DOI: 10.1021/ja808980a. Monitoring Supported-Nanocluster Heterogeneous Catalyst Formation: Product and Kinetic Evidence for a 2-Step, Nucleation and Autocatalytic Growth Mechanism of Pt(0)nFormation from H2PtCl6on Al2O3or TiO2

Monitoring Supported-Nanocluster Heterogeneous Catalyst Formation: Product and Kinetic Evidence for a 2-Step, Nucleation and Autocatalytic Growth Mechanism of Pt(0)nFormation from H2PtCl6on Al2O3or TiO2

10.1021/ja808980a

Crossref journal-article

American Chemical Society (ACS)

Journal of the American Chemical Society (316)

Bibliography

Mondloch, J. E., Yan, X., & Finke, R. G. (2009). Monitoring Supported-Nanocluster Heterogeneous Catalyst Formation: Product and Kinetic Evidence for a 2-Step, Nucleation and Autocatalytic Growth Mechanism of Pt(0)nFormation from H2PtCl6on Al2O3or TiO2. Journal of the American Chemical Society, 131(18), 6389â6396.

Authors 3

Joseph E. Mondloch (first)
Xinhuan Yan (additional)
Richard G. Finke (additional)

References 74 Referenced 60

{'key': 'ref1/cit1', 'volume-title': 'Catalytic Chemistry', 'author': 'Gates B. C.', 'year': '1992'} / Catalytic Chemistry by Gates B. C. (1992)
aHeinemann, H.Development of Industrial Catalysis. InHandbook of Heterogeneous Catalysis;Ertl, G., Knözinger, H., and Weitkamp, J., Eds.VCH:Weinham, 1997; Vol. 1, pp35−38.
{'key': 'ref2/cit2b', 'volume-title': 'Fundamentals of Industrial Catalytic Processes', 'author': 'Bartholomew C. H.', 'year': '2006', 'edition': '2'} / Fundamentals of Industrial Catalytic Processes by Bartholomew C. H. (2006)
10.1002/9783527619528 / Preparation of Solid Catalysts by Ertl G. (1999)
{'key': 'ref3/cit3a', 'volume-title': 'Catalyst Preparation Science and Engineering', 'author': 'Regalbuto J.', 'year': '2007'} / Catalyst Preparation Science and Engineering by Regalbuto J. (2007)
10.1016/S1381-1169(00)00318-6 / J. Mol. Catal. A: Chem. by Lambert J.-F. (2000)
10.1006/jcat.2001.3433 / J. Catal. by Oudenhuijzen M. K. (2002)
10.1021/ja076437p / J. Am. Chem. Soc. by Chupas P. J. (2007)
10.1039/f19736900833 / J. Chem. Soc. Faraday Trans by Herd A. C. (1973)
10.1039/c3975000272b / J. Chem. Soc. Chem. Comm. by Kermarec M. (1975)
10.1039/f19767200674 / J. Chem. Soc. Faraday Trans by Beyer H. (1976)
10.1039/f19767202793 / J. Chem. Soc. Faraday Trans by Jacobs P. A. (1976)
10.1021/ja00112a014 / J. Am. Chem. Soc. by Che M. (1995)
10.1002/anie.200802140 / Angew. Chem., Int. Ed. by Uzun A. (2008)
We have complied a table of the main prior kinetic and mechanistic studies of heterogeneous catalyst formation, and will report that in due course along with our other, in-progress studies. As stated in the main text a few of the conclusions from compiling that table areaadditional or improved experimental techniques for following heterogeneous catalyst formation are needed, and
bmore in depth kinetic and mechanistic studies, including the balanced stoichiometry of the catalytst formation reaction, will be required en route to a better, mechanism-based understanding of how to control the syntheses of heterogeneous catalysts.
For these reasons, the present research falls under one of DOE’s current Grand Challenges in catalysis, namely the design and controlled synthesis of catalytic structures at the molecular and nanometer level, see: Basic Research Needs: Catalysis for Energy; PNNL-17214; Office of Basic Energy Sciences, U.S. Department of Energy; 2007, (http://www.sc.doe.gov/bes/reports/list.html).
10.1023/A:1016711323302 / Catal. Lett. by Somorjai G. A. (2001)
Ma, Z. and Zaera, F. InEncyclopedia of Inorganic Chemsitry,2nd ed.King, B. R., Ed.John Wiley & Sons Ltd:West Sussex, 2005; Vol. 3, pp1768−1784.
10.1016/S0360-0564(08)60017-6 / Adv. Catal. by Che M. (1989)
10.1080/01614948708078611 / Catal. Rev.-Sci. Eng. by Sajkowski D. J. (1987)
10.1021/ar00033a006 / Acc. Chem. Res. by Bond G. C. (1993)
10.1006/jcat.2002.3710 / J. Catal. by Oh H.-S. (2002)
