Sodium clusters in zeolites

The method of loading sodium clusters in zeolites, consisting of the controlled thermal decomposition of physisorbed sodium azide, is discussed. The influence of the azide loading, the azide decomposition rate and the sintering process on the amount of ionic and metallic sodium clusters in zeolite Y was followed by ESR. The method is compared to other metal deposition techniques.     

Structural and stability characteristics of agglomerated clusters

We investigated the cohesion of agglomerates formed by sticking two fractal clusters, each cluster having been previously generated by particle aggregation on a 3D lattice. The degree of cohesion of an agglomerate of a given configuration was defined by the number of connections simultaneously established on the two stuck clusters. All the possible nonoverlapping configurations were investigated and the corresponding porosity and brittleness as well as the pore volume and connection frequencies were determined. The numerical study showed the greater internal cohesion of agglomerates issued from sticking of reaction-limited aggregation (RLA) clusters compared to that of diffusion-limited-aggregation (DLA) clusters. DLA and RLA agglomerates presented continuously decreasing pore volume frequency curves, the latter agglomerates being characterised by a greater frequency of large pores. Comparison with typical controlled fragmentation experiments showed the number of connections to be the prevailing factor in the cohesion of aggregates formed in aqueous suspensions under various conditions. Received: 25 January 2001 Accepted: 16 May 2001     

Structural stability of boron clusters with octahedral and tetrahedral symmetries

The structural stability of cagelike boron clusters with octahedral and tetrahedral symmetries has been investigated by means of first-principles calculations. Twenty-eight cluster models, ranging from B(10) to B(66), were systematically constructed using regular and semiregular polyhedra as prototypes. The binding energies per atom were, on the whole, slightly lower than those of icosahedral clusters B(80) and B(100), which are supposed to be the most stable in the icosahedral group. The larger clusters did not always have higher binding energies. Isothermal molecular dynamics simulations were performed to determine the deformation temperatures at which clusters began to break or change their structures. We found eight clusters that had nonzero deformation temperatures, indicating that they are in metastable states. The octahedral cluster B(18) had the highest deformation temperature among these, similar to that of icosahedral B(80) and B(100). The analysis of the electronic structure of B(18) showed that it attained this high stability owing to Jahn-Teller distortion.     

Structural stability and phase transition in OsC and RuC

The structural stability and phase transition of osmium and ruthenium carbides (OsC and RuC) were investigated by first principles. Nine structures were considered for each carbide. Zinc blende structure has the lowest energy among the considered structures at ambient conditions for both carbides. For OsC at elevated pressures, the most stable phase is zinc blende structure from 0 to 10 GPa, FeSi from 10 to 32 GPa. In these two structures, Os atom is fourfold coordinated. From 32 to 40 GPa, tungsten carbide (WC) and NiAs are energetically competitive with Os atom sixfold coordinated. NiAs becomes energetically the most stable structure above 40 GPa. For RuC, zinc blende structure is the most stable from 0 to 20 GPa. From 20 to 100 GPa, WC structure is the most stable.     

Structural stability and phase transitions in WO3 thin films

Tungsten oxide (WO3) thin films have been produced by KrF excimer laser (lambda = 248 nm) ablation of bulk ceramic WO3 targets. The crystal structure, surface morphology, chemical composition, and structural stability of the WO3 thin films have been studied in detail. Characterization of freshly grown WO3 thin films has been performed using X-ray diffraction (XRD), atomic force microscopy (AFM), energy-dispersive X-ray spectroscopy (EDX), Raman spectroscopy (RS), transmission electron microscopy (TEM), and selected area electron diffraction (SAED) measurements. The results indicate that the freshly grown WO3 thin films are nearly stoichiometric and well crystallized as monoclinic WO3. The surface morphology of the resulting WO3 thin film has grains of approximately 60 nm in size with a root-mean-square (rms) surface roughness of 10 nm. The phase transformations in the WO3 thin films were investigated by annealing in the TEM column at 30-500 degrees C. The phase transitions in the WO3 thin films occur in sequence as the temperature is increased: monoclinic --> orthorhombic --> hexagonal. Distortion and tilting of the WO6 octahedra occurs with the phase transitions and significantly affects the electronic properties and, hence, the electrochemical device applications of WO3.     

