This review includes 70 monomeric high-spin complexes of the following general compositions: [Fe(II)(η3-pdc)(L)3], [Fe(III)(η3-pdc)(L)3]+, [Fe(II)(η3-pdc)2]2− and [Fe(III)(η3-pdc)2]− (pdc = pyridine-2,6-dicarboxylate (−2)). Each Fe(II) atom has a distorted octahedral geometry. The Fe(III) atoms have a distorted octahedral geometry (most common) and in some examples have a distorted pentagonal-bipyramidal geometry. The chelating donor ligands create varieties of n-membered metallocyclic rings: ONO, OCO, NC2N, OC2N, OC2NO and OC3O. Some cooperative effects between Fe(II) and Fe(III) complexes were found and discussed. There are complexes that are examples of distortion isomerism.
Tungsten is an elegant substance, and its compounds have great significance because of their extensive range of applications in diverse fields such as in gas sensors, photocatalysis, lithium ion batteries, H2 production, electrochromic devices, dyed sensitized solar cells, microchip technology, and liquid crystal displays. Tungsten compounds exhibit a more efficient catalytic behavior, and tungsten-dependent enzymes generally catalyze the transfer of an oxygen atom to or from a physiological donor/acceptor with the metal center. Furthermore, tungsten has an n-type semiconductor band gap. Tungsten forms complexes by reacting with several elements such as H, C, N, O, and P as well as other numerous inorganic elements. Interestingly, all tungsten reactions occur at ambient temperature, usually with tetrahydrofuran and dichloromethane under vacuum. Tungsten has extraordinarily high-temperature properties, making it very useful for X-ray production and heating elements in furnaces. Tungsten coordinates with diverse nonmetallic elements and ligands and produces interesting compounds. This article describes an overview of the synthesis of various organometallic compounds of tungsten.
Metallic and bimetallic nanosponges with well-defined size and form have attracted increasing attention due to their unique structural properties and their potential for many applications. In this chapter, the recently developed methods for the synthesis and preparation of metallic and bimetallic nanosponges are presented. These methods can be mainly cataloged in two groups: dealloying-based methods and reduction reaction-based methods. Different topographical reconstruction methods for the investigation of their structural properties are then reviewed briefly. The optical properties of the metallic nanosponges are clearly different from those of the solid counterparts due to the tailored disordered structure. The recent advances in the exploration of the distinct linear and non-linear optical properties of the nanosponges are summarized.
Rare earth metal oxide nanomaterials have drawn much attention in recent decades due to their unique properties and promising applications in catalysis, chemical and biological sensing, separation, and optical devices. Because of the strong structure-property correlation, controllable synthesis of nanomaterials with desired properties has long been the most important topic in nanoscience and nanotechnology and still maintains a grand challenge. A variety of methods, involving chemical, physical, and hybrid method, have been developed to precisely control nanomaterials, including size, shape, dimensionality, crystal structure, composition, and homogeneity. These nanostructural parameters play essential roles in determining the final properties of functional nanomaterials. Full understanding of nanomaterial properties through characterization is vital in elucidating the fundamental principles in synthesis and applications. It allows researchers to discover the correlations between the reaction parameters and nanomaterial properties, offers valuable insights in improving synthetic routes, and provokes new design strategies for nanostructures. In application systems, it extrapolates the structure-activity relationship and reaction mechanism and helps to establish quality model for similar reaction processes. The purpose of this chapter is to provide a comprehensive overview and a practical guide of rare earth oxide nanomaterial design and characterization, with special focus on the well-established synthetic methods and the conventional and advanced analytical techniques. This chapter addresses each synthetic method with its advantages and certain disadvantages, and specifically provides synthetic strategies, typical procedures and features of resulting nanomaterials for the widely-used chemical methods, such as hydrothermal, solvothermal, sol-gel, co-precipitation, thermal decomposition, etc. For the nanomaterial characterization, a practical guide for each technique is addressed, including working principle, applications, materials requirements, experimental design and data analysis. In particular, electron and force microscopy are illuminated for their powerful functions in determining size, shape, and crystal structure, while X-ray based techniques are discussed for crystalline, electronic, and atomic structural determination for oxide nanomaterials. Additionally, the advanced characterization methodologies of synchrotron-based techniques and in situ methods are included. These non-traditional methods become more and more popular because of their capabilities of offering unusual nanostructural information, short experiment time, and in-depth problem solution.
Bimetallic and multimetallic alloy nanoparticles are emerging as a class of critical nanomaterials in electronic, optical and magnetic fields due to their unique physic-chemical properties. In particular, precise control of the nanoparticle size can endow them with broad versatility and high selectivity. This chapter reviews some tremendous achievements in the development of size controlled bimetallic and multimetallic alloy nanoparticles, with special emphasis on general preparation methods, characterization methodologies and instrumentation techniques. Some key factors and future perspectives on the development of size-controlled bimetallic and multimetallic alloy nanoparticles are also discussed.
The minimum reactant concentration required to synthesize Au/M (M = Ag, Pt, Pd, Ru . . .) core-shell nanoparticles by the one-pot microemulsion route was calculated by a simulation model under different synthesis conditions. This minimum concentration was proved to depend on the reduction potential of the slower metal M and on the rigidity of the surfactant film composing the microemulsion. Model results were tested by comparing with Au/M nanoparticles taken from literature. In all cases, experimental data obey model predictions. From this agreement, one can conclude that the smaller the standard potential of the slower reduction metal, the lower the minimum concentration needed to obtain core-shell nanoparticles. In addition, the higher the surfactant flexibility, the higher the minimum concentration to synthesize metal segregated nanoparticles. Model prediction allows to quantify which is the best value of concentration to prepare different pairs of core-shell Au/M nanoparticles in terms of nature of M metal in the couple and microemulsion composition. This outlook may become an advanced tool for fine-tuning Au/M nanostructures.
Conventional inorganic semiconductor quantum dots (QDs) have numerous applications ranging from energy harvesting to optoelectronic and bio-sensing devices primarily due to their unique size and shape tunable band-gap and also surface functionalization capability and consequently, have received significant interest in the last few decades. However, the high market cost of these QDs, on the order of thousands of USD/g and toxicity limit their practical utility in many industrial applications. In this context, graphene quantum dot (GQD), a nanocarbon material and a new entrant in the quantum-confined semiconductors could be a promising alternative to the conventional toxic QDs due to its potential tunability in optical and electronic properties and film processing capability for realizing many of the applications. Variation in optical as well as electronic properties as a function of size, shape, doping and functionalization would be discussed with relevant theoretical backgrounds along with available experimental results and limitations. The review deals with various methods available so far towards the synthesis of GQDs along with special emphasis on characterization techniques starting from spectroscopic, optical and microscopic techniques along with their the working principles, and advantages and limitations. Finally, we will comment on the environmental impact and toxicity limitations of these GQDs and their hybrid nanomaterials to facilitate their future prospects.