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Since the isolation and characterization of graphene, there has been a growing interest in 2D materials owing to their unique properties compared to their 3D counterparts. Recently, a family of 2D materials of early transition metal carbides and nitrides, labelled MXenes, has been discovered (Ti2CTz, Ti3C2Tz, Mo2TiC2Tz, Ti3CNTz, Ta4C3Tz, Ti4N3Tz among many others), where T stands for surface-terminating groups (O, OH, and F). MXenes are mostly produced by selectively etching A layers (where A stands for group A elements, mostly groups 13 and 14) from the MAX phases. The latter are a family of layered ternary carbides and/or nitrides and have a general formula of Mn+1AXn (n = 1-3), where M is a transition metal and X is carbon and/or nitrogen. The produced MXenes have a conductive carbide core and a non-conductive O-, OH- and/or F-terminated surface, which allows them to work as electrodes for energy storage applications, such as Li-ion batteries and supercapacitors. Prior to this work, MXenes were produced in the form of flakes of lateral dimension of about 1 to 2 microns; such dimensions and form are not suitable for electronic characterization and applications. I have synthesized various MXenes (Ti3C2Tz, Ti2CTz and Nb2CTz) as epitaxial thin films, a more suitable form for electronic and photonic applications. These films were produced by HF, NH4HF2 or LiF + HCl etching of magnetron sputtered epitaxial Ti3AlC2, Ti2AlC, and Nb2AlC thin films. For transport properties of the Ti-based MXenes, Ti2CTz and Ti3C2Tz, changing n from 1 to 2 resulted in an increase in conductivity but had no effect on the transport mechanism (i.e. both Ti3C2Tx and Ti2CTx were metallic). In order to examine whether the electronic properties of MXenes differ when going from a few layers to a single flake, similar to graphene, the electrical characterization of a single Ti3C2Tz flake with a lateral size of about 10 μm was performed. These measurements, the first for MXene, demonstrated its metallic nature, along with determining the nature of the charge carriers and their mobility. This indicates that Ti3C2Tz is inherently of 2D nature independent of the number of stacked layers, unlike graphene, where the electronic properties change based on the number of stacked layers. Changing the transition metal from Ti to Nb, viz. comparing Ti2CTz and Nb2CTz thin films, the electronic properties and electronic conduction mechanism differ. Ti2CTz showed metallic-like behavior (resistivity increases with increasing temperature) unlike Nb2CTz where the conduction occurs via variable range hopping mechanism (VRH) - where resistivity decreases with increasing temperature. Furthermore, these studies show the synthesis of pure Mo2CTz in the form of single flakes and freestanding films made by filtering Mo2CTz colloidal suspensions. Electronic characterization of free-standing films made from delaminated Mo2CTz flakes was investigated, showing that a VRH mechanism prevails at low temperatures (7 to ≈ 60 K). Upon vacuum annealing, the room temperature, RT, conductivity of Mo2CTx increased by two orders of magnitude. The conduction mechanism was concluded to be VRH most likely dominated by hopping within each flake. Other Mo-based MXenes, Mo2TiC2Tz and Mo2Ti2C3Tz, showed VRH mechanism at low temperature. However, at higher temperatures up to RT, the transport mechanism was not clearly understood. Therefore, a part of this thesis was dedicated to further investigating the transport properties of Mo-based MXenes. This includes Mo2CTz, out-of-plane ordered Mo2TiC2Tz and Mo2Ti2C3Tz, and vacancy ordered Mo1.33CTz. Magneto-transport of free-standing thin films of the Mo-based MXenes were studied, showing that all Mo-based MXenes have two transport regimes: a VRH mechanism at lower temperatures and a thermally activated process at higher temperatures. All Mo-based MXenes except Mo1.33CTz show that the electrical transport is dominated by inter-flake transfer. As for Mo1.33CTz, the primary electrical transport mechanism is more likely to be intra-flake. The synthesis of vacancy ordered MXenes (Mo1.33CTz and W1.33CTz) raised the question of possible introduction of vacancies in all MXenes. Vacancy ordered MXenes are produced by selective etching of Al and (Sc or Y) atoms from the parent 3D MAX phases, such as (Mo2/3Sc1/3)2AlC, with in-plane chemical ordering of Mo and Sc. However, not all quaternary parent MAX phases form the in-plane chemical ordering of the two M metals; thus the synthesis of the vacancy-ordered MXenes is restricted to a very limited number of MAX phases. I present a new method to obtain MXene flakes with disordered vacancies that may be generalized to all quaternary MAX phases. As proof of concept, I chose Nb-C MXene, as this 2D material has shown promise in several applications, including energy storage, photothermal cell ablation and photocatalysts for hydrogen evolution. Starting from synthetizing (Nb2/3Sc1/3)2AlC quaternary solid solution and etching both the Sc and Al atoms resulted in Nb1.33C material with a large number of vacancies and vacancy clusters. This method may be applicable to other quaternary or higher MAX phases wherein one of the transition metals is more reactive than the other, and it could be of vital importance in applications such as catalysis and energy storage.