Alkali-metal clusters as prototypes for electron solvation in zeolites

Zeolites are unique in that they can play host to a large number of alkali-metal clusters of the type M_n ^+p hitherto unseen in any other system. When isolated, these clusters behave as color centers. The alkali ions reside in ionic sites within the cavities and so the nature of the cluster is very much a function of the zeolite host, the Si:Al ratio, and the method chosen to prepare the cluster. Since these centers are created within zeolite cages rather than as structural defects (as is the case with the alkali halides) high cluster concentrations can be achieved at which point the optical and magnetic properties of the zeolite change profoundly. We review experimental work in this area, as well as our own attempts to understand both the electronic and optical properties of these systems in terms of an electron solvation model.     

Structural phase stability and magnetism in Co2FeO4 spinel oxide

We report a correlation between structural phase stability and magnetic properties of Co₂FeO₄ spinel oxide. We employed mechanical alloying and subsequent annealing to obtain the desired samples. The particle size of the samples changes from 25 nm to 45 nm. The structural phase separation of samples, except sample annealed at 900 °C, into Co-rich and Fe-rich spinel phase has been examined from XRD spectrum, SEM picture, along with EDX spectrum, and magnetic measurements. The present study indicated the ferrimagnetic character of Co₂FeO₄, irrespective of structural phase stability. The observation of mixed ferrimagnetic phases, associated with two Curie temperatures at T_C1 and T_C2 (>T_C1), respectively, provides the additional support of the splitting of single cubic spinel phase in Co₂FeO₄ spinel oxide.     

Silver clusters in the cages of zeolites: A quantum chemical study

The electronic structure of zeolite A is developed in a step by step procedure from the simple O_hH₈Si₈O₁₂ molecule, to the _∞ ¹ [(-O)₂H₄[Si₈O₁₂)] chain, to the _∞ ² [(-O₄)(Si₈O₁₂)] layer, and finally to the silica zeolite A framework _∞ ³ [Si₂₄O₄₈]. It is remarkable how well the calculated band structures of both, _∞ ² [(-O)₄(Si₈O₁₂)] and _∞ ³ [Si₂₄O₄₈] correspond to the experimentally determined band structure of α-quartz with a Fermi level of -10.55 eV. The HOMO region consists in each case of nonbonding 2p-oxygen bands which in a localized language can be denoted as oxygen lone pairs ( | O<). We observe in each case the typical behaviour of an insulator with saturated valencies whose electronic structure can be described as being localized and is already present in the starting O_h-H₈Si₈O₁₂ molecule. The double-8-rings D8R of the _∞ ² [(-O)₄(Si₈O₁₂)] layer have a pore diameter of 4.1 Å, the same as the pore opening of zeolite A. It is large enough to accept up to four Ag, forming _∞ ² [(-O)₄(Si₈O₁₂)Ag_n], n = 1, 2, 3, 4, layers, suitable for modelling the electronic interactions between the zeolite cavity embedded silver clusters and between the clusters and the zeolite framework. With one Ag per D8R the band structure is simply a superposition of the 4d, 5s and 5p levels of a layer of nearly noninteracting Ag and the silicon dioxide layer. The Ag-d band lies below the oxygen lone pairs, the Ag-s band lies about 3 eV above the oxygen lone pairs, and the Ag-5p bands are in the antibonding silicon dioxide region. The first electronic transition is of oxygen lone pair to Ag-5s LMCT type. Increasing silver content results in progressive splitting of the 5σ Ag bands and shifts the first (Ag^m+ _n)? ← (| O<) charge transfer transition to lower energies. The filled Ag 4d-bands lie always significantly below the (| O<) HOCOs (highest occupied crystal orbitals) but their band width increases with increasing silver content. In all cases the zeolite environment separates the Ag clusters through antibonding Ag-(← O<) interactions so that the coupling remains weak and it makes sense to describe the Ag clusters in the D8R as quantum dots weakly interacting with each other.     