10.1016/0021-9517(86)90369-6 / J. Catal. by Tiep L. V. (1986)
10.1007/BF00764500 / Catal. Lett. by Somorjai G. A. (1990)
10.1039/b309577k / Chem. Commun. by Billinge S. J. L. (2004)
{'key': 'ref15/cit15b', 'volume-title': 'Structure of Nanocrystals', 'author': 'Billinge S. J. L.', 'year': '2008'} / Structure of Nanocrystals by Billinge S. J. L. (2008)
The powerful, direct, high-energy X-ray scattering and pair distribution function (PDF) analysis methods have the large advantage of directly monitoring the loss of Pt–Cl bonds and the formation of Pt–Pt bonds.(4c)The primary disadvantage of these methods is that they are time and effort intensive, and thus relatively slow, with it possible to take even 1−2 years to analyze significant results. Hence, there is a pressing need to prescreen systems and then subject only the most interesting systems to those more direct and powerful, but also more expensive and slower, methods. Important in this regard is that advantages (fast; easy; cheap) and disadvantages (indirect) of the present, fast reporter reaction kinetic method are precisely the opposite of the high-energy X-ray scattering and pair distribution function (PDF) analysis methods (slower and expensive, but direct). Hence, the two methods are highly complimentary. For this reason, a collaboration with the Chupas team has been established in which the general plan is to screen systems with the fast kinetic methods reported herein and then subject the most interesting and important systems to the X-ray scattering methods.
10.1021/ja9705102 / J. Am. Chem. Soc. by Watzky M. A. (1997)
10.1016/S1381-1169(99)00098-9 / J. Mol. Catal. A: Chemical by Aiken J. D. (1999)
10.1021/cr010350j / Chem. Rev. by Roucoux A. (2002)
10.1021/ja8017412 / J. Am. Chem. Soc. by Watzky M. A. (2008)
10.1016/0039-6028(85)90857-X / Surf. Sci. by Wang T. (1985)
10.1126/science.272.5270.1924 / Science by Ahmadi T. S. (1996)
10.1002/smll.200701295 / Small by Tao A. R. (2008)
10.1021/cm9704387 / Chem. Mater. by Watzky M. A. (1997)
10.1021/ja9719485 / J. Am. Chem. Soc. by Aiken J. D. (1998)
10.1021/cm0006852 / Chem. Mater. by Widegren J. A. (2001)
10.1021/cm034585i / Chem. Mater. by Hornstein B. J. (2004)
10.1021/cm0400637 / Chem. Mater. by Hornstein B. J. (2004)
10.1021/ja0504439 / J. Am. Chem. Soc. by Besson C. (2005)
10.1021/cm050207x / Chem. Mater. by Besson C. (2005)
10.1021/cm071088j / Chem. Mater. by Finney E. E. (2008)
10.1039/b411493k / Chem. Commun. by Newton M. A. (2005)
10.1021/jp981287d / J. Phys. Chem. B by Williams C. T. (1998)
10.1021/ja00097a047 / J. Am. Chem. Soc. by Lin Y. (1994)
10.1021/cm980699w / Chem. Mater. by Aiken J. D. (1999)
10.1021/cm0006852 / Chem. Mater. by Widegren J. A. (2001)
10.1021/ic00100a012 / Inorg. Chem. by Lin Y. (1994)
10.1016/0166-9834(82)80288-1 / Appl. Catal. by De Jong K. P. (1982)
10.1016/1381-1169(96)00027-1 / J. Mol. Catal. A: Chem. by Bond G. C. (1996)
10.1016/S0926-860X(98)00124-0 / Appl. Catal., A by Sales E. A. (1998)
10.1016/S1293-2558(02)01311-0 / Solid State Sci. by Bonet F. (2002)
10.1016/j.materresbull.2007.11.006 / Mater. Res. Bull. by Zawadzki M. (2008)
10.1039/b802548g / Chem. Commun. by Boutros M. (2008)
An important topic, one that will require its own extensive studies to unravel, is the nature of the precise Pt speciation when H2PtCl6is placed on supports such as Al2O3as well as the kinetic contribution of each species to Pt(0)nformation. There is literature on the speciation of H2PtCl6in aqueous solutions as well as in the presence of Al2O3.(30)However, no real consensus exists at present on either the exact species present in solution or on the Al2O3support. The literature is clear that [PtCl6]2–, aquo species such as [PtCl5(H2O)]−, aquahydroxo species such as [PtCl4(OH)(H2O)]−along with many others exist in aqueous solutions, and that such speciation is highly pH dependent. The exact interaction of the species formed from aqueous H2PtCl6with the Al2O3support is also a controversial subject.