Annual Review of Materials Research - Volume 35, 2005

Recent research trends of the preparation and characterization of highly efficient titanium oxide–based photocatalysts are reviewed on the basis of studies done in our laboratory. Special attention is focused on the preparation and characterization of active sites of highly dispersed titanium oxide species within mesoporous matrices and on titanium oxide–based binary catalysts such as Ti/Si and Ti/B oxides and unique visible light-responsive second-generation TiO2 photocatalysts prepared by an advanced metal-ion-implantation and RF magnetron sputtering deposition method. Highly dispersed titanium oxide species within mesoporous frameworks and titanium oxide–based binary catalysts exhibit high and unique photocatalytic activities for various reactions, such as the direct decomposition of NOx. These species also have photo-induced superhydrophiric properties. It is of significance that visible light-responsive TiO2 photocatalysts can be applied to the decomposition of NOx in air and the degradation of pollutants in water, as well as to the splitting of water under UV and visible light irradiation.

This paper describes the use of extended X-ray absorption fine structure spectroscopy (EXAFS) to examine the structure of molten salts and ionic liquids and species dissolved in them. The EXAFS theory is briefly described as are the methods by which EXAFS of these systems can be studied. A range of applications have used EXAFS to investigate the structure of metallic species in ionic liquids from extraction studies to catalysts. The area of structural investigations of ionic liquids is still being developed, although growing rapidly, whereas the structure of molten salts has been studied using EXAFS in more detail.

The diffusion-multiple approach—the creation of composition gradients and intermetallic phases by long-term annealing of junctions of three or more phases/alloys—enables the generation of a large number of phases and compositions for efficient mapping of phase diagrams, phase properties, and kinetics. With an efficiency much higher than that of a conventional approach, many critical materials data, which otherwise would be too time-consuming and expensive to acquire, can be obtained and employed to accelerate alloy design. The critical data for structural materials design include phase diagrams, diffusion coefficients, precipitation kinetics, solution-strengthening effects, and precipitation-strengthening effects. All these data can be obtained from diffusion multiples. The combination of the diffusion-multiple approach with the CALPHAD approach can impact computational design of structural materials. The diffusion-multiple approach can also be applied to combinatorial screening of functional materials having unique physical, chemical, or other properties when micro-scale measurement techniques are available for these properties. Examples are shown to illustrate the progress made to date on applying the diffusion-multiple approach to accelerated design/discovery of materials.

This review is an introduction to the problem of determining the nature of the diffraction spectra of ordered solids. After explicit computation examples of Bragg diffraction spectra of quasicrystals (bulk, surface) in kinematical and dynamical (high-resolution electron microscopy) situations, we show on simple toy models that long-range order does not necessarily lead to Bragg peaks which, in turn, are not necessarily the signature of the unique long-range periodic order.

It has recently become possible to measure the anisotropic distribution of interfaces in polycrystals and composites. Because classical theories for grain growth and coarsening assume isotropic interface properties, they are incapable of explaining how these distributions arise. The purpose of this paper is to review the results of recent experiments, simulations, and theories that document the effects of anisotropy on the capillarity-driven evolution of granular systems. The results suggest that meaningful predictions of evolving microstructural characteristics can be made using models that incorporate the anisotropy of the interfacial energy and mobility.

The preparation of skeletal catalysts is considered, with particular reference to the preparation of skeletal nickel and skeletal copper. Skeletal catalysts have physical properties that are highly desired for some industrial processes, and the means of controlling these properties to optimize performance is reviewed. The preparation can be affected by the initial alloy composition, the quenching process, the leaching procedure, aging and by the addition of promoters. These processes may affect either or both the chemical and physical characteristics of the catalysts. Preparation procedures need to be adjusted for individual reactions if optimal performance is required. The effect of the preparation conditions on the structure and catalytic performance of these systems is reviewed.

Heterogeneous asymmetric catalysis remains a topic of intense research interest because control of enantioselectivity represents one of the major synthetic challenges today. Successful strategies to achieve high enantioselection have been developed using three key approaches: (a) adsorption of chiral modifiers onto an active metal surface, which is found to be particularly effective for enantioselective hydrogenation; (b) covalent tethering of homogeneous catalysts; and (c) electrostatic interaction between a negatively charged framework and a cation. Other approaches have been advocated, e.g., encapsulation, but in general these lead to lower enantioselectivity for these heterogeneous asymmetric systems when compared with the equivalent homogeneous catalyst. This review covers the strategies for achieving high enantioselection as well as recent interesting features concerning confinement effects, the inversion of enantioselectivity, and specific cases in which enantioselection increases with conversion, all being factors that can guide researchers to identifying improved systems.