Structural study of gold clusters

Density functional theory (DFT) calculations were carried out to study gold clusters of up to 55 atoms. Between the linear and zigzag monoatomic Au nanowires, the zigzag nanowires were found to be more stable. Furthermore, the linear Au nanowires of up to 2 nm are formed by slightly stretched Au dimers. These suggest that a substantial Peierls distortion exists in those structures. Planar geometries of Au clusters were found to be the global minima till the cluster size of 13. A quantitative correlation is provided between various properties of Au clusters and the structure and size. The relative stability of selected clusters was also estimated by the Sutton-Chen potential, and the result disagrees with that obtained from the DFT calculations. This suggests that a modification of the Sutton-Chen potential has to be made, such as obtaining new parameters, in order to use it to search the global minima for bigger Au clusters.     

Structural transition in SF6 clusters

SF₆ clusters are produced during the free jet expansion of a Ne-SF₆ mixture and studied by electron diffraction methods. Present experiments have been performed at constant nozzle diameter, stagnation pressure and stagnation temperature, adjustable parameters being the SF₆ mole fraction X and the nozzle-to-skimmer distancex _s /d. It is possible to warm up SF₆ clusters by increasing either X, and thus the cluster size, orx _s /d, which makes them collide with background molecules downstream of the Mach disk. In both cases, cold clusters made of several hundreds of molecules experience a structural transition, similar to that observed in bulk material, from the triclinic to the bcc plastic structure. A molecular dynamics simulation accounts correctly for intermediate stages of the transition which are visible in experimental patterns. Contrary to bulk results, cluster results show that the structural transition occurs over some temperature range.     

Recent progress in the improvement of hydrothermal stability of zeolites

Zeolites have been successfully employed in many catalytic reactions of industrial relevance. The severe conditions required in some processes, where high temperatures are frequently combined with the presence of steam, highlight the need of considering the evolution of the catalyst structure during the reaction. This review attempts to summarize the recently developed strategies to improve the hydrothermal framework stability of zeolites.

This review attempts to summarize the recently developed strategies to improve the hydrothermal framework stability of zeolites.     

Time-resolved photoluminescence characteristics of subnanometer ZnO clusters confined in the micropores of zeolites

Subnanometric ZnO clusters confined in different micropore zeolites are studied by steady-state and nanosecond time-resolved photoluminescence (PL) spectroscopy. The microsecond-scale lifetime is observed at room temperature for ZnO clusters confined in zeolites, which is significantly different from that of macrocrystalline ZnO on the external surface of zeolites. The dependence of luminescence lifetime on the amount of ZnO in zeolites indicates that the electron-phonon interactions between the ZnO clusters and the zeolite host significantly affect the dynamic relaxation process of ZnO clusters. The long lifetime luminescence of ZnO clusters can be achieved by weakening the coupling of electronic transition to zeolites host phonons. The similar long-lived luminescence is obtained when dispersing ZnO clusters into the porous SiO2. It is suggested that encapsulating the semiconductor cluster in the porous support is a possible way to inhibit or to retard the electron-hole recombination.     

Simulation of energetic stability of facetted l-glutamic acid nanocrystalline clusters in relation to their polymorphic phase stability as a function of crystal size

A molecular modeling approach is used to study the stability of different polymorphic forms of l-glutamic acid through building and optimizing molecular clusters of different sizes and shapes with the latter corresponding to the predicted crystal growth morphologies. The results reveal that the initially nucleating (according to Oswald rule) metastable (alpha) form is the more energetically stable form at small cluster sizes of ca. 200 molecular units, whereas the stable (beta) form is more stable when the cluster size is larger.     