(30b),cRegalbuto(30a)suggests that when fresh H2PtCl6solutions are prepared the major species present in solution is [PtCl3(H2O)3]+, and it is repelled from the protonated [Al2O3]+surface at low pH. However the major species present in aged H2PtCl6solutions in a mid-pH of 5−9 (as defined by those authors(30b)) is [PtCl2(OH)2(H2O)2]0, and this species should more readily interact with the Al2O3support. In the present studies, we use ethyl acetate for the H2PtCl6impregnation step in a deliberate attempt to minimize any subsequent speciation and to emphasize support of the neutral, parent complex. However, during our kinetic runs the H2PtCl6/Al2O3is in contact with the EtOH and cyclohexene solution, so that additional speciation is possible if not probable. Experimentally, we know that the kinetics of H2PtCl6reduction in EtOH plus cyclohexene solutions (but without Al2O3present) are different than the kinetics when Al2O3is present; hence, the support must be playing a role in the observed catalyst formation kinetics. The good news here is that the ability of the catalytic reporter reaction method to rapidly monitor the kinetics of nanoparticle formation will allow the needed survey of a range of supports, metal, and other conditions. Such experiments should yield insights into the Pt speciation and into many other unanswered questions regarding how to best prepare superior supported-nanoparticle heterogeneous catalysts.
10.1016/S0926-860X(02)00116-3 / Appl. Catal., A by Spieker W. A. (2002)
10.1016/S0926-860X(02)00537-9 / Appl. Catal., A by Spieker W. A. (2003)
10.1016/S1381-1169(00)00047-9 / J. Mol. Catal. A: Chem. by Shelimov B. N. (2000)
10.1016/0926-860X(93)80180-X / Appl. Catal., A by Mang T. (1993)
10.1351/pac197850091211 / Pure Appl. Chem. by Brunelle J. P. (1978)
10.1021/ja021436c / J. Am. Chem. Soc. by Widegren J. A. (2003)
aAlthough the 2-step F−W kinetic model is consistent with all of the present data as well as a considerable body of prior kinetics (more than 700 runs) of nanocluster formation under H2,(17, 21)it needs to be emphasized that the F−W kinetic model is a deliberately minimalistic, “Ockham’s razor”-obtained model. As just one example of presently unknown details, the fuller mechanism presumably involves ligated nanocluster, Ma−Lb(M = metal), intermediates as well as possible nanocluster hydride, Mc–Hd, intermediates,(21c, 21g)since naked M(0) atoms are highly energetic and thus relatively unstable.(17, 21c, 21g)Of interest in this regard is that metal-hydrides have been previously postulated to be the aggregating species in supported catalyst formation.(33)Elsewhere we discuss the limitations of the F−W model, limitations that derive ultimately from its minimalistic nature.(37, 38)
aDalla Betta, R. A. and Boudart, M. InInternational Congress on Catalysis,5th ed.North-Holland:Palm Beach, FL, 1972; Vol. 5th Annual, pp1329−1341.
10.1016/0021-9517(81)90131-7 / J. Catal. by Reagan W. J. (1981)
10.1016/j.ccr.2006.08.016 / Coord. Chem. Rev. by Ott L. S. (2007)
10.1002/3527600825 / Kinetics and Mechanism of Reactions of Transition Metal Complexes by Wilkins R. G. (1991)
10.1023/A:1022110200942 / Catal. Lett. by Rodriguez J. A. (2003)
Sigmoidal kinetic curves for protein aggregation fit by the F−W 2-step kinetic model, papers that also contain a detailed discussion of the limitations of the F−W kinetic model (see also elsewhere for a general discussion of the limitations of models in science(38)) all types:
10.1021/bi701899y / Biochemistry by Morris A. M. (2008)
10.1021/bi800726m / Biochemistry by Watzky M. A. (2008)
10.1016/j.bpc.2008.11.003 / Biophys. Chem. by Morris A. M. (2009)
{'key': 'ref38/cit38', 'first-page': ', submitted', 'author': 'Finney E. E.', 'journal-title': 'Chem. Mater.'} / Chem. Mater. by Finney E. E.
10.1021/ja021436c / J. Am. Chem. Soc. by Widegren J. A. (2003)

