. Accordingly, Mo and Ni yielded lower adsorption energies / -9.2626 and -5.2995 eV for substitutionally alloyed surfaces, respectively. MD simulations presented that Co is found to have a splitting effect on H2 in 50 fs, where the first hydrogen atom is immediately adsorbed on Mg substrate. Finally, charge density distributions were realized to verify the distinguished effects of most 3d and 4d transition metals in terms of their catalyzer effects.

In this study, the effect of surface crystallography on hydrogen molecule adsorption properties on FeTi surfaces is presented. Furthermore, the substitutional adsorption of 3d-transition metals on (001), (110) and (111) surfaces of FeTi is studied. Using ab initio pseudopotential methods, the adsorption energies of hydrogen and 3d-transition metals are calculated. In substitutional adsorption of 3d-transition metals, Fe-terminated (111) and Ti-terminated (001) surfaces, are found to express the lowest adsorption energies. The adsorption energy versus adsorbed elements&rsquo / curves are very alike for all the surfaces. According to this, going from the left to right of periodic table, the adsorption energies increase first. The maximum energy belongs to Cr, Mn and Fe for all the surfaces. Then a minimum is observed in Co for all the surfaces and after that the energy increases again. Adsorption energies of atomic and molecular hydrogen are calculated on high symmetry sites of surfaces. As a result, top and bridge sites came out to be the most stable positions for molecular and atomic hydrogen adsorption, respectively, for (001) and (111) surfaces in all terminations. In (110) surface / however, 3-fold (Ti-Ti)L-Fe and 3-fold (Ti-Ti)S-Fe hollow sites express the lowest adsorption energies for molecular and atomic hydrogen, respectively. Considering the minimum adsorption energy sites for hydrogen molecule and atom, a path of dissociation of hydrogen molecule on surfaces is represented. After that by fully relaxing the hydrogen molecule on the surface and using CI-NEB method the activation energy for hydrogen dissociation is calculated. So it has been found that on Fe-terminated (111) and FeTi (110) surfaces the dissociation of hydrogen molecule happens without activation energy. Meanwhile, the activation energy for Fe-terminated (001) surface and Ti-terminated (001) surface, is calculated to be 0.178 and 0.190 eV, respectively.

