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Chalcogenide-Based Nanomaterials as Photocatalysts deals with the different types of chalcogenide-based photocatalytic reactions, covering the fundamental concepts of photocatalytic reactions involving chalcogenides for a range of energy and environmental applications. Sections focus on nanostructure control, synthesis methods, activity enhancement strategies, environmental applications, and perspectives of chalcogenide-based nanomaterials. The book offers guidelines for designing new chalcogenide-based nanoscale photocatalysts at low cost and high efficiency for efficient utilization of solar energy in the areas of energy production and environment remediation. Provides information on the development of novel chalcogenide-based nanomaterials Outlines the fundamentals of chalcogenides-based photocatalysis Includes techniques for heterogeneous catalysis based on chalcogenide-based nanomaterials
Layered materials belong to a class of compounds in which individual, 2-dimensional units are stacked upon each other and held together by weak intermolecular forces. The layered nature of these materials render them ideal for techniques like intercalation, exfoliation, alloying, among others in order to tune their properties. Here, single-source precursors (SSP) from the lanthanides, transition metals, and main group metals will be synthesized and utilized to yield different classes of layered compounds: LnX2, CuCrX2, and Bi2X3, respectively. First, we describe the synthesis of a series of novel lanthanide SSPs, [Ln(Se2PPh2)3(MeCN)x], which were thermolyzed to yield LnSe2-x, an understudied class of 2D layered materials. In a group known for work with rare earth materials, particularly EuS, it was exciting to have discovered a mild route to other lanthanide chalcogenide materials. We explore the synthetic versatility of these precursors through synthesizing alloys of LnSe2-x as well understanding the growth mechanisms in order to yield single- or few- layered sheets. Next, we describe the synthesis of layered ternary transition metal chalcogenides, CuCrX2 and CuCr2X4 which form as hexagonal nanoplates. We utilized SSPs of Cr(III) and Cu(I)/(II) to understand the role of oxidation state, as well as precursor ratio and reaction temperatures, in order to gain phase control and avoid secondary phases. Lastly, we briefly discuss SSPs for synthesizing layered main group chalcogenide nanomaterials, Bi2X3. Bismuth based materials are in interesting comparison to lanthanides due to their similarity in size and charge but lack of f-block valence electrons. Here, we demonstrate the clear advantage of utilizing a SSP through affording defect-free phase-pure material as clear hexagonal nanoplates (compared to separate Bi(III) and Se reagents).
This book explores the recent advances in designing and synthesizing one- and two-dimensional metal chalcogenide nanostructures, along with their practical applications, helping readers understand what has happened, and what is currently happening in the field of nanotechnology. It also includes a comprehensive table showing 1D and 2D nanostructured metal chalcogenides, which presents the recent developments from a synthetic point of view. Further, it describes the wide applicability of anisotropic metal chalcogenides, such as in electronics, energy storage and conversion, and sensors. Lastly it discusses the current understanding of the thermodynamic and kinetic aspects associated with the forming mechanisms of anisotropic metal chalcogenide nanostructures. This book is a valuable reference resource for practitioners and researchers, enabling them to obtain a quick overview of anisotropic metal chalcogenide nanomaterials through synthetic approaches and related applications. Presenting representative applications of anisotropic metal chalcogenide nanomaterials that are important in the industrial sector, it is also of interest to academics and industry specialists.
We found that bulk metals and metal chalcogenides dissolve in primary amine-dithiol solvent mixtures at ambient conditions. Thin-films of CuS, SnS, ZnS, Cu2Sn(Sx, Se1-x)3, and Cu2ZnSn(SxSe1-x)4 (0 d"x d"1) were deposited using the as-dissolved solutions. Furthermore, Cu2ZnSn(SxSe1-x)4 solar cells with efficiencies of 6.84% and 7.02% under AM1.5 illumination were fabricated from two example solution precursors, respectively.