Dates

Type	When
Created	16 years, 4 months ago (April 20, 2009, 2:23 p.m.)
Deposited	1 year, 5 months ago (March 12, 2024, 3:35 p.m.)
Indexed	1 month, 2 weeks ago (July 19, 2025, 11:19 p.m.)
Issued	16 years, 4 months ago (April 20, 2009)
Published	16 years, 4 months ago (April 20, 2009)
Published Online	16 years, 4 months ago (April 20, 2009)
Published Print	16 years, 3 months ago (May 13, 2009)

Funders 0

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BibTeX

@article{Mondloch_2009, title={Monitoring Supported-Nanocluster Heterogeneous Catalyst Formation: Product and Kinetic Evidence for a 2-Step, Nucleation and Autocatalytic Growth Mechanism of Pt(0)nFormation from H2PtCl6on Al2O3or TiO2}, volume={131}, ISSN={1520-5126}, url={http://dx.doi.org/10.1021/ja808980a}, DOI={10.1021/ja808980a}, number={18}, journal={Journal of the American Chemical Society}, publisher={American Chemical Society (ACS)}, author={Mondloch, Joseph E. and Yan, Xinhuan and Finke, Richard G.}, year={2009}, month=apr, pages={6389–6396} }

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      "volume-title": "Catalytic Chemistry",
      "author": "Gates B. C.",
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    },
    {
      "key": "ref2/cit2a",
      "unstructured": "aHeinemann, H.Development of Industrial Catalysis. InHandbook of Heterogeneous Catalysis;Ertl, G., Kn\u00f6zinger, H., and Weitkamp, J., Eds.VCH:Weinham, 1997; Vol. 1, pp35\u221238."
    },
    {
      "key": "ref2/cit2b",
      "volume-title": "Fundamentals of Industrial Catalytic Processes",
      "author": "Bartholomew C. H.",
      "year": "2006",
      "edition": "2"
    },
    {
      "key": "ref3/cit3",
      "doi-asserted-by": "crossref",
      "DOI": "10.1002/9783527619528",
      "volume-title": "Preparation of Solid Catalysts",
      "author": "Ertl G.",
      "year": "1999"
    },
    {
      "key": "ref3/cit3a",
      "volume-title": "Catalyst Preparation Science and Engineering",
      "author": "Regalbuto J.",
      "year": "2007"
    },
    {
      "key": "ref4/cit4a",
      "doi-asserted-by": "crossref",
      "first-page": "5",
      "DOI": "10.1016/S1381-1169(00)00318-6",
      "volume": "162",
      "author": "Lambert J.-F.",
      "year": "2000",
      "journal-title": "J. Mol. Catal. A: Chem."
    },
    {
      "key": "ref4/cit4b",
      "doi-asserted-by": "crossref",
      "first-page": "135",
      "DOI": "10.1006/jcat.2001.3433",
      "volume": "205",
      "author": "Oudenhuijzen M. K.",
      "year": "2002",
      "journal-title": "J. Catal."
    },
    {
      "key": "ref4/cit4c",
      "doi-asserted-by": "crossref",
      "first-page": "13822",
      "DOI": "10.1021/ja076437p",
      "volume": "129",
      "author": "Chupas P. J.",
      "year": "2007",
      "journal-title": "J. Am. Chem. Soc."
    },
    {
      "key": "ref5/cit5a",
      "doi-asserted-by": "crossref",
      "first-page": "833",
      "DOI": "10.1039/f19736900833",
      "volume": "69",
      "author": "Herd A. C.",
      "year": "1973",
      "journal-title": "J. Chem. Soc. Faraday Trans"
    },
    {
      "key": "ref5/cit5b",
      "doi-asserted-by": "crossref",
      "first-page": "272",
      "DOI": "10.1039/c3975000272b",
      "volume": "8",
      "author": "Kermarec M.",
      "year": "1975",
      "journal-title": "J. Chem. Soc. Chem. Comm."
    },
    {
      "key": "ref5/cit5c",
      "doi-asserted-by": "crossref",
      "first-page": "674",
      "DOI": "10.1039/f19767200674",
      "volume": "72",
      "author": "Beyer H.",
      "year": "1976",
      "journal-title": "J. Chem. Soc. Faraday Trans"
    },
    {
      "key": "ref5/cit5d",
      "doi-asserted-by": "crossref",
      "first-page": "2793",
      "DOI": "10.1039/f19767202793",
      "volume": "72",
      "author": "Jacobs P. A.",
      "year": "1976",
      "journal-title": "J. Chem. Soc. Faraday Trans"
    },
    {
      "key": "ref6/cit6a",
      "doi-asserted-by": "crossref",
      "first-page": "2008",
      "DOI": "10.1021/ja00112a014",
      "volume": "117",
      "author": "Che M.",
      "year": "1995",
      "journal-title": "J. Am. Chem. Soc."
    },
    {
      "key": "ref7/cit7",
      "doi-asserted-by": "crossref",
      "first-page": "9245",
      "DOI": "10.1002/anie.200802140",
      "volume": "47",
      "author": "Uzun A.",
      "year": "2008",
      "journal-title": "Angew. Chem., Int. Ed."
    },
    {
      "key": "ref8/cit8",
