Dans cette thèse, des matériaux 2D ont été étudiés principalement par méthodes ab initio de type DFT, ainsi que par des techniques expérimentales. Le manuscrit se focalise sur le polymorphisme, les bords et la fonctionnalisation du matériau 2D MoS2. Nous montrons que la fonctionnalisation avec des espèces similaires peut être étendue à d’autres matériaux 2D en incluant des études sur le graphène. Nous étudions par des calculs DFT la stabilité relative des polymorphes et des reconstructions des bords de monocouches de MoS2, et nous proposons des modèles qualitatifs pour comprendre la stabilité. La fonctionnalisation du MoS2 par des stratégies covalentes et non covalentes a également été étudiée en lien avec des expérimentateurs. En particulier, nos calculs indiquent que le MoS2 peut être fonctionnalisé de manière covalente avec des dérivés de 1,2- dithiolane. Cette fonctionnalisation se fait préférentiellement sur les bords, produisant un hybride stable. Ceci peut être utilisé pour produire un système avec un groupe pyrène photoactif qui interagit de manière significative avec MoS2. Les résultats expérimentaux obtenus par nos collaborateurs sont conformes à nos résultats théoriques et une interaction entre le fragment pyrène photoexcité et MoS2 a été mise en évidence. La fonctionnalisation directe non covalente de la surface de MoS2 avec du pyrène a également été étudiée théoriquement et expérimentalement, en trouvant une interaction similaire à celle du cas précédent. Finalement, nous montrons que des dérivés de pyrène peuvent être utilisés pour la fonctionnalisation de matériaux liés au graphène, système d’intérêt pour le stockage de l'énergie. / In this thesis, ab initio DFT methods and complementary experimental techniques are used to study 2D materials. The manuscript focuses on our studies on the polymorphism, edges and functionalization of the 2D-material MoS2. Additionally, we show that functionalization with similar species can be extended to other 2D materials by including studies on the functionalization of graphene. We have studied using DFT calculations the relative stability of different MoS2 polymorphs and associated edge reconstructions, and have proposed qualitative models for understanding the stability trends. Functionalization of MoS2 by covalent and non-covalent strategies is also explored in collaboration with experimental partners. In particular, our calculations indicate that MoS2 can be covalently functionalized, preferentially at edges, leading to a final stable hybrid. This strategy is used to functionalize MoS2 with a photoactive pyrene group that shows significant interaction with MoS2. Experimental results obtained by our collaborators are consistent with our theoretical findings, and an interaction between the photoexcited pyrene moiety and MoS2 is found. A similar interaction is found for direct noncovalent functionalization of the basal plane of MoS2 both theoretically and experimentally. Finally, we show that pyrene derivatives can also be used for functionalizing graphenerelated materials for energy storage applications.

Piezoelectricity in two-dimensional (2D) transition metal dichalcogenides (TMDs) has attracted significant attention due to their unique crystal structure and the lack of inversion centers when the bulk TMDs thin down to monolayer. Although the piezoelectricity effect in atomic-thickness TMDs has been demonstrated, they are not scalable. Herein, we demonstrate a piezoelectric effect from large-scale, sputtered MoS2 and WS2 using a robust defect-engineering based on the thermal-solvent annealing and solvent immersion process. This yields a higher piezoelectric output over 20 times after annealing or solvent immersion. Indeed, the piezoelectric responses are strengthened with the increases of defect density. Moreover, the MoS2 or WS2 piezoelectric device array shows an exceptional piezoelectric sensitivity with a high-level uniformity and excellent environmental stability under ambient conditions. A detailed study of the sulfur vacancy-dependent property and its resultant asymmetric structure-induced piezoelectricity is reported. The proposed approach is scalable and can produce advanced materials for flexible piezoelectric devices to be used in emerging bioinspired robotics and biomedical applications.

