Transmission electron microscopy (TEM) has become one of the most powerful techniques in the fields of material science, inorganic chemistry and nanotechnology. In terms of resolutions, advanced TEM may reach a high spatial resolution of 0.05 nm, a high energy-resolution of 7 meV. In addition, in situ TEM can help researcher to image the process happened within 1 ms. This paper reviews the recent technical approaches of applying advanced TEM characterization on nanomaterials for catalysis. The text is organized according to the demanded information of nanocrystals from the perspective of application: for example, size, composition, phase, strain, and morphology. The electron beam induced effect and in situ TEM are also introduced. As a result, I hope this review can help the scientists in related fields to take advantage of advanced TEM to their own researches.
Selected, peer reviewed papers from the First Joint Advanced Electron Microscopy School for Nanomaterials and the Workshop on Nanomaterials (AEM-NANOMAT’09), Saltillo (Coahuila) México, September 29th-October 2nd, 2009
Catalysis will continue to be vitally important to the advancement and sustainability of industrialized societies. Unfortunately, the petroleum-based resources that currently fuel the energy and consumer product needs of an advancing society are becoming increasingly difficult and expensive to extract as supplies diminish and the quality of sources degrade. Therefore, the development of sustainable energy sources and the improvement of the carbon efficiency of existing chemical processes are critical. Further challenges require that these initiatives are accomplished in an environmentally friendly fashion since the effects of carbon-based emissions are proving to be a serious threat to global climate stability. In this dissertation, materials being developed for sustainable energy and process improvement initiatives are studied. Our approach is to use materials characterization, namely advanced electron microscopy, to analyze the targeted systems at the nano- or Ångstrom-scale with the goal of developing useful relationships between structure, composition, crystalline order, morphology, and catalytic performance. One area of interest is the complex Mo-V-M-O (M=Te, Sb, Ta, Nb) oxide system currently being developed for the selective oxidation/ammoxidation of propane to acrylic acid or acrylonitrile, respectively. Currently, the production of acrylic acid and acrylonitrile rely on propylene-based processes, yet significant cost savings could be realized if the olefin-based feeds could be replaced by paraffin-based ones. The major challenge preventing this feedstock replacement is the development of a suitable paraffin-activating catalyst. Currently, the best candidate is the Mo-V-Nb-Te-O complex oxide catalyst that is composed of two majority phases that are commonly referred to as M1 and M2. However, there is a limited understanding of the roles of each component with respect to how they contribute to catalyst stability and the reaction mechanism. Aberration-corrected electron microscopy was used to systematically examine, atomic column by atomic column, the effect of elemental substitution on the long-range crystalline order, atomic coordinates, and site occupancies of the various formulations such that trends could be developed linking these properties to catalytic yields. To accomplish this task, an algorithm was developed that enabled the direct extraction of atomic coordinates and site occupancies from high-angle annular dark-field (HAADF) images to within 1% and 15% uncertainty, respectively. Furthermore, this general method could be applied to various crystalline systems and may dramatically improve the quality of initial structural models used in Rietveld refinements. Improvement in the quality of starting models may increase the structural and chemical complexity of inorganic structures that can be solved by using "powder methods" alone. In addition to the development of these trends, HAADF analyses also revealed the presence of coherent compositional miscibility gaps, rotational twin domains, and structural intergrowths in the complex Mo-V-M-O oxide system. Other catalytic systems that are addressed in this dissertation include Pd, Ag, and bimetallic Pd-Ag catalysts for the selective hydrogenation of acetylene in excess ethylene, alkali and alkaline earth promoted Ru catalysts for the production of clean hydrogen through the decomposition of ammonia, the production of Pt nanoparticles using dendrimer templates, and Pt-Re bimetallic catalysts for the conversion of glycerol to hydrocarbons and syn gas. In each of these studies, electron microscopy was used as a complimentary tool to synthetic and reaction studies to better understand interactions between the nanoparticles and the support/template, to determine the effect of adding various promoters, or to understand the nanoscale structural and chemical changes associated with the formation of bimetallic nanoparticles. A final area addressed in this dissertation is the interaction between the electron beam and the specimen. In one particular study directed toward the characterization of Ni-Bi nanomaterials, it was discovered that exposure to an intense electron beam initiated particle fragmentation that led to the formation of a field of nanoparticles. Subsequent microscopy studies of the resulting nanoparticle field revealed bimetallic nanoparticles, core-shell structures, Ångstrom-scale atomic clusters, and individual atoms that decorated the surrounding carbon substrate. The identification of these structures along with the analysis of the parent material enabled the development of a fragmentation mechanism.