The inorganic titanium dioxide TiO2 and metal-free graphitic carbon nitride (g-C3N4) are the two most important photocatalysts owing to their low cost, non-toxicity, high thermal and chemical stability, as well as high reactivity. However, these two materials also suffer from certain drawbacks such as a relatively high rate of electron-hole pair recombination, a slightly large bandgap that requires UV-light for activation (TiO2), and a relatively small surface area (g-C3N4).This thesis focuses to overcome above drawbacks by combining TiO2 with low bandgap metal chalcogenide semiconducting nanoparticles as a strategy to create an efficient charge separation at the interface of the heterojunctions and to extend the absorption to visible region. This thesis also attempts to improve the photocatalytic efficiency of g-C3N4 by synthesizing it with high surface area and, finely, by combining it with TiO2. After describing briefly the motivation behind the work and the existing literature on the subject matter in the first chapter, the Chapter 2 describes precursor-mediated synthesis and photocatalytic activity of binary coinage metal chalcogenide nanoparticles and their composites with TiO2 under mild conditions. We successfully isolate and characterize kinetically and/or thermally unstable molecular species during the reactions, thus providing an insight into the molecule-to-nanoparticle mechanisms. The metal chalcogenide-titania nanocomposites show superior activity for the photodegradation of formic acid under ultraviolet light, as compared to titania (P25), which is a well-established benchmark for photocatalysis under UV light. Chapter 3 describes the synthesis of ternary coinage metal chalcogenides and their composites with titania. A direct room temperature reaction of tBu2Se with copper and silver trifluoroacetates gives copper-silver-selenide nanoparticles that are formed via a highly reactive intermediate molecular species [Ag2Cu(TFA)4(tBu2Se)4]. We also employed the pre-formed copper chalcogenide NPs as precursors and reacted it with di-tertiary butyl chalcogenide to obtain ternary metal chalcogenide nanoparticles and their composites with TiO2 in pure phase and with high yield. Photocatalytic studies for the degradation of formic acid under ultraviolet radiations show that the ternary CuAgSe-TiO2 nanocomposites are even better photocatalysts than the binary chalcogenide-TiO2 nanocomposites described in Chapter 2. The second part of this thesis described in Chapter 4 diverges from the earlier chapters to concentrate on the coupling of titania with graphitic carbon nitride. In the first step, we develop a simple single-step calcination approach to synthesize graphitic nanoparticles with a high surface area (200 m2/g). We test the prepared photocatalyst for the degradation of formic acid and phenol under visible light, and analyze the effect of factors such as surface area, irradiance and concentration of carbon nitride on the photocatalytic performance. Results show that the performance increases linearly with surface area and irradiance, whereas it first increases and gradually reaches plateau as concentration of the photocatalyst is increased. In the second step, we couple carbon nitride with titania using mechanical mixing. The prepared nanocomposites are then evaluated for the photodegradation of formic acid under both ultraviolet and visible lights. Finally, the Chapter 5 describes the experimental details of the synthesis and characterization of the molecular precursors, metal chalcogenide nanoparticles, g-C3N4 nanosheets as well as their composites with TiO2. It also describes in detail the experimental setup for the photocatalytic studies.
Ternary Quantum Dots: Synthesis, Properties, and Applications reviews the latest advances in ternary (I-III-VI) chalcopyrite quantum dots (QDs), along with their synthesis, properties and applications. Sections address the fundamental key concepts of ternary quantum dots, progress in synthesis strategies (i.e., organic and aqueous synthesis), and characterization methods (i.e., transmission electron microscopy, dynamic light scattering, etc.). Properties of ternary quantum dots are comprehensively reviewed, including optical, chemical and physical properties. The factors and mechanisms of the cytotoxicity of ternary quantum dot-based nanomaterials are also described. Since ternary chalcopyrite quantum dots are less toxic and more environmentally benign than conventional binary II-VI chalcogenide quantum dots, they are being investigated to replace conventional quantum dots in a range of applications. Thus, this book reviews QDs in various applications, such as solar cells, photocatalytic, sensors and bio-applications. Reviews fundamental concepts of ternary quantum dots and quantum dot-nanocomposites including the most relevant synthesis strategies, key properties, and characterization techniques Delves into the cytotoxicity of quantum dots looking at the factors and mechanisms that influence cytotoxicity including demonstration of cytotoxicity assays for in vitro and in vivo tests Touches on the many applications of ternary quantum dots including biomedical applications, applications in solar cells, sensing applications, and photocatalytic applications
Transition metal chalcogenides (TMC) is a broad class of materials comprising binary, ternary, quaternary, and multinary oxides, sulfides, selenides, and tellurides. These materials have application in different areas such as solar cells, photocatalysis, sensors, photoinduced therapy, and fluorescent labeling. Due to the technological importance of this class of material, it is necessary to find synthetic methods to produce them through procedures aligned with the Green Chemistry. In this sense, this chapter presents opportunities to make the solution chemistry synthesis of TMC greener. In addition to synthesis, the chapter presents different techniques of experimental planning and analysis, such as design of experiments, life cycle assessment, and machine learning. Then, it explains how Green Chemistry can benefit from each one of these techniques, and how they are related to the Green Chemistry Principles. Focus is placed on binary chalcogenides (sulfides, selenides, and tellurides), and the quaternary sulfide Cu2ZnSnS4 (CZTS), due to its application in many fields like solar energy, photocatalysis, and water splitting. The Green Chemistry synthesis, characterization, and application of these materials may represent sustainable and effective ways to save energy and resources without compromising the quality of the produced material.
Nanomaterials via Single-Source Precursors: Synthesis, Processing and Applications presents recent results and overviews of synthesis, processing, characterization and applications of advanced materials for energy, electronics, biomedicine, sensors and aerospace. A variety of processing methods (vapor, liquid and solid-state) are covered, along with materials, including metals, oxides, semiconductor, sulfides, selenides, nitrides, and carbon-based materials. Production of quantum dots, nanoparticles, thin films and composites are described by a collection of international experts. Given the ability to customize the phase, morphology, and properties of target materials, this “rational approach to synthesis and processing is a disruptive technology for electronic, energy, structural and biomedical (nano)materials and devices. The use of single-source chemical precursors for materials processing technology allows for intimate elemental mixing and hence production of complex materials at temperatures well below traditional physical methods and those involving direct combination of elements. The use of lower temperatures enables thin-film deposition on lightweight polymer substrates and reduces damage to complex devices structures such as used in power, electronics and sensors. Discusses new approaches to synthesis or single-source precursors (SSPs) and the concept of rational design of materials Includes materials processing of SSPs in the design of new materials and novel devices Provides comprehensive coverage of the subject (materials science and chemistry) as related to SSPs and the range of potential applications