Polyoxoanion- and tetrabutylammonium-stabilized, near-monodisperse, 40 ± 6 Å Rh(0)∼1500 to Rh(0)∼3700 nanoclusters: Synthesis, characterization, and hydrogenation catalysis

Chemistry of Materials

Volumn 11, Issue 4, 1999, Pages 1035-1047

  Aiken III, John D ^a   Finke, Richard G ^a  

^a Immunology and Pathology   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0000597407     PISSN: 08974756     EISSN: None     Source Type: Journal    
DOI: 10.1021/cm980699w     Document Type: Article

References (60)

1. Reviews on nanoclusters: (a) Jena, P.; Rao B. K.; Khanna, S. N. Physics and Chemistry of Small Clusters; Plenum: New York, 1987.
2. (b) Andres, R. P.; Averback, R. S.; Brown, W. L.; Brus, L. E.; Goddard, W. A., III; Kaldor, A.; Louie S. G.; Moscovits, M.; Peercy, P. S.; Riley, S. J.; Siegel, R. W.; Spaepen, F.; Wang, Y. J. Mater. Res. 1989, 4, 704. This is a Panel Report from the United States Department of Energy, Council on Materials Science on "Research Opportunities on Clusters and Cluster-assembled Materials".
3. (c) Thomas, J. M. Pure Appl. Chem. 1988, 60, 1517.
4. (d) Henglein, A. Chem. Rev. 1989, 89, 1861.
5. (e) A superb series of papers, complete with a record of the insightful comments by the experts attending the conference, is available in: Faraday Discuss., Chem. Soc. 1991, 92, 1-300.
6. (f) Bradley, J. S. In Clusters and Colloids. From Theory to Applications; Schmid, G., Ed.; VCH: New York, 1994; pp 459-544.
7. (g) Schmid, G. In Aspects of Homogeneous Catalysis; Ugo, R., Ed.; Kluwer: Dordrecht, The Netherlands, 1990; Chapter 1.
8. (h) Active Metals: Preparation, Characterization, and Applications; Fürstner, A., Ed.; VCH: Weinheim, Germany, 1996.
9. (i) Physics and Chemistry of Metal Cluster Compounds, de Jongh, L. J., Ed.; Kluwer: Dordrecht, The Netherlands, 1994.
10. (j) Schmid, G. Chem. Rev. 1992, 92, 1709.
11. (k) A Review of Modern Transition-Metal Nanoclusters: Their Synthesis, Characterization, and Applications in Catalysis. Aiken, J. D., III; Finke, R. G. J. Mol. Catal. A: Chem. 1999, in press.
12. (b) Aiken, J. D., III; Lin, Y.; Finke, R. G. J. Mol. Cat. A: Chem. 1996, 114, 29-51.
13. (a) Lin, Y.; Finke, R. G. J. Am. Chem. Soc. 1994, 116, 8335-8353.
14. Lin, Y.; Finke, R. G. Inorg. Chem. 1994, 33, 4891-4910. This paper reports how we discovered the Ir(0) nanoclusters (by developing a more general solution to the classic "Is it heterogeneous, or homogeneous catalysis" problem).
15. Watzky, M. A.; Finke, R. G. J. Am. Chem. Soc. 1997, 119, 10382.
16. El-Sayed's recent work also provides evidence for a nanocluster surface-growth pathway: Petroski, J. M.; Wang, Z. L.; Green, T. C.; El-Sayed, M. A. J. Phys. Chem. B 1998, 102, 3316.
17. Watzky, M. A.; Finke, R. G. Chem. Mater. 1997, 9, 3083-3095.
18. 2. See: Nagata, T.; Pohl, M.; Weiner, H.; Finke R. G. Inorg. Chem. 1997, 36, 1366.
19. For other examples of Rh nanoclusters, see: (a) Bönnemann, H.; Brijoux, W.; Brinkmann, R.; Dinjus, E.; Joussen, T.; Korall, B.; Angew Chem., Int. Ed. Engl. 1991, 30, 1312.
