Properties of Small Metal Particles

The Characterization and Properties of Small Metal Particles. Y. Takasu and A. M. Bradshaw, Surf. Defect. Prop. Solids p. 401 1978). 2. Cluster Model Theory. R. P. Messmer, in "The Nature of the Chemisorption Bond G. Ertl and T. Rhodin, eds. North-Holland Publ., Amsterdam, 1978. 3. Clusters and Surfaces. E. L. Muetterties, T. N. Rhodin, E. Band, C. F. Brucker, and W. R. Pretzer, Cornell National Science Center, Ithaca, New York, 1978. 4. Determination of the Properties of Single Atom and Multiple Atom Clusters. J. F. Hamilton, in "Chemical Experimentation Under Extreme Conditions (B. W. Rossiter, ed.) (Series, "Physical Methods of Organic Chemistry ), Wiley (Interscience), New York (1978). 

These questions lead on to further fundamental questions concerning the shapes and properties of small metal particles. For example, what is the stable shape for a small metal particle How is this affected by size, method of preparation, temperature, gaseous environment, precursor compound, support morphology, etc. Do small metal particles have different electronic properties from bulk metal Do surface electronic properties depend on particle size, and if so, do they vary in the same way as bulk electronic properties When, indeed, is a particle small enough to have unusual properties ... 

To answer these questions requires some understanding of the properties of small metal particles, both structural and electronic. In this review we shall examine first the evidence relating to metal particles prepared by direct methods, e.g., vapour deposition or condensation in the gas phase. Then we shall consider whether this information can be applied to the case of supported metals where both precursor decomposition and support effects may add to the complexity of the total system. We shall then consider whether further changes in catalytic properties occur after preparation, i.e., during the catalytic reaction. Finally, we shall summarize some of the more recent evidence concerning the nature of structure sensitivity. 

Electronic Properties of Small Metal Particles (a) Theoretical Considerations. — Catalytic processes involve chemisorption at surfaces. The strength of the chemisorption bond will affect the catalytic activity, and is itself expected to be very sensitive to the electronic properties of the surface metal atoms. (The wide variation in catalytic activity among metals having the same structure is evidence for the paramount importance of electronic properties.) Within the particle size range typically encountered with supported catalysts (see Table 1) it is important to establish whether there will be variations in electronic properties with number of metal atoms. We examine first the theoretical evidence relating to this point. This work has been reviewed frequently31 152-155 so only a few brief comments will be made here. 

All the experimental results summarized in this section have been interpreted in the original papers as evidence that there is a change in electronic properties of small metal particles due to their size. Most researchers agree that upwards of 150 atoms is required to attain bulk-like properties. The narrowing of the electron bands is attributed to the fact that in a small crystal there are fewer molecular orbitals which go to make up the electron band. This particular point is not in dispute. However, what has been challenged is the interpretation of shifts in the position of the centroid of the d-band, or... 

The foregoing sections have been concerned with the effect of particle size on the structure and properties of small metal particles. Several general comments can be made concerning the influence of particle size on catalytic properties. 

The conclusion is that particle size effects on catalytic activity or selectivity due to variations in the inherent properties of small metal particles (geometric or electronic) are unlikely to be important for particles larger than about 1.5-2.0 nm. If size effects are observed for larger particles it is necessary to consider the nature and origin of such effects. 

Henglein, A. Physicochemical properties of small metal particles in solution Microelectrode reactions, chemisorption, composite metal particles, and the atom-to-metal transition, J. Phys. Chem. 1993, 97, 5457. 

It is not surprising therefore that the optical properties of small metal particles have received a considerable interest worldwide. Their large range of applications goes from surface sensitive spectroscopic analysis to catalysis and even photonics with microwave polarizers [9-15]. These developments have sparked a renewed interest in the optical characterization of metallic particle suspensions, often routinely carried out by transmission electron microscopy (TEM) and UV-visible photo-absorption spectroscopy. The recent observation of large SP enhancements of the non linear optical response from these particles, initially for third order processes and more recently for second order processes has also initiated a particular attention for non linear optical phenomena [16-18]. Furthermore, the paradox that second order processes should vanish at first order for perfectly spherical particles whereas experimentally large intensities were collected for supposedly near-spherical particle suspensions had to be resolved. It is the purpose of tire present review to describe the current picture on the problem. 

Chemisorptive properties of small metal particles depend upon the size of the particle. We find that the orbital spectrum of halogen (Cl) is dependent upon the size of the silver particle to... 

E. Structure and Electronic Properties of Small Metal Particles... 

Henglein A, (1993) Chemical and Optical Properties of Small Metal Particles in Aqueous Solution Israel J Chem. 33 77... 

Nepiyko, S.A. (1985) Physical Properties of Small Metal Particles, Kiev, Naukova Dumka (in Russian). 

See also a review on metal colloids in ionic crystals [8]. — See also a report on electronic properties of small metallic particles [9]. — According to a review on quantum size effects [10]. d = 22.4 + 3.2 A in original paper [4]. ... 

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