      "unstructured": "We have complied a table of the main prior kinetic and mechanistic studies of heterogeneous catalyst formation, and will report that in due course along with our other, in-progress studies. As stated in the main text a few of the conclusions from compiling that table areaadditional or improved experimental techniques for following heterogeneous catalyst formation are needed, and"
    },
    {
      "key": "ref8/cit8b",
      "unstructured": "bmore in depth kinetic and mechanistic studies, including the balanced stoichiometry of the catalytst formation reaction, will be required en route to a better, mechanism-based understanding of how to control the syntheses of heterogeneous catalysts."
    },
    {
      "key": "ref9/cit9",
      "unstructured": "For these reasons, the present research falls under one of DOE\u2019s current Grand Challenges in catalysis, namely the design and controlled synthesis of catalytic structures at the molecular and nanometer level, see: Basic Research Needs: Catalysis for Energy; PNNL-17214; Office of Basic Energy Sciences, U.S. Department of Energy; 2007, (http://www.sc.doe.gov/bes/reports/list.html)."
    },
    {
      "key": "ref10/cit10",
      "doi-asserted-by": "crossref",
      "first-page": "1",
      "DOI": "10.1023/A:1016711323302",
      "volume": "76",
      "author": "Somorjai G. A.",
      "year": "2001",
      "journal-title": "Catal. Lett."
    },
    {
      "key": "ref11/cit11",
      "unstructured": "Ma, Z. and Zaera, F. InEncyclopedia of Inorganic Chemsitry,2nd ed.King, B. R., Ed.John Wiley & Sons Ltd:West Sussex, 2005; Vol. 3, pp1768\u22121784."
    },
    {
      "key": "ref12/cit12",
      "doi-asserted-by": "crossref",
      "first-page": "55",
      "DOI": "10.1016/S0360-0564(08)60017-6",
      "volume": "36",
      "author": "Che M.",
      "year": "1989",
      "journal-title": "Adv. Catal."
    },
    {
      "key": "ref13/cit13a",
      "doi-asserted-by": "crossref",
      "first-page": "325",
      "DOI": "10.1080/01614948708078611",
      "volume": "29",
      "author": "Sajkowski D. J.",
      "year": "1987",
      "journal-title": "Catal. Rev.-Sci. Eng."
    },
    {
      "key": "ref13/cit13b",
      "doi-asserted-by": "crossref",
      "first-page": "490",
      "DOI": "10.1021/ar00033a006",
      "volume": "26",
      "author": "Bond G. C.",
      "year": "1993",
      "journal-title": "Acc. Chem. Res."
    },
    {
      "key": "ref13/cit13c",
      "doi-asserted-by": "crossref",
      "first-page": "375",
      "DOI": "10.1006/jcat.2002.3710",
      "volume": "210",
      "author": "Oh H.-S.",
      "year": "2002",
      "journal-title": "J. Catal."
    },
    {
      "key": "ref13/cit13d",
      "doi-asserted-by": "crossref",
      "first-page": "449",
      "DOI": "10.1016/0021-9517(86)90369-6",
      "volume": "99",
      "author": "Tiep L. V.",
      "year": "1986",
      "journal-title": "J. Catal."
    },
    {
      "key": "ref14/cit14",
      "doi-asserted-by": "crossref",
      "first-page": "169",
      "DOI": "10.1007/BF00764500",
      "volume": "7",
      "author": "Somorjai G. A.",
      "year": "1990",
      "journal-title": "Catal. Lett."
    },
    {
      "key": "ref15/cit15a",
      "doi-asserted-by": "crossref",
      "first-page": "749",
      "DOI": "10.1039/b309577k",
      "author": "Billinge S. J. L.",
      "year": "2004",
      "journal-title": "Chem. Commun."
    },
    {
      "key": "ref15/cit15b",
      "volume-title": "Structure of Nanocrystals",
      "author": "Billinge S. J. L.",
      "year": "2008"
    },
    {
      "key": "ref16/cit16",
      "unstructured": "The powerful, direct, high-energy X-ray scattering and pair distribution function (PDF) analysis methods have the large advantage of directly monitoring the loss of Pt\u2013Cl bonds and the formation of Pt\u2013Pt bonds.(4c)The primary disadvantage of these methods is that they are time and effort intensive, and thus relatively slow, with it possible to take even 1\u22122 years to analyze significant results. Hence, there is a pressing need to prescreen systems and then subject only the most interesting systems to those more direct and powerful, but also more expensive and slower, methods. Important in this regard is that advantages (fast; easy; cheap) and disadvantages (indirect) of the present, fast reporter reaction kinetic method are precisely the opposite of the high-energy X-ray scattering and pair distribution function (PDF) analysis methods (slower and expensive, but direct). Hence, the two methods are highly complimentary. For this reason, a collaboration with the Chupas team has been established in which the general plan is to screen systems with the fast kinetic methods reported herein and then subject the most interesting and important systems to the X-ray scattering methods."
