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Volumn 133, Issue 20, 2011, Pages 7744-7756

Supported-nanoparticle heterogeneous catalyst formation in contact with solution: Kinetics and proposed mechanism for the conversion of Ir(1,5-COD)Cl/γ-Al2O3 to Ir(0)∼900/ γ-Al2O3

Author keywords

[No Author keywords available]

Indexed keywords

AUTOCATALYTIC; FORMATION MECHANISM; FORMATION SYSTEMS; HETEROGENEOUS CATALYSIS; HETEROGENEOUS CATALYST; IR(ETCP)(1 ,5-COD); KINETIC DATA; MECHANISTIC STUDIES; NANOPARTICLE FORMATION; NANOPARTICLE GROWTHS; NANOPARTICLE SCIENCE; NANOPARTICLE SYNTHESIS; NUCLEATION AND GROWTH; PRECATALYSTS; QUANTITATIVE KINETICS; RATE CONSTANT K; SHAPE-CONTROLLED; STABILIZATION SYSTEMS; SURFACE GROWTH; TWO-STEP MECHANISMS;

EID: 79957745767     PISSN: 00027863     EISSN: 15205126     Source Type: Journal    
DOI: 10.1021/ja110550h     Document Type: Article
Times cited : (27)

References (115)
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    • Additional examples of supported-nanoparticle heterogeneous catalyst preparation in contact with solution include: De Jong, K. P.; Geus, J. W. Appl. Catal., A 1982, 4, 41
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    • "Weakly ligated/labile ligand" nanoparticles are simply nanoparticles with ideally 100% removable or replaceable ligands prepared using only the desired reactants (or solvent) for the catalytic reaction at hand. Related concepts, such as putatively "solvent-only" stabilized nanoparticles, are discussed in: Ott, L. S.; Finke, R. G. Inorg. Chem. 2006, 45, 8382. A recent review has also been published (3h) detailing nanoparticle stabilization and the use of anion free metal precursors that, in principle, can generate such "weakly ligated/labile ligand" or "solvent only" stabilized nanoparticles. See footnote 41 in ref 14 for related work on putatively "naked nanoparticles"
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    • Our prior work (14) is certainly not the first example of a well-characterized organometallic precatalyst. Extensive examples of well-characterized organometallic precatalysts can be found in: Zakharov, V. A.; Yermakov, Y. I. Catal. Rev.-Sci. Eng. 1979, 19, 67
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    • Modern Surface Organometallic Chemistry; Basset, J.-M.; Psaro, R.; Roberto, D.; Ugo, R., Eds.; Wiley-VCH: Weinheim, 2009. However, ours is the first study that starts from a well-characterized speciation-controlled supported organometallic precatalyst and focuses on supported-nanoparticle heterogeneous catalyst formation in contact with solution, and which contains the necessary kinetic data to rule out alternative mechanisms en route to a kinetically supported proposed mechanism.
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    • 3 supported-nanoparticle heterogeneous catalyst (confirmed for the present system by transmission electron microscopy (TEM) and XAFS (14)). In addition, a prototype system should: (iv) yield an active and long-lived catalyst, and hence (v) provide a system where the initial kinetic and mechanistic studies of the in situ catalyst formation are worth the effort. The prototype system should also yield (vi) reproducible and quantitative kinetic data so that quantitative conclusions and mechanistic insights can be drawn; and ideally (vii) comparison to a kinetically and mechanistically well-studied nanoparticle formation system in solution should also be possible for any insights that comparison might allow. (4, 34, 45) Last, once that prototype system is in hand, one would also like to (viii) systematically vary key synthetic variables such as the support, solvent, and metal precursor to reveal their affects on supported-nanoparticle formation in contact with solution.
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    • 3 wt % as was done in the present studies.
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    • 3 precatalyst preparation and subsequent supported-nanoparticle heterogeneous catalyst formation kinetics. (14) Hence, it follows that only samples prepared under the same synthetic conditions should be (and were) plotted in Figures 2 and 3
    • 3 precatalyst preparation and subsequent supported-nanoparticle heterogeneous catalyst formation kinetics. (14) Hence, it follows that only samples prepared under the same synthetic conditions should be (and were) plotted in Figures 2 and 3.
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    • In neat cyclohexane, the UV-vis spectrum of the filtered solution (Figure S3 in the Supporting Information) reveals that no Ir(1,5-COD)Cl(solvent) is present in solution. However, in acetone, two metal-to-ligand charge transfer bands are present from 340 to 540 nm (detailed in the Supporting Information), data consistent with the presence of a square planar Ir(I) complex in acetone. (39)
    • In neat cyclohexane, the UV-vis spectrum of the filtered solution (Figure S3 in the Supporting Information) reveals that no Ir(1,5-COD)Cl(solvent) is present in solution. However, in acetone, two metal-to-ligand charge transfer bands are present from 340 to 540 nm (detailed in the Supporting Information), data consistent with the presence of a square planar Ir(I) complex in acetone. (39)
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    • 2 and, therefore, is not MTL under these conditions). (4)
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    • sus and [acetone] data
    • sus and [acetone] data.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.