An essential companion for catalysis researchers and professionals studying economically viable and eco-friendly catalytic strategies for energy conversion In the two-volume Heterogeneous Nanocatalysis for Energy and Environmental Sustainability, a team of distinguished researchers deliver a comprehensive discussion of fundamental concepts in, and practical applications of, heterogeneous nanocatalysis for alternative energy production, biomass conversion, solar energy, green fuels, H2 production, fuel cells, electrochemical energy conversion processes, CO2 conversion, clean water, and environmental protection. The volumes cover the design and catalytic performance of various nanocatalysts, including nanosized metals and metal oxides, supported metal nanoparticles, inverse oxide-metal nanocatalysts, core-shell nanocatalysts, nanoporous zeolites, nanocarbon composites, and metal oxides in confined spaces. Each chapter contains a critical discussion of the opportunities and challenges posed by the use of nanosized catalysts for practical applications. Volume 1 – Energy Applications focuses on the conversion of renewable energy (biomass/solar) into green fuels and chemicals, ammonia synthesis, clean hydrogen production, and electrochemical energy conversion processes using a variety of nanosized catalysts. It also offers: A thorough introduction to heterogeneous catalysis and nanocatalysis, as well as a discussion of catalytic active sites at nano-scale range Comprehensive explorations of the methods for control and activation of nanosized catalysts Practical discussions of C3N4-based nanohybrid catalysts for solar hydrogen production via water splitting Nanosized catalysts in visible light photocatalysis for sustainable organic synthesis Applications of MXenes in electrocatalysis Perfect for researchers, postgraduate students, chemists, and engineers interested in heterogeneous catalysis and nanocatalysis, Heterogeneous Nanocatalysis for Energy and Environmental Sustainability will also earn a place in the libraries of professionals working in alternative energy production, biomass conversion, solar energy, green fuels, H2 production, fuel cells, electrochemical energy conversion processes, CO2 conversion, clean water, and environmental protection.
The book provides an introduction to nanostructured materials and guides the reader through their different engineering applications. It gives an overview of nanostructured materials applied in the fields of physics, chemistry, biology, medicine, and materials science. Materials for different applications in engineering such as those used in opto-electronics, energy, tribology, bio-applications, catalysis, reinforcement and many more have been described in this book. The book will be of interest to researchers and students who want to learn about applications of nanostructured materials in engineering.
MXene, a two-dimensional (2D) transition metal carbide, nitride, and carbonitride, was discovered in 2011. MXene has great potential as a cocatalyst in the field of photocatalysis due to its unique properties and structure. MXene-Based Photocatalysts: Fabrication and Applications introduces readers to the fundamentals, preparation, microstructure characterization, and a variety of applications of MXene-based photocatalysts. The book is a comprehensive reference for MXene materials and provides an overview of the current literature on MXene-based photocatalysts. FEATURES Discusses preparation methods of MXenes Describes the morphology and microstructure of MXenes Offers strategies for fabricating MXene-based photocatalysts Details the reaction mechanism of MXene-based photocatalysts Covers applications in photocatalytic water-splitting, photocatalytic CO2 reduction, photocatalytic degradation, photocatalytic nitrogen fixation, and photocatalytic H2O2 production This book serves as an invaluable guide for advanced students, industry professionals, professors, and researchers in the field of materials science and engineering, photocatalysis, energy, and environmental applications.