20. (b) Reetz, M. T.; Quaiser, S. A.; Angew Chem. Int., Ed. Engl. 1995, 34, 2240.
21. (c) Schmid, G. Struct. Bonding 1985, 62, 51-85.
22. (d) Yonezawa, T.; Tominaga, T.; Richard, D. J. Chem. Soc., Dalton Trans. 1996, 783.
23. (e) Lewis, L. N.; Uriarte, R. J.; Lewis, N. J. Mol. Catal. 1991, 66, 105-113.
24. (f) See also footnote 8 in: Schmid, G.; Maihack, V.; Lantermann, F.; Peschel, S. J. Chem. Soc., Dalton Trans. 1996, 589-595.
25. 8- (M ) Ir, Rh): (1). (a) Nomiya, K.; Pohl, M.; Mizuno, N.; Lyon, D. K.; Finke, R. G. Inorg. Synth. 1997, 31, 186-201.
26. (b) Pohl, M.; Lyon, D. K.; Mizuno, N.; Nomiya, K.; Finke, R. G. Inorg. Chem. 1995, 34, 1413.
27. (c) Pohl, M.; Finke, R. G. Organometallics 1993, 12, 1453-1457.
28. (d) Finke, R. G.; Lyon, D. K.; Nomiya, K.; Sur, S.; Mizuno, N. Inorg. Chem. 1990, 29, 1784-1787.
29. (a) Weddle, K. S.; Aiken, J. D. III; Finke, R. G. J. Am. Chem. Soc. 1998, 120, 5653-5666.
30. (b) Bönnemann, H.; Brijoux, W. Active Metals: Preparation, Characterization, Applications; Fürstner, A., Ed.; VCH: Weinheim, Germany, 1996, p 371.
31. (c) Logan, D. A.; Sharoudi, K.; Datye, A. K. J. Phys. Chem. 1991, 95, 5568.
32. We have recently used Rh(0) nanoclusters to demonstrate the effect that H2 gas-to-solution mass-transfer limitations have on the resulting nanoclusters, namely the need to avoid mass-transfer conditions in the synthesis of near-monodisperse nanoclusters: Aiken, J. D., III; Finke, R. G. J. Am. Chem. Soc. 1998, 120, 9545-9554.
33. Aiken, J. D., III; Finke, R. G. Polyoxoanion- and Tetrabutylammonium- Stabilized Rh(0)n Nanoclusters: Unprecedented Nanocluster Catalytic Lifetime In Solution, in preparation.
34. (b) Aiken, J. D., III; Finke, R. G. A Comparison of CS2 Catalyst Poisoning of 5% Rh/ Al2O3 To Polyoxoanion- and Tetrabutylammonium-Stabilized Rh(0) Nanoclusters, in preparation.
35. Pope, M. T. Heteropoly Blues in Mixed Valence Compounds;Brown, D. B., Ed., Reidel: Dordrecht, The Netherlands, 1980; p 365.
36. 9f
37. The plasmon resonance gives rise to this tailing absorption; for a compilation of the absorption spectra of several colloidal metallic elements, see: Creighton, J. A.; Eadon, D. G.; J. Chem. Soc., Faraday Trans. 1991, 87, 3881.
38. Schmid correctly notes that "The higher the number the metal atoms the more probable deviations from the ideal magic number will be. The controlled synthesis of such large, chemically stabilized clusters will become more difficult going from shell to shell." Developments in Transition Metal Cluster ChemistrysThe Way to Large Clusters. Schmid, G. Struct. Bonding 1985, 62, 51.
39. Indeed, some nanoclusters, such as those of Six or Nax, are believed to have "fluidlike" surfaces, with many structures within even 0.1 eV above the equilibrium structures. See Brus and Siegel's discussion, especially p 719 in the reference which follows, where theynote that "total energy calculations have shown that there are many metastable configurations in a 0.1 eV (i.e., 2-3 kcal/mol) range above the equilibrium state, and that their number increases significantly with the cluster size": Research Opportunities on Clusters and Cluster- Assembled MaterialssA Department of Energy, Council on Materials Science Panal Report. Andres, R. P.; et al. J. Mater. Res. 1989, 4, 704; see p 719.