    },
    {
      "key": "ref17/cit17",
      "doi-asserted-by": "crossref",
      "first-page": "10382",
      "DOI": "10.1021/ja9705102",
      "volume": "119",
      "author": "Watzky M. A.",
      "year": "1997",
      "journal-title": "J. Am. Chem. Soc."
    },
    {
      "key": "ref18/cit18a",
      "doi-asserted-by": "crossref",
      "first-page": "1",
      "DOI": "10.1016/S1381-1169(99)00098-9",
      "volume": "145",
      "author": "Aiken J. D.",
      "year": "1999",
      "journal-title": "J. Mol. Catal. A: Chemical"
    },
    {
      "key": "ref18/cit18b",
      "doi-asserted-by": "crossref",
      "first-page": "3757",
      "DOI": "10.1021/cr010350j",
      "volume": "102",
      "author": "Roucoux A.",
      "year": "2002",
      "journal-title": "Chem. Rev."
    },
    {
      "key": "ref19/cit19",
      "doi-asserted-by": "crossref",
      "first-page": "11959",
      "DOI": "10.1021/ja8017412",
      "volume": "130",
      "author": "Watzky M. A.",
      "year": "2008",
      "journal-title": "J. Am. Chem. Soc."
    },
    {
      "key": "ref20/cit20a",
      "doi-asserted-by": "crossref",
      "first-page": "181",
      "DOI": "10.1016/0039-6028(85)90857-X",
      "volume": "163",
      "author": "Wang T.",
      "year": "1985",
      "journal-title": "Surf. Sci."
    },
    {
      "key": "ref20/cit20b",
      "doi-asserted-by": "crossref",
      "first-page": "1924",
      "DOI": "10.1126/science.272.5270.1924",
      "volume": "272",
      "author": "Ahmadi T. S.",
      "year": "1996",
      "journal-title": "Science"
    },
    {
      "key": "ref20/cit20c",
      "doi-asserted-by": "crossref",
      "first-page": "310",
      "DOI": "10.1002/smll.200701295",
      "volume": "4",
      "author": "Tao A. R.",
      "year": "2008",
      "journal-title": "Small"
    },
    {
      "key": "ref21/cit21a",
      "doi-asserted-by": "crossref",
      "first-page": "3083",
      "DOI": "10.1021/cm9704387",
      "volume": "12",
      "author": "Watzky M. A.",
      "year": "1997",
      "journal-title": "Chem. Mater."
    },
    {
      "key": "ref21/cit21b",
      "doi-asserted-by": "crossref",
      "first-page": "9545",
      "DOI": "10.1021/ja9719485",
      "volume": "120",
      "author": "Aiken J. D.",
      "year": "1998",
      "journal-title": "J. Am. Chem. Soc."
    },
    {
      "key": "ref21/cit21c",
      "doi-asserted-by": "crossref",
      "first-page": "312",
      "DOI": "10.1021/cm0006852",
      "volume": "13",
      "author": "Widegren J. A.",
      "year": "2001",
      "journal-title": "Chem. Mater."
    },
    {
      "key": "ref21/cit21d",
      "doi-asserted-by": "crossref",
      "first-page": "139",
      "DOI": "10.1021/cm034585i",
      "volume": "16",
      "author": "Hornstein B. J.",
      "year": "2004",
      "journal-title": "Chem. Mater."
    },
    {
      "key": "ref21/cit21dd",
      "doi-asserted-by": "crossref",
      "first-page": "3972",
      "DOI": "10.1021/cm0400637",
      "volume": "16",
      "author": "Hornstein B. J.",
      "year": "2004",
      "journal-title": "Chem. Mater."
    },
    {
      "key": "ref21/cit21e",
      "doi-asserted-by": "crossref",
      "first-page": "8179",
      "DOI": "10.1021/ja0504439",
      "volume": "127",
      "author": "Besson C.",
      "year": "2005",
      "journal-title": "J. Am. Chem. Soc."
    },
    {
      "key": "ref21/cit21f",
      "doi-asserted-by": "crossref",
      "first-page": "4925",
      "DOI": "10.1021/cm050207x",
      "volume": "17",
      "author": "Besson C.",
      "year": "2005",
      "journal-title": "Chem. Mater."
    },
    {
      "key": "ref21/cit21g",
      "doi-asserted-by": "crossref",
      "first-page": "1956",
      "DOI": "10.1021/cm071088j",
      "volume": "20",
      "author": "Finney E. E.",
      "year": "2008",
      "journal-title": "Chem. Mater."
    },
    {
      "key": "ref22/cit22",
      "doi-asserted-by": "crossref",
      "first-page": "118",
      "DOI": "10.1039/b411493k",
      "author": "Newton M. A.",
      "year": "2005",
      "journal-title": "Chem. Commun."
    },
    {
      "key": "ref23/cit23",
      "doi-asserted-by": "crossref",
      "first-page": "4785",
      "DOI": "10.1021/jp981287d",
      "volume": "102",
