Hostname: page-component-586b7cd67f-rdxmf Total loading time: 0 Render date: 2024-11-23T15:45:48.787Z Has data issue: false hasContentIssue false
  • English
  • Français

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
Get access

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

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)

References

REFERENCES

1Heaton, B.T., Philos. Trans. R. Soc. London A308, 95 (1982).Google Scholar
2Heaton, B.T., Sabounchei, J., Kernaghan, S., Nakayama, H., Eguchi, T., Takeda, S., Nakamura, N., and Chihara, A., Bull. Chem. Soc. Jpn. 63, 3019 (1990).CrossRefGoogle Scholar
3Bovin, J-O., Wallenberg, R., and Smith, D.J., Nature 317, 47 (1985).CrossRefGoogle Scholar
4Wallenberg, L.R., Bovin, J-O., Petford-Long, A.K., and Smith, D.J., Ultramicroscopy 20, 71 (1986).CrossRefGoogle Scholar
5Vargaftik, M.N., Zagorodnikov, V.P., Stolarov, I.P., Moiseev, I.I., Kochubey, D.I., Likholobov, V.A., Chuvilin, A.L., and Zamaraev, K.T., J. Mol. Catal. 53, 315 (1989).CrossRefGoogle Scholar
6Ceriotti, A., Demartin, F., Longoni, G., Manassero, M., Marchionna, M., Piro, G., and Sansoni, M., Angew. Chem. Int. Ed. Engl. 24, 696 (1985).Google Scholar
7Ceriotti, A., Fait, A., Longoni, G., Masciocchi, N., Resconi, L., Manassero, M., Piro, G., Demartin, F., and Sansoni, M., J. Am. Chem. Soc. 108, 5370 (1986).Google Scholar
8Ceriotti, A., Chini, P., Longoni, G., Waschecheck, D.M., Wucherer, E.J., Dahl, L. F., Marchionna, M., and Montag, R. A., unpublished results from Proceedings of the NATO Advanced Research Workshop on Surface Organometallic Chemistry (1986).Google Scholar
9Vidal, J.L., Fiato, R.A., Cosby, L.A., and Pruett, R.L., Inorg. Chem. 17, 2575 (1978).CrossRefGoogle Scholar
10Ceriotti, A., Demartin, F., Heaton, B.T., Ingallina, P., Longoni, G., Manassero, M., Marchionna, M., and Masciocchi, M., J. Chem. Soc. Chem. Commun., 786 (1989).Google Scholar
11Iijima, S. and Ichikawa, M., J. Catal. 94, 313 (1985).CrossRefGoogle Scholar
12Heaton, B.T., Ingallina, P., Devenish, R., Humphreys, C.J., Ceriotti, A., Longoni, G., and Marchionna, M., J. Chem. Soc. Chem. Commun., 765 (1987).Google Scholar
13McComb, D. W., Paterson, J. H., Buglass, J. G., and Friedman, S. L., Inst. Phys. Conf. Ser. 119, 43 (1991).Google Scholar
14Contrata, W., Zhang, H., Teo, B.K., Michel, M.E., and Machel, J.M., in Clusters and Cluster-Assembled Materials, edited by Averback, R. S., Bernholc, J., and Nelson, D.L. (Mater. Res. Soc. Symp. Proc. 206, Pittsburgh, PA, 1991), p. 169.Google Scholar
15Fujimoto, T., Fukuoka, A., Nakamura, J., and Ichikawa, M., J. Chem. Soc. Chem. Commun. 845 (1989).Google Scholar
16Mulley, S., Ph.D. Thesis, University of Liverpool (1989).Google Scholar
17Heinemann, K. and Soria, F., Ultramicroscopy 20, 1 (1986).CrossRefGoogle Scholar
18Liu, J. and Cowley, J.M., Ultramicroscopy 34, 119 (1990).CrossRefGoogle Scholar
19Heinemann, K. and Poppa, H., Appl. Phys. Lett. 16, 515 (1970).CrossRefGoogle Scholar
20Hobbs, L., in Quantitative Electron Microscopy, edited by Chapman, J. N. and Craven, A. J., Scottish Universities Summer School in Physics (1984).Google Scholar
21Howitt, D.G., Medlin, D.L., and Walker, T.M., EMSA Bull. 18, 69 (1988) and references therein.Google Scholar
22Howie, A., Marks, L. D., and Pennycook, S. J., Ultramicroscopy 8, 163 (1982).CrossRefGoogle Scholar
23Schmid, G. and Klein, N., Angew. Chem. 98, 910 (1986).CrossRefGoogle Scholar
24Sattler, K., Ultramicroscopy 20, 55 (1986).Google Scholar
25Anderson, J.R., Sci. Prog. Oxf. 69, 461 (1985) and references therein.Google Scholar
26Fryer, J.R. and McConnell, C.H., Inst. Phys. Conf. Ser. 98, 211 (1989).Google Scholar
27Lamber, R., Jaeger, N., and Schulz-Ekloff, G., Surf. Sci. 197, 402 (1988).CrossRefGoogle Scholar
28Castro, T., Choi, E., Li, Y. Z., Andres, R. P., and Reifenberger, R., in Clusters and Cluster-Assembled Materials, edited by Averback, R. S., Bernholc, J., and Nelson, D. L. (Mater. Res. Soc. Symp. Proc. 206, Pittsburgh, PA, 1991), p. 159.Google Scholar
29Rez, P. and Glaisher, R.W., Ultramicroscopy 35, 65 (1991).CrossRefGoogle Scholar
30Gryaznov, D. G., Kaprelov, A. M., and Belov, A. Y., Philos. Mag. Lett. 63, 275 (1991).CrossRefGoogle Scholar
31Pearson, W. B., Handbook of Lattice Spacings and Structures of Metals and Alloys, International series of monographs on metal physics and physical metallurgy 4 (1967).Google Scholar
32Shunk, F. A., Constitution of Binary Alloys, 2nd supplement (McGraw-Hill Book Company, New York, 1969).Google Scholar
33Wallenberg, L. R., Bovin, J-O., and Schmid, G., Surf. Sci. 156, 256 (1985).CrossRefGoogle Scholar