We review here the theory of the early stages of oxidation of the (110) surface of Ni1−x Alx, based on ab initio calculations using a plane-wave pseudopotential method. The clean surface and several oxidized surfaces have been investigated, with oxygen coverages up to 2ML of oxygen (1ML = 3 O atoms per 2 surface Al atoms). The theory to date is a description in terms of equilibrium thermodynamics, with a comparison of the free energies of several surfaces of different composition, implemented at the atomic scale. Three environmental parameters are singled out as control variables in this treatment, namely the alloy composition x (assumed to be near 0.5), the temperature T and the partial pressure of oxygen pO2. With certain reasonable approximations an analytic formula for the surface energy σ is derived in terms of these variables and some constants that are calculated ab initio together with others that are derived from experimental thermodynamic tables. At oxygen pressures just above the threshold for bulk oxidation of NiAl, the calculations explain the observed formation of a thin film of alumina in place of NiAl surface layers, with the consequent dissolution of Ni into the bulk. Ab initio calculations illustrate how the energetics of supplying Al to the surface depends on bulk stoichiometry, which alters the relative stability of different surface oxidation states so as to favour oxidation more if the alloy is Al-rich than if it is Ni-rich.

In recent years substantial progress has been made in the control of the properties of porous materials on the nano-, meso-, and macroscale. The feature of solids can, in favorable cases, be tailored to such an extent that one is justified in using the term engineering of porous catalytic materials. This review highlights recent developments concerning (a) the control of the pore structure of zeolites, (b) the creation of single site type catalysts based on ordered mesoporous oxides, (c) the catalytic potential of porous coordination compounds, and (d) the advances with respect to direct production of desired shapes of porous catalytic materials.

Chemical analysis at high spatial resolution is the domain of analytical transmission electron microscopy. Owing to rapid instrumental developments during the past decade, electron energy-loss spectroscopy offers now a spatial resolution close to 0.1 nm and an energy resolution close to 0.1 eV. This development has been accompanied by the introduction of numerous new techniques and methods for data acquisition and analysis, which are outlined in the present article. Recent results for a wide range of material systems are addressed. These comprise first-principles calculations, which have contributed to enormous progress in the calculation of near-edge fine structures, and fingerprinting methods, which are still important for the interpretation of experimental data.

There is a pressing need for cleaner fuels (free or aromatics and of minimal sulfur content) or ones that convert chemical energy directly to electricity, silently and without production of noxious oxides and particulates; chemical, petrochemical and pharmaceutical processes that may be conducted in a one-step, solvent-free manner and that use air as the preferred oxidant; and industrial processes that minimize consumption of energy, production of waste, or the use of corrosive, explosive, volatile, and nonbiodegradable materials. All these needs and other desiderata, such as the in situ production and containment of aggressive and hazardous reagents, and the avoidance of use of ecologically harmful elements, may be achieved by designing the appropriate heterogeneous inorganic catalyst, which ideally should be cheap, readily preparable and fully characterizable, preferably under in situ reaction conditions. A range of nanoporous and nanoparticle catalysts that meet most of the stringent demands of sustainable development and responsible (clean) technology is described. Specific examples that are highlighted include the production of adipic acid (precursor of polyamides and urethanes) without the use of concentrated nitric acid nor the production of greenhouse gases such as nitrous oxide; the production of caprolactam (precursor of nylon) without the use of oleum and hydroxylamine sulfate; and the terminal oxyfunctionalization of linear alkanes in air. The topic of biocatalysis and sustainable development is also briefly discussed for the epoxidation of terpenes and fatty acid methyl esters; for the generation of polymers, polylactides, and polyesters; and for the production of 1,3-propanediol from corn.

This review covers the synthesis, characterization, and physico-chemical properties of microporous and mesoporous aluminophosphates and silicoaluminophosphates molecular sieves. Particular emphasis is given to the materials that have found applications as acid catalysts. We consider the evolution of the synthesis procedures from the first discoveries to the current methodologies and give perspectives for new possible synthesis strategies. Emphasis is given to the use of specially prepared precursors/reactants designed for the use as molecular sieves. Experimental (especially MAS-NMR and FTIR spectroscopy) and theoretical approaches to the description of the Si insertion into the ALPO framework and to the acidic properties of SAPOs and MeAPSOs materials are discussed.

This review illustrates how catalytically active molecular structures are created on oxide surfaces by attachment of metal complexes with subsequent structural transformation and molecular imprinting on the surfaces. Also discussed is how the designed surfaces are characterized in situ by physical techniques including conventional and time-resolved X-ray absorption fine structure. The structural transformation and molecular imprinting for attached metal complexes can provide a new class of catalytic materials with a high complexity for selective catalysis including shape-selective and asymmetric catalysis.

