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Volumn 17, Issue 20, 2005, Pages 4925-4938

Nanocluster nucleation, growth, and then agglomeration kinetic and mechanistic studies: A more general, four-step mechanism involving double autocatalysis

Author keywords

[No Author keywords available]

Indexed keywords

AGGLOMERATION KINETICS; AUTOCATALYSIS; NANOCLUSTER NUCLEATION; SURFACE GROWTH;

EID: 26944471176     PISSN: 08974756     EISSN: None     Source Type: Journal    
DOI: 10.1021/cm050207x     Document Type: Article
Times cited : (160)

References (81)
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    • 8 merit mention in this regard and are listed below.
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    • (b) See also the addition/correction published in Chem. Mater. 2004, 16, 3972 which teaches an initially incorrect use of the pseudo-elementary step concept.
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    • Transition metal nanoclusters
    • Feldheim, D. L., Foss, C. A., Jr., Eds.; Marcel Dekker: New York
    • For further discussion of the advantages incurred by treating nanocluster science by the principles of smaller molecule chemistry inso-far as possible, but also the lower precision that one can expect for many measurements on nano- and other macro-molecules (i.e., and in comparison to conventional small molecules), see: Finke, R. G. Transition Metal Nanoclusters. In Metal Nanoparticles, Synthesis, Characterization and Applications; Feldheim, D. L., Foss, C. A., Jr., Eds.; Marcel Dekker: New York, 2001; pp 17-53.
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    • For example, see elsewhere for a case where kinetic studies of compositionally well-characterized nanoclusters has allowed a model of how tridentate ligands appear to preferentially bind to the {111} facets of selected nanocluster surfaces: Finke, R. G.; Özkar, S. Coord. Chem. Rev. 2004, 248 (12), 135.
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    • Finke, R.G.1    Özkar, S.2
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    • note
    • n+1. Note that LaMer's mechanism is completely different from the mechanism for transition-metal nanocluster (slow, continuous) nucleation, then (nondiffusion controlled) autocatalytic surface growth published in 1997.2 LaMer's mechanism is also completely different from the expanded, more general mechanism published herein for transition-metal nanocluster formation and then agglomeration under reductive conditions.
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    • (b) Aiken, J. D., III; Finke, R. G. J. Mol. Catal. A: Chem. 1999, 145, 1-44 (see p 6 and the references cited in ref 3).
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    • (d) An example involving nitrile hydrolysis: Izzo, B.; Harrell, C. L.; Klein, M. T. AIChE J. 1997, 43 (8), 2048.
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    • 2), especially in comparison to the uncertainties discussed in the present paper (Table 1) resulting from curve fitting for four rate constants in an overall five-dimensional space.
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    • 30
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    • note
    • 11 In the present case this means that just following via our cyclohexene reporter reaction only one species (i.e., C), out of the three chemically important species (A, B, and C), is insufficient to distinguish mechanisms which display different curves for A and B, yet show very similar behavior for C as a function of time. This is why experiments such as the NMR detection of A vs time reported in the main text are crucial, even though those experiments provide a very limited amount of data for curve fitting.
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    • 2, with its site of coordinative unsaturation) compared to the mechanism of cyclohexene reduction may also be at work here.
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    • note
    • 26b,e
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    • see for example Figure 2 therein. We thank a referee for this reference and for their input on this important point
    • (b) Leff, D.; Ohara, P. C.; Heath, J. R.; Gelbart, W. M. J. Phys. Chem. 1995, 99, 7036; see for example Figure 2 therein. We thank a referee for this reference and for their input on this important point.
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    • (g) Interestingly, a SciFinder search of "decreasing heats of adsorption with increasing surface coverage" yielded 66 hits, suggesting the greater generality of this phenomenon, although many of the references were on systems other than ligands attached to transition-metal surfaces.
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    • 30 (i.e., cf. the up to 5-fold greater R value for a protein single-crystal structure vs a small molecule R value). They may also prove to be relatively small error bars for reactions involving two autocatalytic steps.
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    • note
    • The other available kinetic packages that allow fitting are, as far as we have been able to discern: Gepasi (http://www.gepasi.org), the package Kinsim/Fitsim (http://biochem.wustl.edu/cflab/message.html), ZiTa (http://www.staff.u-szeged.hu/~peintler/index.html), and Dynafit (http://uwmml.pharmacy.wi.sc.edu). Additional information is provided in the Supporting Information. We are working with the author of Dynafit to see if that promising package cannot be customized to be more useful for treating nonbiological problems (e.g., where the ability to treat fractional coefficients for rate equations, as seen herein, will be possible).
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    • Transition metal nanoclusters
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    • See p 27 and ref 4 elsewhere for a discussion of the loss of precision observed in many macromolecule or materials systems and where one is measuring a collective or bulk property, and especially if the resultant material contains some polydispersity: Finke, R. G. Transition Metal Nanoclusters. In Metal Nanoparticles, Synthesis, Characterization and Applications; Feldheim, D. L., Foss, C. A., Jr., Eds.; Marcel Dekker: New York, 2001.
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    • note
    • 31b,c cannot supply even a single, complete mechanism with elementary or pseudoelementary steps and rate constants (mostly a "word mechanism" is used instead, which is typical of proposed mechanisms since the time of LaMer's work6 as discussed briefly elsewhere2). Clearly, kinetic and mechanistic studies of self-assembly materials syntheses presents a generally quite difficult challenge.
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    • Finney, E. E.; Finke, R. G. Unpublished results and experiments in progress
    • Finney, E. E.; Finke, R. G. Unpublished results and experiments in progress.
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    • Exceptions where such Pt or Pd quantitation is performed are as follows: (a) Reetz, M. T.; Helbig, W. J. Am. Chem. Soc. 1994, 116, 7401.
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    • Pope, M. T., Müller, A., Eds.; Kluwer Academic Publishers: The Netherlands
    • (b) Errington, R. J.; Lax, C.; Richards, D. G.; Clegg, W.; Fraser, K. A. In Polyoxometalates; Pope, M. T., Müller, A., Eds.; Kluwer Academic Publishers: The Netherlands, 1994; pp 105-114.
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    • See refs 2a,b, 3, 11, and 12 cited herein
    • (c) See refs 2a,b, 3, 11, and 12 cited herein.
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    • A SciFinder search reveals that kinetic and mechanistic studies of self-assembly reactions are fairly rare in any area of chemical science, despite the importance of and emphasis on self-assembly to make more complex structures and materials. Lead references to studies of small, metal-template systems are as follows: (a) Hasenknopf, B.; Lehn, J.-M.; Boumediene, N.; Leize, E.; Van Dorsselaer, A. Angew. Chem., Int. Ed. 1998, 37, 3265.
    • (1998) Angew. Chem., Int. Ed. , vol.37 , pp. 3265
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* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.