Metal-Organic Frameworks (MOFs) are highly porous materials built from inorganic nodes joined by organic linkers forming extended crystalline networks. One of the distinguishing features of metal-organic frameworks is the ability to adaptively change their crystal structure in response to external stimuli with significant porosity switching. Such structural switchability of MOFs offers new opportunities in gas separation, selective recognition, sensing, and energy storage. However, there are still open questions in understanding factors affecting switchability. The electronic structure of the metal in the building blocks, host-guest interactions, but also particle size, morphology, surface, desolvation conditions are involved into the responsiveness of the system. One of the representative of switchable metal-organic frameworks is pillared-layer DUT-8 (M2(2,6-ndc)2(dabco), M = Ni, Co, Cu, Zn, 2,6-ndc = 2,6-naphthalenedicarboxylate, dabco = 1,4-diazabicyclo[2.2.2]octane). Depending on the metal node and particle size, it is possible to synthesize either switchable or rigid materials differing in physisorption isotherm profiles. In order to understand switching behaviour of DUT-8, the important parameters influencing structural switchability are addressed in my work. For this purpose, the impact of crystal size and morphology, as well as crystal surface on adsorption-induced structural transformations of DUT-8(Ni) were investigated. DUT-8(Ni) shows reversible structural transition between open (op) and closed pore phase (cp) upon adsorption/removal of guest molecules. To understand which particular crystal surfaces dominate the phenomena observed, crystals similar in size and differing in morphology were involved in a systematic study. The analysis of the data shows that the width of the rods (corresponding to the crystallographic directions along the layer) represents a critical parameter governing the dynamic properties upon adsorption of nitrogen at 77 K. This observation is related to the anisotropy of the channel-like pore system and the nucleation mechanism of the solid-solid phase transition triggered by gas adsorption. To investigate the influence of external surface on adsorption-induced switchability, DUT-8(Ni) samples were exposed to different treatment techniques. By means of analytical methods, it was revealed that the surface of samples was modified leading to a significant increase of the gate-opening pressure, reflecting the increase of activation barrier for phase switching form cp to op upon adsorption of nitrogen at 77 K. Furthermore, the properties of DUT-8(Zn) were studied precisely, focusing on the variation of particle size and morphology, host-guest interactions, desolvation conditions, selectivity and thermoresponsivity. Depending on the synthesis conditions, DUT-8(Zn) can be synthesised in macro-sized regime (150 µm) and micron-sized regime (0.5 µm). The solvent removal process (pore desolvation stress contracting the framework) significantly controls the cp/op ratio after desolvation and, subsequently, the adsorption induced switchability characteristics of the system. Among the applied desolvation techniques, the solvent exchange with subsequent heating causes phase transition from open (op) to closed pore phase (cp). After desolvation, the dense cp phase of DUT-8(Zn) shows no adsorption-induced reopening and therefore is non-porous for N2 at 77 K and CO2 at 195 K. However, polar molecules with a higher adsorption enthalpy, such as chloromethane at 249 K and dichloromethane (DCM) at 298 K can reopen the macro-sized crystals upon adsorption, while micron-sized crystals retain the cp phase. For macro-sized particles (160 µm), the outer surface energy is negligible and only the type of metal (Zn, Co, Ni) controls the DCM-induced gate opening pressure. The node hinge stiffness increases from Zn to Ni as confirmed by DFT calculations, X-ray crystal structural analysis, and low frequency Raman spectroscopy. This softer Zn-based node hinges and overall increased stabilization of cp vs. op phase shift the critical particle size at which switchability starts to become suppressed to even lower values. Hence, the three factors affecting switchability (energetics of the empty host, (Eop–Ecp) (i), particle size (ii), and desolvation stress (iii)) appear to be of the same order of magnitude and should be considered collectively, not individually. Crystal downsizing (0.5 µm) facilitates the responsivity of DUT-8(Zn) towards different guest molecules, not opening for macro-sized crystals. Among investigated adsorptives, the alcohols are in the center of attention due to ability to induce so called shape-memory effect in micron-sized crystals. The adsorption of alcohols stimulates the change of initial shape of pores (cp) into a temporary shape (op) which is maintained even after desorption. To brighten the crystal size range and to study the dependence of gate opening pressure from crystal size and morphology, differently shaped crystals in micron-sized regime were produced by face-selective coordination modulation. Morphology modification allowed to determine the critical parameter controlling switchable transformations in DUT-8(Zn). Thus, the crystal size engineering and morphology modification provide an opportunity not only to control the structural dynamics of MOFs, but also to tailor responsivity towards guest molecules, influencing the selective adsorption behaviour.

The work presented in this thesis deals with experimental and theoretical studies related to the growth of crystalline alumina thin films. Alumina, Al2O3, is a polymorphic material utilized in a variety of applications, e.g., in the form of thin films. Many of the possibilities of alumina, and the problems associated with thin film synthesis of the material, are due to the existence of a range of different crystalline phases. Controlling the formation of the desired phase and the transformations between the polymorphs is often difficult. In the experimental part of this work, it was shown that the thermodynamically stable alpha phase, which normally is synthesized at substrate temperatures of around 1000 °C, can be grown using reactive sputtering at a substrate temperature of 500 °C by controlling the nucleation surface. This was done by predepositing a Cr2O3 nucleation layer. Moreover, it was found that an additional requirement for the formation of the α phase is that the depositions are carried out at low enough total pressure and high enough oxygen partial pressure. Based on these observations, it was concluded that energetic bombardment, plausibly originating from energetic oxygen, is necessary for the formation of α alumina (in addition to the effect of the chromia nucleation layer). Further, the effects of impurities, especially residual water, on the growth of crystalline films were investigated by varying the partial pressure of water in the ultra high vacuum (UHV) chamber. Films deposited onto chromia nucleation layers exhibited a columnar structure and consisted of crystalline α-alumina if deposited under UHV conditions. However, as water to a partial pressure of 1x10-5 Torr was introduced, the columnar growth was interrupted. Instead, a microstructure consisting of small, equiaxed grains was formed, and the gamma-alumina content was found to increase with increasing film thickness. When gamma-alumina was formed under UHV conditions, no effects of residual water on the phase formation was observed. Moreover, the H content was found to be low (< 1 at. %) in all films. Consequently, this shows that effects of residual gases during sputter deposition of oxides can be considerable, also in cases where the impurity incorporation in the films is found to be low. In the modeling part of the thesis, density functional theory based computational studies of adsorption of Al, O, AlO, and O2 on different alpha-alumina (0001) surfaces have been performed. The results give possible reasons for the difficulties in growing the α phase at low temperatures through the identification of several metastable adsorption sites, and also provide insights related to the effects of hydrogen on alumina growth. / Report code: LiU-TEK-LIC-2007:1.