40. (b) Martins, J. L.; Buttet, J.; Car, R. Phys. Rev. B 1985, 31, 1804.
41. (c) Ballone, P.; Andreoni, W.; Car, R; Parrinello, M. Phys. Rev. Lett. 1988, 60, 271.
42. For the aggregation of Au clusters under the TEM electron beam see: Schmid, G. Struct. Bonding 1985, 62, 51-85.
43. (b) For an account where the stabilizing ligand shell is lost and the Au nuclei rearrange see: Schmid, G. Polyhedron 1988, 7, 2321-2329.
44. (c) For the observation of rapid changes in the structure and size of Pt55 clusters, and for accounts of mobile surface atoms in nanoclusters under a TEM beam, see: Schmid, G. Chem. Rev. 1992, 92, 1709-1727.
45. (d) For individual crystallite aggregation under a TEM beam see: Che, M; Bennet, C. O. Adv. Catal. 1989, 36, 55.
46. see: Volkov, V. V.; Van Tendeloo, G.; Tsirkov, G. A.; Cherkashina, N. V.; Vargaftik, M. N.; Moiseev, I. I.; Novotortsev, V. M.; Kvit, A. V. and Chuvilin, A. L. J. Cryst. Growth 1996, 163, 377.
47. Duff, D. G.; Curtis, A. C.; Edwards, P. P.; Jefferson, D. A.; Johnson, B. F. G.; Logan, D. E. J. Chem. Soc., Chem. Comm. 1987, 1264-1266.
48. Ahmadi, T. S.; Wang, Z. L.; Green, T. C.; Henglein, A.; El- Sayed, M. A. Science 1996, 272, 1924-1926.
49. (b) Ahmadi, T. S.; Wang, Z. L.; Henglein, A.; El-Sayed, M. A. Chem. Mater. 1996, 8, 1161-1163.
50. 3. See: Rodriguez, A.; Amiens, C.; Chaudret, B.; Casanove, M.-J.; Lecante, P.; Bradley, J. S. Chem. Mater. 1996, 8, 1978.
51. See Table 29.3 in: Wells, A. F. Structural Inorganic Chemistry, 4th ed.; Clarendon Press: Oxford, England, 1975; p 1015.
52. See: van Bentham, R. A. T. M. Palladium Cluster Catalyzed Oxidative Cyclizations in the Synthesis of Aminoalkenols and Diamines; University of Amsterdam: Amsterdam, 1995; Chapter 8, p 130.
53. Porterfield, W. W. Inorganic Chemistry; Addison-Wesley Publishing: Reading, MA, 1983; p 84.
54. (a) Georgiades, G. C.; Sermon, P. A. J. Chem. Soc. Chem. Commun. 1985, 975.
55. (b) Whitesides, G. M.; Hackett, M.; Brainard, R. L.; Lavalleye, J.-P. P. M.; Sowinski, A. F.; Izumi, A. N.; Moore, S. S.; Brown, D. W.; Staudt, E. M. Organometallics 1985, 4, 1819.
56. (c) Moyes, R. B.; Wells, P. B. Adv. Catal. 1973, 23, 121.
57. (a) Weiner, H.; Aiken, J. D., III; Finke, R. G. Inorg. Chem. 1996, 35, 7905- 7913 and references therein. Note that this manuscript has two typographical errors: p 7910, right-hand column, 12th line: "84% excess" should read "2% excess"; p 7910, footnote 20, 4th line: "5%" should read "0.5%".
58. (b) Finke, R. G.; Lyon, D. K.; Nomiya, K.; Weakley, T. J. Acta Crystallogr., Sect. C 1990, 46, 1592.
59. (c) Edlund, D. J.; Saxton, R. J.; Lyon, D. K.; Finke, R. G. Organometallics 1988, 7, 1692-1704.
60. Thomas, G.; Goringe, M. J. Transmission Electron Microscopy of Materials; John Wiley and Sons: New York, 1979.