Chemistry of the First Row Transition Metals pdf epub mobi txt 电子书 下载 2026

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出版者:Oxford Univ Pr

作者:McCleverty, Jon A.

出品人:

页数:100

译者:

出版时间:1999-4

价格:$ 28.25

装帧:Pap

isbn号码:9780198501510

丛书系列:

图书标签:

• Transition Metals
• Inorganic Chemistry
• Coordination Chemistry
• Organometallic Chemistry
• Chemical Bonding
• Spectroscopy
• Redox Chemistry
• Catalysis
• First Row Metals
• Chemical Properties

The Art and Science of Material Synthesis: A Comprehensive Guide This volume delves into the intricate world of modern material synthesis, focusing not on the established chemistry of the first-row transition metals, but rather on the pioneering methodologies, theoretical frameworks, and diverse applications that underpin the creation of novel, functional materials across the periodic table. The scope here extends far beyond the d-block elements often dominating introductory inorganic texts, engaging instead with the complexities of main-group chemistry, lanthanides, actinides, and the emerging field of organic-inorganic hybrid structures. Part I: Theoretical Foundations and Design Principles The initial sections lay a robust theoretical groundwork essential for rational material design. We explore the contemporary evolution of Density Functional Theory (DFT) and its application in predicting thermodynamic stability, electronic structure, and phase transitions in complex solid-state systems. A significant focus is placed on the limitations of standard approximations (like LDA and GGA) when dealing with strongly correlated systems, particularly Mott insulators and charge-transfer insulators, providing detailed case studies on the necessary inclusion of on-site Coulomb repulsion terms ($U$) and spin-orbit coupling (SOC) for accurate band gap prediction in materials outside the typical metallic or simple semiconductor regimes. Furthermore, the volume examines emergent concepts in crystal engineering. This includes detailed discussions on supramolecular chemistry principles applied to inorganic frameworks—specifically the exploitation of halogen bonding ($ ext{XB}$), pnictogen bonding ($ ext{Pnictogen-B}$), and quadrupole-dipole interactions for directing the self-assembly of porous materials. We analyze how subtle changes in molecular precursors dictate the resulting crystallographic space group and, critically, the macroscopic properties like porosity and surface area. The emphasis shifts from traditional stoichiometric control to kinetic control influenced by solvent environment and reaction temperature gradients. Part II: Advanced Synthesis Methodologies The core of this book is dedicated to mastering non-classical synthetic routes that circumvent the limitations of high-temperature solid-state reactions. A. Solution-Phase Techniques: A dedicated chapter examines solvothermal and hydrothermal synthesis, moving beyond simple precipitation. We analyze the role of supercritical fluids—particularly supercritical $ ext{CO}_2$—as tunable reaction media for synthesizing size-controlled nanoparticles and nanowires of metal oxides (e.g., $ ext{TiO}_2$, $ ext{ZrO}_2$) and phosphors. The critical parameters discussed include the critical point density, pressure cycling protocols, and the use of templating agents that act as structure-directing agents (SDAs) rather than simple surfactants. Specific attention is given to the synthesis of complex perovskites ($ ext{ABX}_3$ structures) via low-temperature solution processing, detailing techniques to mitigate undesirable secondary phase formation (e.g., lead-halide segregation). B. Vapor-Phase Deposition and Atomic Layer Control: This section provides an in-depth comparison of Chemical Vapor Deposition (CVD), Physical Vapor Deposition (PVD), and the highly precise Atomic Layer Deposition (ALD). ALD is treated not merely as a thin-film technique but as a powerful tool for creating high-aspect-ratio nanostructures and multilayer heterostructures with angstrom-level precision. The mechanistic nuances of self-limiting surface reactions are explored, focusing on precursors for depositing binary and ternary nitrides ($ ext{GaN}$, $ ext{AlON}$) and high-k dielectrics ($ ext{HfO}_2$, $ ext{Al}_2 ext{O}_3$), emphasizing the importance of minimizing parasitic reactions through careful pulse timing and purging strategies. C. Mechanochemical Synthesis: A substantial portion is dedicated to the burgeoning field of mechanochemistry, utilizing high-energy ball milling (HEBM) to drive solid-state reactions at ambient temperatures. This technique is presented as a powerful, solvent-minimized alternative for synthesizing metal-organic frameworks ($ ext{MOFs}$) and covalent organic frameworks ($ ext{COFs}$) that are often unstable or difficult to grow via traditional solution methods. The chapter details particle size reduction kinetics, phase transformation under mechanical stress, and the unique defect structures introduced by milling, which can enhance catalytic activity by increasing the density of active sites. Part III: Functional Material Classes Beyond the First Row The latter part of the volume systematically surveys specific classes of materials whose function relies on chemistries distinct from those governed by $3d$ orbitals. A. Lanthanide and Actinide Chemistry in Luminescence and Catalysis: We explore the unique spectroscopic properties arising from $4f$ and $5f$ electron shell shielding. For lanthanides (e.g., Europium, Terbium), the focus is on developing highly efficient sensitizer-activator energy transfer mechanisms in phosphors for solid-state lighting and bioimaging probes. This involves detailed analysis of the antenna effect using organic ligands optimized for broadband absorption. For actinides, the discussion centers on their role in specialized nuclear fuel matrices and advanced separation chemistry, focusing on the relativistic effects that significantly alter orbital energies and bonding character compared to lighter elements. B. Main Group Semiconductors and Topological Insulators: The book examines the resurgence of main-group elements (Group 13-16) in high-performance electronics. This includes the synthesis and characterization of III-V and II-VI semiconductors (e.g., $ ext{GaAs}$, $ ext{ZnSe}$) using tailored epitaxial growth techniques. Crucially, it addresses the synthesis of Topological Insulators (TIs), such as compounds based on Bismuth and Antimony ($ ext{Bi}_2 ext{Se}_3$), analyzing how precise stoichiometry control is vital for maintaining the bulk insulating nature while preserving the protected, spin-polarized surface states—a property entirely dependent on strong spin-orbit coupling inherent in these heavier elements. C. Hybrid Materials and Functional Interfaces: The final chapters address the challenges of integrating organic and inorganic components. This includes the synthesis of complex chalcogenides (sulfides, selenides) designed for thermoelectric energy conversion, where the organic component is used to significantly reduce the lattice thermal conductivity ($kappa_L$) via anharmonic scattering, while the inorganic framework maintains high electrical conductivity ($sigma$). The synthetic challenges of achieving durable interfaces between conductive polymers and crystalline metal oxides for advanced photovoltaic applications are also discussed, focusing on surface functionalization techniques to minimize charge recombination losses. Throughout the text, the synthesis procedures are supported by requisite characterization techniques—ranging from high-resolution transmission electron microscopy ($ ext{HR-TEM}$) to synchrotron-based X-ray absorption spectroscopy ($ ext{XAS}$)—to validate the resulting structure, purity, and functional performance of the synthesized materials.

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