Advanced Nanomaterials for Catalysis and Energy: Synthesis, Characterization and Applications outlines new approaches to the synthesis of nanomaterials (synthesis in flow conditions, laser electrodispersion of single metals or alloys on carbon or oxide supports, mechanochemistry, sol-gel routes, etc.) to provide systems with a narrow particle size distribution, controlled metal-support interaction and nanocomposites with uniform spatial distribution of domains of different phases, even in dense sintered materials. Methods for characterization of real structure and surface properties of nanomaterials are discussed, including synchrotron radiation diffraction and X-ray photoelectron spectroscopy studies, neutronography, transmission/scanning electron microscopy with elemental analysis, and more. The book covers the effect of nanosystems' composition, bulk and surface properties, metal-support interaction, particle size and morphology, deposition density, etc. on their functional properties (transport features, catalytic activity and reaction mechanism). Finally, it includes examples of various developed nanostructured solid electrolytes and mixed ionic-electronic conductors as materials in solid oxide fuel cells and asymmetric supported membranes for oxygen and hydrogen separation. Outlines synthetic and characterization methods for nanocatalysts Relates nanocatalysts' properties to their specific applications Proposes optimization methods aiming at specific applications
Third volume of a 40volume series on nanoscience and nanotechnology, edited by the renowned scientist Challa S.S.R. Kumar. This handbook gives a comprehensive overview about Transmission electron microscopy characterization of nanomaterials. Modern applications and state-of-the-art techniques are covered and make this volume an essential reading for research scientists in academia and industry.
In this chapter, the author will review several advanced microscopy techniques developed at the NASA Glenn Research Center in the last 5 years. Topical areas include: unconventional approach to investigate the fine nanoporous structure of aerogels by scanning electron microscopy, new limits for transmission electron microscopy investigation of dispersion and chirality of single-walled carbon nanotubes within a polymer matrix, the importance of microstructure of porous tin dioxide nanostructure that lead to first time detection of methane at room temperature without doping or catalyst, in situ SEM methods to study the thermal stability of nanoparticles on Graphene/Cu based materials, electron beam irradiation effects on carbon nanotube yarns electrical properties, and nanoindentation work of multiphase thermoelectric material.