This edition of Progress in Ceramic Technology series contains a select compilation of articles on the topic of nanomaterials processing of powders; thin films, wires and tubes; and composites that were previously published in The American Ceramic Society Bulletin, Journal of the American Ceramic Society, International Journal of Applied Ceramic Technology, Ceramic Engineering and Science Proceedings (CESP) and Ceramic Transactions (CT).
Comprehensive resource summarizing current approaches to generating hydrogen from water and reducing CO2 into various hydrocarbons Green Energy Harvesting: Materials for Hydrogen Generation and Carbon Dioxide Reduction provides an in-depth treatment of the subject by exploring the fundamentals required for the selection of the materials, their synthesis methods, and possible ways to modify them for higher efficiency and enhanced stability. The prospects of adopting these sustainable solutions at a commercial level are summarized. Special emphasis is given to the figure-of-merits for currently developed systems for hydrogen generation and CO2 reduction and to an assessment of available materials in terms of efficacy and efficiency. Green Energy Harvesting also includes information on: Renewable energy in general, including the role of renewable hydrogen and hydrocarbon fuels, and possible renewable energy sources A fundamental understanding hydrogen generation and CO2 reduction Device development and deployment status for commercial usage and applications of H2 and hydrocarbon fuels in various sectors Electrocatalysts, 2D materials, and hybrid materials for CO2 reduction and H2 generation Green Energy Harvesting is a highly useful guide for both novice and experienced researchers involved in renewable energy and carbon dioxide utilization that explains the current state of the field and discusses future perspectives.
Metal Oxide–Carbon Hybrid Materials: Synthesis, Properties and Applications reviews the advances in the fabrication and application of metal oxide–carbon-based nanocomposite materials. Their unique properties make them ideal materials for gas-sensing, photonics, catalysis, opto-electronic, and energy-storage applications. In the first section, the historical background to the hybrid materials based on metal oxide–carbon and the hybridized metal oxide composites is provided. It also highlights several popular methods for the preparation of metal oxide–carbon composites through solid-state or solution-phase reactions, and extensively discusses the materials' properties. Fossil fuels and renewable energy sources cannot meet the ever-increasing energy demands of an industrialized and technology-driven global society. Therefore, the role of metal oxide–carbon composites in energy generation, hydrogen production, and storage devices, such as rechargeable batteries and supercapacitors, is of extreme importance. These problems are discussed in in the second section of the book. Rapid industrialization has resulted in serious environmental issues which in turn have caused serious health problems that require the immediate attention of researchers. In the third section, the use of metal oxide–carbon composites in water purification, photodegradation of industrial contaminants, and biomedical applications that can help to clean the environment and provide better healthcare solutions is described. The final section is devoted to the consideration of problems associated with the development of sensors for various applications. Numerous studies performed in this area have shown that the use of composites can significantly improve the operating parameters of such devices. Metal Oxide–Carbon Hybrid Materials: Synthesis, Properties and Applications presents a comprehensive review of the science related to metal oxide–carbon composites and how researchers are utilizing these materials to provide solutions to a large array of problems. - Reviews the fundamental properties and fabrication methods of metal-oxide–carbon composites - Discusses applications in energy, including energy generation, hydrogen production and storage, rechargeable batteries, and supercapacitors - Includes current and emerging applications in environmental remediation and sensing
This book describes the rapidly expanding field of two-dimensional (2D) transition metal carbides and nitrides (MXenes). It covers fundamental knowledge on synthesis, structure, and properties of these new materials, and a description of their processing, scale-up and emerging applications. The ways in which the quickly expanding family of MXenes can outperform other novel nanomaterials in a variety of applications, spanning from energy storage and conversion to electronics; from water science to transportation; and in defense and medical applications, are discussed in detail.
In this comprehensive yet compact monograph, Michel W. Barsoum, one of the pioneers in the field and the leading figure in MAX phase research, summarizes and explains, from both an experimental and a theoretical viewpoint, all the features that are necessary to understand and apply these new materials. The book covers elastic, electrical, thermal, chemical and mechanical properties in different temperature regimes. By bringing together, in a unifi ed, self-contained manner, all the information on MAX phases hitherto only found scattered in the journal literature, this one-stop resource offers researchers and developers alike an insight into these fascinating materials.