Kinetic stability of complex molecular clusters

This investigation is concerned with modeling the evaporation, or decay, of n-nonane molecular clusters. We use a unique cluster decay model that was first developed to estimate the decay time scale of argon clusters using molecular-dynamics simulations. In this study we seek to enhance the model so that it represents a more complex cluster decay dynamic, suitable for n-nonane clusters. Experimental measurements of nucleation rates of n-nonane droplets have been used to deduce the rate at which a molecule escapes from the cluster. Typically for an n-nonane cluster containing 40 molecules, at an experimental temperature of 225 K, the empirical decay time, which is the inverse of the decay rate, is estimated to be 50 ns. For this time scale, the direct observation of n-nonane cluster decay from a molecular-dynamics trajectory is not feasible, since decay events are so rare. However, the cluster decay model uses a combination of molecular dynamics and stochastic dynamics in order to resolve the problem associated with long decay time scales. The model is based on a Langevin treatment that views cluster decay as single-particle escape from a confining potential of mean force. It is used to predict kinetic decay times of n-nonane clusters. We discover this result differs significantly from a classically derived decay time scale determined from a continuum thermodynamic treatment of the population balance equations of clusters. However, the dynamically generated results obtained from the kinetic decay model compare more favorably than the classical results with the empirical decay times that are deduced from experimental measurements of n-nonane clusters.     

Structural evolution of subnano platinum clusters

We present a theoretical study of the structural evolution of small minimum energy platinum clusters, using density functional theory (DFT). Three growth pathways were identified. At the subnanoscale, clusters with triangular packing are energetically most favorable. At a cluster size of approximately n = 19, a structural transition from triangular clusters to icosahedral clusters occurs. A less energetically favorable transition from triangular clusters to fcc‐like clusters takes place at around n = 38. Ionization potentials, electron affinities, and magnetic moments of the triangular clusters were also calculated. Understanding the structures and properties will facilitate studies of the chemical reactivity of Pt nanoclusters toward small molecules. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2007     

Reactivity and stability of bimetallic clusters

Using two independent vaporization lasers, bimetallic clusters composed of transition elements and A1 were generated by the laser vaporization method. Reactivity toward hydrogen adsorption of bimetallic clusters was compared with genuine clusters. It was found that A1 which has no reactivity toward hydrogen plays a role of either inhibitor or accelerator of the reaction when A1 is mixed with Nb or Co. Unusual stability of Co₁₂ V₁ in contrast to the high reactivity of Co_12–13 is attributed to the rigid geometric structure where V occupies the central position.     

Structural evolution of larger gold clusters

The preferred structures of larger gold clusters comprised of 100 to 1000 atoms (1.4–C3.0 nm equivalent diameter) have been determined theoretically via exhaustive search and energy-minimization methods and experimentally by synchrotron x-ray diffraction analysis of purified powder samples of small gold nanocrystals passivated by alkylthiol(ate) self-assembled monolayers. Theory predicts a persistent, close competition, across the entire size-range, among three structure-types: Marks-type decahedral (Dh) structures, monocrystals of a particular (TO+) truncated-octahedral (or ‘Wulffi’) morphology, and symmetrically twin-faulted variants (t-TO+) of the second; all other forms are much less stable. Quantitative comparison of the experimental diffraction patterns with patterns calculated from the structures provides clear evidence for a high abundance of the Dh and t-TO+ forms, but also reveals a definite transition from the former to the latter structures in the 1.7 to 2.0 nm range (~ 200 atoms). Further, the observed (mean) lattice contraction is only about half that predicted, suggesting that the surfactant monolayer acts to reduce the surface energy of the clusters. Taken together, these results suggest that the surfactant monolayer may play a small but important role in differentially stabilizing the higher energy {100}-type facets present to a greater extent in the TO-type structures.     

Structural fluctuation and atom-permutation in transition-metal clusters

The atomic structure and thermodynamic properties of transition-metal clusters containingN atoms are investigated forN=6 and 7 using the method of molecular dynamics, where Gupta's potential taking into account many-body interaction is employed. The caloric curve (total energy — temperature curve) and the structural fluctuations are studied. The “fluctuating state” is found forN=6 in the region of the temperature near below the melting point, where clusters undergo structural transition from one isomer to others without making any topological change. The fluctuating state differs from the coexistence state in that the former involves no atomic diffusion, and goes to a structural phase transition of the bulk whenN is increased. On the other hand, the motion of atom-permutation is found in the low-temperature region of the liquid state, being induced by the cooperative motion of two atoms. It is discussed that such a motion easily occurs along the surface and may be considered to be one of the characteristics of small clusters. The fluctuating state is discussed in relation to the structural fluctuation of gold clusters observed experimentally.