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2-Dimensional (2D) materials are characterised by atomic thickness and significantly larger edge-lengths, producing particles which are highly confined in 1 direction. Reducing a material to one or few atomic layers gives rise to structural and electronic properties that deviate significantly from those of the bulk crystal. For this reason 2D nanosheets have been investigated for potential application in sensing, catalysis, capacitance, photovoltaics and for flexible circuits (among others).Despite rapid progress in understanding the synthesis and properties of 2D nanosheets in recent years, there remain significant problems surrounding the development of scalable production methods, understanding and tuning fundamental properties, and controlling the size and monodispersity of semiconductor crystals. In addition, new materials with novel properties are constantly sought in order to meet specific requirements. Although the tools developed over the last 12 years can often be applied to the fabrication of these materials, understanding their behaviour and limitations is ongoing. The following thesis discusses the routes to the fabrication of 2-dimensional materials and explores the production of MoS2, black phosphorus and tin(II) sulfide nanosheets. The aim of each piece of work is determined by the level of development of the field; MoS2 nanosheets have been known for several years and therefore the work presented was motivated by a desire to impart size control for specific applications. The study of phosphorene and 2D tin(II) sulfide is in its infancy; as such the focus remains on scalable nanosheet exfoliation and developing an understanding of their properties. The following studies on phosphorene report the exfoliation of nanosheets in organic and aqueous surfactant solutions and an investigation of the stability and breakdown products of the resulting colloidal suspensions. The stabilisation of phosphorene in aqueous media paves the way for its use in biological systems. Band-gap tuning in IV-VI analogues of phosphorene is demonstrated by size-selection of exfoliated SnS nanosheets. Although the physical characteristics of nanosheets and their incorporation into devices receive some attention, this thesis will focus mainly on the synthetic aspects of 2D materials research.

For applications of MoS2 in batteries, supercapacitors, electrocatalysts, solar cells and water quality sensors, a substantially increased conductivity is required in order to achieve reasonable currents. Popularly, the metallic 1T-MoS2 phase is used, which can be prepared via a lithium intercalation process, requiring inert atmosphere processing and safety procedures. In this thesis, I demonstrate a safer and more efficient process to yield conductive MoS2 (c-MoS2). This simple and effective way to prepare few layer c-MoS2 utilizes ambient conditions and 0.06 vol% aqueous hydrogen peroxide. Part of the research effort has been to enhance the conductivity of MoS2 using the idea of green solvents (like pure water). The bulk conductivities of both peroxide and water exfoliated MoS2 are up to seven orders of magnitude higher than that of the semiconducting 2H-MoS2 phase. The samples were characterized with Hall measurements, X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy. Trace amounts of hydrogen molybdenum bronze (HxMoO3-y) and sub stoichiometric MoO3-y were shown to help tune the conductivity of the nanometer-scale thin films without impacting the sulfur-to-molybdenum ratio. c-MoS2 was further functionalized with thiols to determine the number of residual reactive sites. I also studied the mechanism of surface functionalization of MoS2 with diazonium molecules (both direct and in-situ approach) to understand the surface properties of our material and tune the chemical and mechanical properties of conductive MoS2. An important goal of my work is to control the conductivity of the MoS2 thin films in safe and facile ways that enable their application in low-cost chemiresistive sensors for liquid environments. I fabricated chemiresistive sensors with centimeter channel lengths while maintaining low measurement voltages for pH sensing. I further measured the catalytic activity of c-MoS2 films in 0.5 M H2SO4 electrolyte solution using linear sweep voltammetry (LSV) which showed a lower Tafel value at 10 mA/cm2 current density. The lower Tafel value demonstrated that c-MoS2 has potential to use as catalyst for hydrogen evolution reaction. My study furthers the understanding of conductive forms of MoS2 and opens up a new pathway for next generation electronic and energy conversion devices. / Thesis / Doctor of Philosophy (PhD) / For applications of MoS2 in batteries, supercapacitors, electrocatalysts, solar cells and water quality sensors, a substantially increased conductivity is required in order to achieve reasonable currents. Popularly, the metallic 1T-MoS2 phase is used, which can be prepared via a lithium intercalation process, requiring inert atmosphere processing and safety procedures. In this thesis, I demonstrate a safer and more efficient process to yield conductive MoS2 (c-MoS2). This simple and effective way to prepare few layer c-MoS2 utilizes ambient conditions and 0.06 vol% aqueous hydrogen peroxide. Part of the research effort has been to enhance the conductivity of MoS2 using the idea of green solvents (like pure water). The bulk conductivities of both peroxide and water exfoliated MoS2 are up to seven orders of magnitude higher than that of the semiconducting 2H-MoS2 phase. The samples were characterized with Hall measurements, X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy. Trace amounts of hydrogen molybdenum bronze (HxMoO3-y) and sub stoichiometric MoO3-y were shown to help tune the conductivity of the nanometer-scale thin films without impacting the sulfur-to-molybdenum ratio. c-MoS2 was further functionalized with thiols to determine the number of residual reactive sites. I also studied the mechanism of surface functionalization of MoS2 with diazonium molecules (both direct and in-situ approach) to understand the surface properties of our material and tune the chemical and mechanical properties of conductive MoS2. An important goal of my work is to control the conductivity of the MoS2 thin films in safe and facile ways that enable their application in low-cost chemiresistive sensors for liquid environments. I fabricated chemiresistive sensors with centimeter channel lengths while maintaining low measurement voltages for pH sensing. I further measured the catalytic activity of c-MoS2 films in 0.5 M H2SO4 electrolyte solution using linear sweep voltammetry (LSV) which showed a lower Tafel value at 10 mA/cm2 current density. The lower Tafel value demonstrated that c-MoS2 has potential to use as catalyst for hydrogen evolution reaction. My study furthers the understanding of conductive forms of MoS2 and opens up a new pathway for next generation electronic and energy conversion devices.

