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The application of transmission electron microscopy to the study of high nuclearity carbonyl clusters (HNCC's)

Published online by Cambridge University Press:  31 January 2011

R.W. Devenish ,
S. Mulley ,
B.T. Heaton  and
G. Longoni
R.W. Devenish
Affiliation:
Department of Materials Science and Engineering, University of Liverpool, P.O. Box 147, Liverpool L69 3BX, United Kingdom
S. Mulley
Affiliation:
Department of Chemistry, University of Liverpool, P.O. Box 147, Liverpool L69 3BX, United Kingdom
B.T. Heaton
Affiliation:
Department of Chemistry, University of Liverpool, P.O. Box 147, Liverpool L69 3BX, United Kingdom
G. Longoni
Affiliation:
Dipartimento di Chimica Fisica ed Inorganica, Università di Bologna, 40136, Bologna, Italy
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Abstract

The properties of a variety of HNCC's supported on holey carbon films have been investigated by transmission and analytical electron microscopy; a review of how these techniques can be used to study these crystallographically well-characterized clusters is also presented. Images of the metallic skeleton corresponding to a single cluster unit have been observed for [Ni38Pt6(CO)48H]5−, [Ni34C4(CO)38H]5−, [Pt38(CO)44Hx]2−, [Rh17S2(CO)32]3−, [Ni12Sn(CO)22]2−, and [Ni22Ge(CO)22]2−, and analytical data at low electron beam intensities are consistent with their crystallographically established structures. At increasing current densities, agglomeration into larger particles occurs and these larger particles (2–5 nm) gradually lose the chemical identity of the precursor. Ultimately at current densities of the order of 107 A/m2 metal segregation and/or metal alloy particles having close-packed crystal structures are formed together with graphitic carbon from decomposition of the CO ligands. Possible mechanisms for this beam damage are discussed. There is evidence of cluster/substrate interaction resulting in increased stability compared to that observed in solution and in the normal crystalline state.

Type
Articles
Information
Journal of Materials Research , Volume 7 , Issue 10 , October 1992 , pp. 2810 - 2816
Copyright
Copyright © Materials Research Society 1992

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References

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