Catalyst life (with activity and selectivity) is one of the three essential properties of a practical catalyst, both in laboratory and industrial usage. For most catalysts in which the active phase is a metal, high activity requires a high metal surface area. In all cases, for long life, the metal surface area has to be maintained. The various modes of catalyst deactivation leading to loss of metal surface area are described (sintering, poisoning, coking, etc.). The choice of catalyst components for both active metal phases and for support phases is shown to be subject to thermodynamic and kinetic limits. Routes for the preparation of catalysts need to be and can be designed to give not only active, but also stable catalysts. Examples described include copper/zinc catalysts for hydrogenation/dehydrogenation reactions, iron catalysts for ammonia synthesis, nickel catalysts for hydrogenation reactions, automobile exhaust catalysts, and Raney catalysts.

The key role of electron microscopy in understanding and creating advanced catalyst materials and processes in selective alkane oxidation, environmental control, and alternative energy sources is reviewed. In many technological processes, catalysts are increasingly nanoscale heterogeneous materials. With growing regulatory guidelines requiring efficient and environmentally compatible catalytic processes, it is crucial to have a fundamental understanding of the catalyst nanostructure and modes of operation under reaction conditions to design novel catalysts and processes. The review highlights the pioneering development and applications of atomic resolution in situ-environmental transmission electron microscopy (ETEM) for probing dynamic catalysis directly at the atomic level, high-resolution electron microscopy, and analytical spectroscopic methods in the development of alkane catalyzation, environmental protection, and new energy sources.

Renewable energy resources, of which wind energy is prominent, are part of the solution to the global energy problem. Wind turbine and the rotorblade concepts are reviewed, and loadings by wind and gravity as important factors for the fatigue performance of the materials are considered. Wood and composites are discussed as candidates for rotorblades. The fibers and matrices for composites are described, and their high stiffness, low density, and good fatigue performance are emphasized. Manufacturing technologies for composites are presented and evaluated with respect to advantages, problems, and industrial potential. The important technologies of today are prepreg (pre-impregnated) technology and resin infusion technology. The mechanical properties of fiber composite materials are discussed, with a focus on fatigue performance. Damage and materials degradation during fatigue are described. Testing procedures for documentation of properties are reviewed, and fatigue loading histories are discussed, together with methods for data handling and statistical analysis of (large) amounts of test data. Future challenges for materials in the field of wind turbines are presented, with a focus on thermoplastic composites, new structural materials concepts, new structural design aspects, structural health monitoring, and the coming trends and markets for wind energy.

In the nanoscience era, the properties of many exciting new materials and devices will depend on the details of their composition down to the level of single atoms. Thus the characterization of the structure and electronic properties of matter at the atomic scale is becoming ever more vital for economic and technological as well as for scientific reasons. The combination of atomic-resolution Z-contrast scanning transmission electron microscopy (STEM) and electron energy loss spectroscopy (EELS) represents a powerful method to link the atomic and electronic structure to macroscopic properties, allowing materials, nanoscale systems, and interfaces to be probed in unprecedented detail. Z-contrast STEM uses electrons that have been scattered to large angles for imaging. The relative intensity of each atomic column is roughly proportional to Z², where Z is the atomic number. Recent developments in correcting the aberrations of the lenses in the electron microscope have pushed the achievable spatial resolution and the sensitivity for imaging and spectroscopy in the STEM into the sub-Ångstrom (sub-Å) regime, providing a new level of insight into the structure/property relations of complex materials. Images acquired with an aberration-corrected instrument show greatly improved contrast. The signal-to-noise ratio is sufficiently high to allow sensitivity even to single atoms in both imaging and spectroscopy. This is a key achievement because the detection and measurement of the response of individual atoms has become a challenging issue to provide new insight into many fields, such as catalysis, ceramic materials, complex oxide interfaces, or grain boundaries. In this article, the state-of-the-art for the characterization of all of these different types of materials by means of aberration-corrected STEM and EELS are reviewed.

The review highlights the state-of-the-art research regarding the application of modern in situ spectroscopic, microscopic, and electrochemical techniques to improve the understanding of the interaction of organic molecules with metal surfaces. We also consider the chemical and electrochemical processes that lead to a de-adhesion of polymers from metal surfaces. Spectroscopic techniques such as surface-enhanced infrared or Raman spectroscopy provide molecular understanding of organic molecules and water at buried metal surfaces. This information is complementary to adhesion studies by means of atomic force microscopy and de-adhesion studies of polymer layers from metals by means of a scanning Kelvin probe. Adhesion and de-adhesion mechanisms are discussed, especially those involving humid and corrosive environments, which are the predominant and most important for metal/polymer composites in engineering applications.