      "author": "Williams C. T.",
      "year": "1998",
      "journal-title": "J. Phys. Chem. B"
    },
    {
      "key": "ref24/cit24",
      "doi-asserted-by": "crossref",
      "first-page": "8335",
      "DOI": "10.1021/ja00097a047",
      "volume": "116",
      "author": "Lin Y.",
      "year": "1994",
      "journal-title": "J. Am. Chem. Soc."
    },
    {
      "key": "ref25/cit25",
      "doi-asserted-by": "crossref",
      "first-page": "1035",
      "DOI": "10.1021/cm980699w",
      "volume": "11",
      "author": "Aiken J. D.",
      "year": "1999",
      "journal-title": "Chem. Mater."
    },
    {
      "key": "ref26/cit26",
      "doi-asserted-by": "crossref",
      "first-page": "312",
      "DOI": "10.1021/cm0006852",
      "volume": "13",
      "author": "Widegren J. A.",
      "year": "2001",
      "journal-title": "Chem. Mater."
    },
    {
      "key": "ref27/cit27",
      "doi-asserted-by": "crossref",
      "first-page": "4891",
      "DOI": "10.1021/ic00100a012",
      "volume": "33",
      "author": "Lin Y.",
      "year": "1994",
      "journal-title": "Inorg. Chem."
    },
    {
      "key": "ref28/cit28a",
      "doi-asserted-by": "crossref",
      "first-page": "41",
      "DOI": "10.1016/0166-9834(82)80288-1",
      "volume": "4",
      "author": "De Jong K. P.",
      "year": "1982",
      "journal-title": "Appl. Catal."
    },
    {
      "key": "ref28/cit28b",
      "doi-asserted-by": "crossref",
      "first-page": "261",
      "DOI": "10.1016/1381-1169(96)00027-1",
      "volume": "109",
      "author": "Bond G. C.",
      "year": "1996",
      "journal-title": "J. Mol. Catal. A: Chem."
    },
    {
      "key": "ref28/cit28c",
      "doi-asserted-by": "crossref",
      "first-page": "273",
      "DOI": "10.1016/S0926-860X(98)00124-0",
      "volume": "172",
      "author": "Sales E. A.",
      "year": "1998",
      "journal-title": "Appl. Catal., A"
    },
    {
      "key": "ref28/cit28d",
      "doi-asserted-by": "crossref",
      "first-page": "665",
      "DOI": "10.1016/S1293-2558(02)01311-0",
      "volume": "4",
      "author": "Bonet F.",
      "year": "2002",
      "journal-title": "Solid State Sci."
    },
    {
      "key": "ref28/cit28e",
      "doi-asserted-by": "crossref",
      "first-page": "3111",
      "DOI": "10.1016/j.materresbull.2007.11.006",
      "volume": "43",
      "author": "Zawadzki M.",
      "year": "2008",
      "journal-title": "Mater. Res. Bull."
    },
    {
      "key": "ref28/cit28f",
      "doi-asserted-by": "crossref",
      "first-page": "2920",
      "DOI": "10.1039/b802548g",
      "author": "Boutros M.",
      "year": "2008",
      "journal-title": "Chem. Commun."
    },
    {
      "key": "ref29/cit29",
      "unstructured": "An important topic, one that will require its own extensive studies to unravel, is the nature of the precise Pt speciation when H2PtCl6is placed on supports such as Al2O3as well as the kinetic contribution of each species to Pt(0)nformation. There is literature on the speciation of H2PtCl6in aqueous solutions as well as in the presence of Al2O3.(30)However, no real consensus exists at present on either the exact species present in solution or on the Al2O3support. The literature is clear that [PtCl6]2\u2013, aquo species such as [PtCl5(H2O)]\u2212, aquahydroxo species such as [PtCl4(OH)(H2O)]\u2212along with many others exist in aqueous solutions, and that such speciation is highly pH dependent. The exact interaction of the species formed from aqueous H2PtCl6with the Al2O3support is also a controversial subject.(30b),cRegalbuto(30a)suggests that when fresh H2PtCl6solutions are prepared the major species present in solution is [PtCl3(H2O)3]+, and it is repelled from the protonated [Al2O3]+surface at low pH. However the major species present in aged H2PtCl6solutions in a mid-pH of 5\u22129 (as defined by those authors(30b)) is [PtCl2(OH)2(H2O)2]0, and this species should more readily interact with the Al2O3support. In the present studies, we use ethyl acetate for the H2PtCl6impregnation step in a deliberate attempt to minimize any subsequent speciation and to emphasize support of the neutral, parent complex. However, during our kinetic runs the H2PtCl6/Al2O3is in contact with the EtOH and cyclohexene solution, so that additional speciation is possible if not probable. Experimentally, we know that the kinetics of H2PtCl6reduction in EtOH plus cyclohexene solutions (but without Al2O3present) are different than the kinetics when Al2O3is present; hence, the support must be playing a role in the observed catalyst formation kinetics. The good news here is that the ability of the catalytic reporter reaction method to rapidly monitor the kinetics of nanoparticle formation will allow the needed survey of a range of supports, metal, and other conditions. Such experiments should yield insights into the Pt speciation and into many other unanswered questions regarding how to best prepare superior supported-nanoparticle heterogeneous catalysts."