Graphene, an atomically thin material consisting of a hexagonal, highly packed carbon lattice, is of great interests in its magnetic properties. These interests can be categorized in several fields: graphene-based magnetic materials and their applications, large diamagnetism of graphene, and the heterostructures of graphene and other two dimensional materials. In the first aspect, magnetic moments can be in theory introduced to graphene by minimizing its size or introducing structural defects, leading to a very light magnetic material. Furthermore, weak spin-orbital interaction, and long spin relaxation length make graphene promising for spintronics. The first part of this thesis addressed our experimental investigation in defect-induced magnetism of graphene. Non-interacted spins of graphene have been observed by intentionally introducing vacancies and adatoms through ion-irradiation and fluorination, respectively. The defect concentration or the magnetic moments introduced in this thesis cannot provide enough interaction for magnetic coupling. Furthermore, the spins induced by vacancies and adatoms can be controlled through shifting the Fermi energy of graphene using molecular doping, where the adatoms were alternatively introduced by annealing in the inert environment. The paramagnetic responses in graphene induced by vacancy-type defects can only be diverted to half of its maximum, while those induced by sp3 defects can be almost completely suppressed. This difference is supposed that vacancy-type defects induced two localized states (pie and sigma). Only the latter states, which is also the only states induced by sp3 defects, involves in the suppression of magnetic moments at the maximum doping achieved in this thesis. The observation through high resolution transmission electron microscope (HR-TEM) provides more information to the hypothesis of the previous magnetic findings. Reconstructed single vacancy is the majority of defects discovered in proton-irradiated graphene. This result verifies the defect-induced magnetic findings in our results, as well as the electronic properties of defected graphene in the literatures. On the other hand, the diamagnetic susceptibility of neutral graphene is suggested to be larger than that of graphite, and vanish rapidly as a delta-like function when graphene is doped. In our result, surprisingly, the diamagnetic susceptibility varies little when the Fermi level is less than 0.3 eV, in contrast with the theory. When the Fermi energy is higher than 0.3 eV, susceptibility then reduces significantly as the trend of graphite. The little variation in susceptibility near the Dirac point is probably attributed to the spatial confinement of graphene nanoflakes, which are the composition of graphene laminates. In the end of this thesis, we discuss the magnetic properties in one of the other two dimensional materials, molybdenum disulfide (MoS2). It is a potential material for graphene-based heterostructure applications. The magnetic moments in MoS2 are shown to be induced by either edges or vacancies, which are introduced by sonication or proton-irradiation, respectively, similar to the suggestions by theories. However, no significant ferromagnetic finding has been found in all of our cases.