Research in noble metal nanoparticles has led to exciting progress in a versatile array of applications. For the purpose of better tailoring of nanoparticles activities and understanding the correlation between their structures and properties, control over the composition, shape, size and architecture of bimetallic and multimetallic nanomaterials plays an important role on revealing their new or enhanced functions for potentials application. Advance electron microscopy techniques were used to provide atomic scale insights into the structure-properties of different materials: PtPd, Au-Au 3 Cu, Cu-Pt, AgPd/Pt and AuCu/Pt nanoparticles. The objective of this work is to understand the physical and chemical properties of nanomaterials and describe synthesis, characterization, surface properties and growth mechanism of various bimetallic and multimetallic nanoparticles. The findings have provided us with novel and significant insights into the physical and chemical properties of noble metal nanoparticles. Different synthesis routes allowed us to synthesize bimetallic: Pt-Pd, Au-Au 3 Cu, Cu-Pt and trimetallic: AgPd/Pt, AuCu/Pt, core-shell and alloyed nanoparticles with monodispersed sizes, controlled shapes and tunable surface properties. For example, we have synthesized the polyhedral PtPd core-shell nanoparticles with octahedral, decahedral, and triangular plates. Decahedral PtPd core-shell structures are novel morphologies for this system. For the first time we fabricated that the Au core and Au 3 Cu alloyed shell nanoparticles passivated with CuS2 surface layers and characterized by Cs-corrected scanning transmission electron microscopy. The analysis of the high-resolution micrographs reveals that these nanoparticles have decahedral structure with shell periodicity, and that each of the particles is composed by Au core and Au 3 Cu ordered superlattice alloyed shell surrounded by CuS 2 surface layer. Additionally, we have described both experimental and theoretical methods of synthesis and growth mechanism of highly monodispersed Cu-Pt nanoclusters. The advance electron microscopy of microanalysis allowed us to study the distribution of Cu and Pt with atomistic resolution. The microanalysis revealed that Pt is embedded randomly in the Cu lattice. A novel grand canonical - Langevin dynamics simulation showed the formation of alloy structures in good agreement with the experimental evidence. Finally, we demonstrated the synthesis of AgPd-Pt trimetallic nanoparticles with two different morphologies: multiply twinned core-shell, and hollow particles. We also investigated the growth mechanism of the nanoparticles using grand canonical-Monte Carlo simulations. We found that the Pt regions grow at overpotentials on the AgPd nanoalloys, forming 3D islands at the early stages of the deposition process and presenting very good agreement between the simulated structures and those observed experimentally. Similarly, we also investigated AuCu/Pt core-shell trimetallic nanoparticles, presenting new way to control the nanoparticles morphologies due to the presence of third metal (Pt). Where, we observed the Pt layers are overgrowth on the as prepared AuCu core by Frank-van der Merwe (FM) and Stranski-Krastanov (SK) growth modes. In addition, these nanostructure presents high index facet surfaces with {211} and (321} families, that are highly open structure surfaces and interesting for the catalytic applications. The results of these studies will be useful for the future applications and the design of advanced functional nanomaterials.
Microscopy Methods in Nanomaterials Characterization fills an important gap in the literature with a detailed look at microscopic and X-ray based characterization of nanomaterials. These microscopic techniques are used for the determination of surface morphology and the dispersion characteristics of nanomaterials. This book deals with the detailed discussion of these aspects, and will provide the reader with a fundamental understanding of morphological tools, such as instrumentation, sample preparation and different kinds of analyses, etc. In addition, it covers the latest developments and trends morphological characterization using a variety of microscopes. Materials scientists, materials engineers and scientists in related disciplines, including chemistry and physics, will find this to be a detailed, method-orientated guide to microscopy methods of nanocharacterization. Takes a method-orientated approach that includes case studies that illustrate how to carry out each characterization technique Discusses the advantages and disadvantages of each microscopy characterization technique, giving the reader greater understanding of conditions for different techniques Presents an in-depth discussion of each technique, allowing the reader to gain a detailed understanding of each
Catalysis by Materials with Well-Defined Structures examines the latest developments in the use of model systems in fundamental catalytic science. A team of prominent experts provides authoritative, first-hand information, helping readers better understand heterogeneous catalysis by utilizing model catalysts based on uniformly nanostructured materials. The text addresses topics and issues related to material synthesis, characterization, catalytic reactions, surface chemistry, mechanism, and theoretical modeling, and features a comprehensive review of recent advances in catalytic studies on nanomaterials with well-defined structures, including nanoshaped metals and metal oxides, nanoclusters, and single sites in the areas of heterogeneous thermal catalysis, photocatalysis, and electrocatalysis. Users will find this book to be an invaluable, authoritative source of information for both the surface scientist and the catalysis practitioner Outlines the importance of nanomaterials and their potential as catalysts Provides detailed information on synthesis and characterization of nanomaterials with well-defined structures, relating surface activity to catalytic activity Details how to establish the structure-catalysis relationship and how to reveal the surface chemistry and surface structure of catalysts Offers examples on various in situ characterization instrumental techniques Includes in-depth theoretical modeling utilizing advanced Density Functional Theory (DFT) methods
