Supported metal nanoclusters cluster

The importance of supported metal nanoclusters and nanoparticles in catalysis and the rough analogy between supported nanoclusters and organo-metallic cluster compounds (those with metal-metal bonds) in catalysis have motivated researchers to find connections between these two classes of materials. Thus, an obvious synthetic goal has been size-selected metal nanoclusters on supports. 

A limitation of supported metal nanoclusters prepared from molecular metal carbonyl clusters is that, so far, clusters of only several metals (Ru, Rh, Ir, and Os) have been made in high yields (80 to 90%, with the likely impurity species being mononuclear metal complexes). However, this disadvantage is offset by the advantage of the characterizations, which show that some clusters are stable even during catalysis, at least under mild conditions. 

XAS can be used in several different ways to determine local structural information about catalysts in reactive atmospheres. This structural information may be static or dynamic it may be geometric or electronic. The depth of information that can be ascertained is often dependent upon the type of catalyst, for example, supported metal nanoclusters versus bulk or surface oxides. It may also be controlled by some property of the catalyst, for example, the concentration of the element in the catalyst that is being investigated. In this section a few examples are provided to highlight the importance and relevance of XAFS in catalyst characterization. The examples are focused on (1) structural information characterizing samples in reactive atmospheres, (2) transformation of one species to another, (3) oxidation state determination, (4) determination of supported metal cluster size and shape, and (5) electronic structure. These examples illustrate the type of information that can be learned about the catalyst from XAFS spectroscopy. 

In the preparation and activation of a catalyst, it is often the case that the chemical form of the active element used in the synthesis differs from the final active form. For example, in the preparation of supported metal nanoclusters, a solution of a metal salt is often used to impregnate the oxide support. The catalyst is then typically dried, calcined, and finally reduced in H2 to generate the active phase highly dispersed metal clusters on the oxide support. If the catalyst contains two or more metals, then bimetallic clusters may form. The activity of the catalyst may depend on the metal loading, the calcination temperature, and the reduction temperature, among others. 

In the last decade much attention has been paid to metal nano-clusters including supported nanoparticles as one of the promising advanced nanoscopic materials. Elements easily forming supported metal nanoclusters are Group VIII and IB transition metals as follows Pt, Ir, Pd, Rh, Ru, Ni, Co, and Au, Ag, Cu. It is interesting to note that the heat of formation of the oxides of these metals is low (usually below -AHf = 40 kcal/mol at 25 °C referred to one oxygen atom ). 

The materials described in this chapter are denoted in the literature mostly as metal clusters or metal nanoclusters . However, the terminology metal clusters spans various scientific disciplines and has consequently multiple meanings, including plasmonic nanoparticles and various nanosized metallic structures. Therefore alternative names have been given, although they are at the moment supported only by a fraction of the scientific community quantum clusters [26], nanodots [27], metal quantum dots [25] and superatoms [28]. 

An alternative to this physical method of preparing structurally uniform metal clusters on supports involves chemistry by which molecular metal carbonyl clusters (e.g., [Rh6(CO)i6]) serve as precursors on the support. These precursors are decarbonylated with maintenance of the metal frame to give supported nanoclusters (e.g., Rh6). Advantages of this chemical preparation method are its applicability to many porous supports, such as zeolites (and not just planar surfaces) and the opportunities to use spectroscopic methods to follow the chemistry of synthesis of the precursor on the support and its subsequent decarbonylation. Zeolites, because their molecular-scale cages are part of a regular (crystalline) structure, offer the prospect of regular three-dimensional arrays of nanoclusters. 

Supported nanoclusters made from metal carbonyl clusters are emphasized here, because there are numerous characterization data on which to base the discussion. The synthetic methods are illustrated by the following examples. 

Supported nanoclusters have been prepared by decarbonylation of neutral or anionic metal carbonyl clusters on supports. The decarbonylation chemistry is not fully understood. The chemistry accompanying removal of the CO ligands from metal carbonyl clusters on metal oxides evidently involves hydroxyl groups or water on the surface of the metal oxide. 

The methods of structure determination of supported nanoclusters are essentially the same as those mentioned previously for supported metal complexes. EXAFS spectroscopy plays a more dominant role for the metal clusters than for the complexes because it provides good evidence of metal-metal bonds. Combined with density functional theory, EXAFS spectroscopy has provided much of the structural foundation for investigation of supported metal clusters. EXAFS spectroscopy provides accurate determinations of metal-metal distances ( 1-2%), but it gives only average structural information and relatively imprecise values of coordination numbers. EXAFS spectroscopy provides structure data that are most precise when the clusters are extremely small (containing about six or fewer atoms) and nearly uniform (Alexeev and Gates, 2000). 

Theoretical studies of the properties of the individual components of nanocat-alytic systems (including metal nanoclusters, finite or extended supporting substrates, and molecular reactants and products), and of their assemblies (that is, a metal cluster anchored to the surface of a solid support material with molecular reactants adsorbed on either the cluster, the support surface, or both), employ an arsenal of diverse theoretical methodologies and techniques for a recent perspective article about computations in materials science and condensed matter studies [254], These theoretical tools include quantum mechanical electronic structure calculations coupled with structural optimizations (that is, determination of equilibrium, ground state nuclear configurations), searches for reaction pathways and microscopic reaction mechanisms, ab initio investigations of the dynamics of adsorption and reactive processes, statistical mechanical techniques (quantum, semiclassical, and classical) for determination of reaction rates, and evaluation of probabilities for reactive encounters between adsorbed reactants using kinetic equation for multiparticle adsorption, surface diffusion, and collisions between mobile adsorbed species, as well as explorations of spatiotemporal distributions of reactants and products. 

The latter point brings us to an important question in the field of catalysis by supported metal particles to which extent is the chemical reactivity of a (sub-) nanocluster affected by the interaction with the substrate Very few theoretical studies were dedicated to this problem, and most of them are related to the surface of MgO, an oxide which interacts weakly widi the supported particle, as shown above. Still, the knowledge accumulated in the course of the years on the structure of surface defects and morphology of the MgO surface allows one to analyze some of the mechanisms which can modify the chemical properties of a supported cluster as a function of the site where nucleation has occurred. 

The above classification suggests that under properly chosen condition the subject of this chapter, i.e. metal ion-metal nanocluster ensemble sites (MIMNES) can be formed in most of the above types of catalysts. For instance, from bimetallic clusters of type (i) and (ii) MIMNES can be formed under conditions of mild oxidation. In catalysts type (iii) MIMNES should exist both under oxidative and reductive environment. In catalysts type (iv) any metal-support interaction with the involvement of non-reducible oxide can also be considered as MIMNES. The only requirement for the formation of MIMNES is the atomic closeness of the two types of sites. 

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