Intercalation is known to be an efficient method for tuning the band structure of layered materials to bring out superconductivity, without significantly altering the crystal structure of the host material. Graphite intercalation compounds and intercalated transitional metal dichalcogenides (TMDs) are two most studied representatives. This thesis presents an experimental study of several new superconductors obtained by intercalation of layered materials, including MoS2, black phosphorus and a topological insulator Bi2Se3. Polymorphism is an essential feature of MoS2. While, superconductivity in doped 2H-MoS2 has been extensively studied. Superconductivity in its 1T and 1T' counterparts has been neither observed, nor even predicted theoretically. In this thesis, we have investigated potassium (K)-intercalated MoS2 and found that doping with K induces both structural and superconducting phase transitions. We demonstrate that all three phases of MoS2 - 2H, 1T and 1T'- become superconducting as a result of intercalation, with critical temperature Tc of 6.9 K, 2.8 K and 4.6 K, respectively. Black phosphorus has been 'rediscovered' in the last few years due to its layered structure and unique electronic properties. This thesis describes successful intercalation of black phosphorus with several alkali metals (Li, K, Rb, Cs) and alkaline earth metal Ca, with all five compounds showing superconductivity. Importantly, and very unexpectedly, the found superconductivity of intercalated black phosphorus is independent of the intercalant, with all five compounds having exactly the same superconducting characteristics (Tc, critical fields, anisotropy). We suggest that the superconductivity is due to heavily doped phosphorene layers, with alkali metal atoms acting mainly as charge reservoirs. Superconducting topological insulators, such as Bi2Se3, are regarded as the most promising candidates for topological superconductivity. However, the nature of superconductivity in doped Bi2Se3, such as CuxBi2Se3, SrxBi2Se3 and NbxBi2Se3, remains controversial and so far no convincing evidence of topological superconductivity has been reported for these materials. In this thesis, we report superconductivity in a new family of superconductors derived from Bi2Se3, by intercalation with K, Rb and Cs metals. All three superconductors exhibit qualitatively identical but highly anomalous behaviour of magnetisation, with several new features consistent with the properties of topological superconductors. Specifically, the new materials exhibit a highly unusual extra diamagnetic screening in the Meissner state and two coexisting superconducting phase, including surface superconductivity that we attribute to heavily doped surface states of the original topological insulator (Bi2Se3). This work provides a new platform in the study of the interplay between the topological and superconducting orders. In conclusion, superconductivity has been induced in MoS2, black phosphorus and Bi2Se3 through alkali or alkaline earth metal intercalation. The study of these new superconducting materials has been summarised in the thesis.

Higher alcohols synthesized via CO hydrogenation reactions have been a topic of intense study both in industry and academia for over thirty years. A variety of transition metals and promoters have been used in catalysts for this reaction. MoS₂, in particular, is popular due to its low cost, resistance to sulfur poisoning, and ability to selectively produce higher alcohols over hydrocarbons. The bulk material has a rich history in hydrodesulfurization reactions (HDS), and as such, a great deal is known about the material's structure and reactivity. However, even with this deep body of knowledge about the bulk catalyst, no one has yet been able to implement an industrially viable variation of the catalyst to make higher alcohols. Supported MoS₂ has also been studied for the same purpose. Generally, supports are employed to improve catalyst productivity per gram of Mo by dispersing the metal and increasing the amount of catalytically active surface area. However, product selectivity may also be influenced by chemical properties of the supports. Specifically, gamma alumina has been shown to raise hydrocarbon formation due to intrinsic surface acidity. The effects of basic supports are reported on the CO hydrogenation reaction are reported. K promoted Mo is supported on two basic materials - commercial sepiolite (Si₁₂Mg₈O₃₀(OH)₄) and hydrotalcite-derived Mg/Al mixed metal oxides (MMO). The catalysts are reacted with syngas, and the resultant product selectivities are compared at isoconversions. Activated carbon supported Mo and bulk MoS₂ are also used as controls. It is shown that MMO provides a unique promotional effect by suppressing methanol formation and favoring higher alcohols. The specific role of MMO in the reaction is investigated by combining it in three different ways with Mo. 1) MMO is impregnated with Mo in the classic fashion. 2) Bare MMO or MMO/K is placed as a secondary bed downstream of the principle catalyst (K promoted Mo supported on MMO). 3) Bare MMO or MMO/K is mixed with the principle catalyst to make a homogeneous bed. It is shown that MMO by itself is somewhat inert in the reaction while MMO/K has some higher alcohol forming activity. More importantly however, it is shown that the MMO:Mo ratio has far greater effects on selectivity than the morphology of MoS₂. There is evidence however that MoS₂ morphology can affect activity. It is hypothesized that a greater degree of stacking in MoS₂ domains leads to reduced activity. The existence of coupling and homologation pathways are investigated by feeding methanol or ethanol into the syngas as it enters the catalyst bed. By comparing changes in the productivity of different higher alcohols with the liquid feed, it is shown that an MMO supported catalyst is much more reactive with methanol and somewhat more reactive with ethanol than its bulk MoS₂ counterpart. It is shown that for both the bulk and supported catalysts, the addition of a Cx alcohol results in the largest increase in Cx+1 products, suggesting that alcohol homologation is in fact the most favored route to higher alcohols by these materials.

