Reactivity supported metal nanoclusters

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. 

The electronic structure, morphology, and chemical reactivity of metal nanoclusters have attracted considerable attention due to their extensive technological importance. Chemical reactions and their catalytic relevance have been investigated on a variety of well-characterized, supported model catalysts prepared by vapor deposition of catalytically relevant metals onto ultrathin oxide films in ultrahigh vacuum conditions. Such ultrathin film supports are usually prepared by vaporizing a parent metal onto a refractory metal substrate in an oxygen atmosphere at a high temperature. These unique model systems are particularly well suited for surface-... 

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. 

Methods of Controlled Surface Reactions (CSRs) and Surface Organometallic Chemistry (SOMC) were developed with the aim to obtain surface species with Sn-Pt interaction. In CSRs two approaches have been used (i) electrochemical, and (ii) organometallic. Characteristic feature of the organometallic approach is that both CSR and SOMC results in almost exclusively supported alloy type bimetallic nanoclusters. Studies on the reactivity of tin organic compounds towards hydrogen adsorbed on different transition and noble metals have revealed new aspects for the preparation of supported bimetallic catalysts. 

Lukehart and coworkers [26] successfully prepared a Pt-Ru/graphitic carbon nanofiber nanocomposite exhibiting high relative performance as a direct methanol fuel cell anode catalyst Multistep deposition and reactive decomposition of a single-soiuce molecular precursor of Pt and Ru metal on herringbone graphitic carbon nanofibers affords a Pt-Ru/GNF nanocomposite containing Pt-Ru alloy nanoclusters widely dispersed on the GNF support The nanocomposite has a total metal content of 42 wt% with a bulk Pt/Ru atomic ratio of about 1 1 and... 

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