The present thesis concerns catalytic conversion of syngas (H2+ CO) into a blend of methanol and higher alcohols, an attractive way of producing fuels and chemicals. This route has the potential to reduce the oil dependence in the transport sector and, with the use of biomass for the syngas generation, produce CO2-neutral fuels. Alkali promoted MoS2-based catalysts show a high selectivity to higher alcohols, while at the same time being coke resistant, sulfur tolerant and displaying high water-gas shift activity. This makes this type of catalyst especially suitable for being used with syngas derived from biomass or coal which typically has a low H2/CO-ratio. This thesis discusses various important aspects of higher alcohol synthesis using MoS2-based catalysts and is a summary of four scientific papers. The first part of the thesis gives an introduction to how syngas can be produced and converted into different fuels and chemicals. It is followed by an overview of higher alcohol synthesis and a description of MoS2-based catalysts. The topic alcohol for use in internal combustion engines ends the first part of the thesis. In the second part, the experimental part, the preparation of the MoS2-based catalysts and the characterization of them are handled. After describing the high-pressure alcohol reactor setup, the development of an on-line gas chromatographic system for higher alcohol synthesis with MoS2 catalysts is covered (Paper I). This method makes activity and selectivity studies of higher alcohol synthesis catalysts more accurate and detailed but also faster and easier. Virtually all products are very well separated and the established carbon material balance over the reactor closed well under all tested conditions. The method of trace level sulfur analysis is additionally described. Then the effect of operating conditions, space velocity and temperature on product distribution is highlighted (Paper II). It is shown that product selectivity is closely correlated with the CO conversion level and why it is difficult to combine both a high single pass conversion and high alcohol selectivity over this catalyst type. Correlations between formed products and formation pathways are additionally described and discussed. The CO2 pressure in the reactor increases as the CO conversion increases, however, CO2 influence on formation rates and product distribution is to a great extent unclear. By using a CO2-containing syngas feed the effect of CO2 was studied (Paper III). An often emphasized asset of MoS2-based catalysts is their sulfur tolerance. However, the use of sulfur-containing feed and/or catalyst potentially can lead to incorporation of unwanted organic sulfur compounds in the product. The last topic in this thesis covers the sulfur compounds produced and how their quantity is changed when the feed syngas contains H2S (Paper IV). The effect on catalyst activity and selectivity in the presence of H2S in the feed is also covered. / <p>QC 20150115</p>

Achieving tunability of two dimensional (2D) transition metal dichalcogenides (TMDs) functions calls for the introduction of hybrid 2D materials by means of localized interactions with zero dimensional (0D) materials. A metal-semiconductor interface, as in gold (Au) - molybdenum disulfide (MoS2), is of great interest from the standpoint of fundamental science as it constitutes an outstanding platform to investigate optical and electronic properties due to charge transfer. The applied aspects of such systems introduce new options for electronics, photovoltaics, detectors, catalysis, and biosensing. Here in this dissertation, we study the charge transfer interaction between Au nanoparticals and MoS2 flakes and its effect on Photoluminescence and electronic transport properties. The MoS2 was mechanically exfoliated from bulk single crystal. Number of layers in the flake was identified with the help of AFM and Raman Spectra. Au was deposited by physical vapor deposition method (PVD) in multiple steps to decorate MoS2 flakes. We first study the photoluminescence of pristine and Au decorated MoS2 and shows that in the presence of Au, the photoluminescence of MoS2 quenches significantly. We infer that the PL quenching can be attributed to a change in the electronic structure of the MoS2-Au system. The difference in Fermi level of a of MoS2 and Au results in a 0.4 eV energy level offset, which causes a band bending in the MoS2-Au hybrid. Upon illumination, the electrons in the excited state of MoS2 transfer to Au, leaving a hole behind, thus cause p-doping in MoS2. As electrons from MoS2 are transferred to Au, they do not decay back to their initial ground state, leading to PL quenching in the hybrid system. To study the effect of Au deposition on electronic properties of ultra-thin and multilayers MoS2 flakes, we have fabricated MoS2 FETs from (1) ultra-thin sample (2-4 MoS2 layers) and (2) multilayers samples (more than 20 layers). After each deposition of Au, we measured the electrical characteristics of FET at room temperature. We show that the threshold voltage shifts towards the positive gate voltage as we increase the thickness of Au. This shift in threshold voltage is indicative of p doping of the MoS2. We further show that the field effect mobility of MoS2 FET decrease with Au thickness. We have quantitatively estimated the charge transferring from MoS2 to Au.