    },
    {
      "key": "ref30/cit30a",
      "doi-asserted-by": "crossref",
      "first-page": "219",
      "DOI": "10.1016/S0926-860X(02)00116-3",
      "volume": "232",
      "author": "Spieker W. A.",
      "year": "2002",
      "journal-title": "Appl. Catal., A"
    },
    {
      "key": "ref30/cit30b",
      "doi-asserted-by": "crossref",
      "first-page": "53",
      "DOI": "10.1016/S0926-860X(02)00537-9",
      "volume": "243",
      "author": "Spieker W. A.",
      "year": "2003",
      "journal-title": "Appl. Catal., A"
    },
    {
      "key": "ref30/cit30c",
      "doi-asserted-by": "crossref",
      "first-page": "91",
      "DOI": "10.1016/S1381-1169(00)00047-9",
      "volume": "158",
      "author": "Shelimov B. N.",
      "year": "2000",
      "journal-title": "J. Mol. Catal. A: Chem."
    },
    {
      "key": "ref30/cit30d",
      "doi-asserted-by": "crossref",
      "first-page": "239",
      "DOI": "10.1016/0926-860X(93)80180-X",
      "volume": "106",
      "author": "Mang T.",
      "year": "1993",
      "journal-title": "Appl. Catal., A"
    },
    {
      "key": "ref30/cit30e",
      "doi-asserted-by": "crossref",
      "first-page": "1211",
      "DOI": "10.1351/pac197850091211",
      "volume": "50",
      "author": "Brunelle J. P.",
      "year": "1978",
      "journal-title": "Pure Appl. Chem."
    },
    {
      "key": "ref31/cit31",
      "doi-asserted-by": "crossref",
      "first-page": "10301",
      "DOI": "10.1021/ja021436c",
      "volume": "125",
      "author": "Widegren J. A.",
      "year": "2003",
      "journal-title": "J. Am. Chem. Soc."
    },
    {
      "key": "ref32/cit32a",
      "unstructured": "aAlthough the 2-step F\u2212W kinetic model is consistent with all of the present data as well as a considerable body of prior kinetics (more than 700 runs) of nanocluster formation under H2,(17, 21)it needs to be emphasized that the F\u2212W kinetic model is a deliberately minimalistic, \u201cOckham\u2019s razor\u201d-obtained model. As just one example of presently unknown details, the fuller mechanism presumably involves ligated nanocluster, Ma\u2212Lb(M = metal), intermediates as well as possible nanocluster hydride, Mc\u2013Hd, intermediates,(21c, 21g)since naked M(0) atoms are highly energetic and thus relatively unstable.(17, 21c, 21g)Of interest in this regard is that metal-hydrides have been previously postulated to be the aggregating species in supported catalyst formation.(33)Elsewhere we discuss the limitations of the F\u2212W model, limitations that derive ultimately from its minimalistic nature.(37, 38)"
    },
    {
      "key": "ref33/cit33a",
      "unstructured": "aDalla Betta, R. A. and Boudart, M. InInternational Congress on Catalysis,5th ed.North-Holland:Palm Beach, FL, 1972; Vol. 5th Annual, pp1329\u22121341."
    },
    {
      "key": "ref33/cit33b",
      "doi-asserted-by": "crossref",
      "first-page": "89",
      "DOI": "10.1016/0021-9517(81)90131-7",
      "volume": "69",
      "author": "Reagan W. J.",
      "year": "1981",
      "journal-title": "J. Catal."
    },
    {
      "key": "ref34/cit34",
      "doi-asserted-by": "crossref",
      "first-page": "1075",
      "DOI": "10.1016/j.ccr.2006.08.016",
      "volume": "251",
      "author": "Ott L. S.",
      "year": "2007",
      "journal-title": "Coord. Chem. Rev."
    },
    {
      "key": "ref35/cit35",
      "doi-asserted-by": "crossref",
      "DOI": "10.1002/3527600825",
      "volume-title": "Kinetics and Mechanism of Reactions of Transition Metal Complexes",
      "author": "Wilkins R. G.",
      "year": "1991",
      "edition": "2"
    },
    {
      "key": "ref36/cit36",
      "doi-asserted-by": "crossref",
      "first-page": "247",
      "DOI": "10.1023/A:1022110200942",
      "volume": "85",
      "author": "Rodriguez J. A.",
      "year": "2003",
      "journal-title": "Catal. Lett."
    },
    {
      "key": "ref37/cit37",
      "unstructured": "Sigmoidal kinetic curves for protein aggregation fit by the F\u2212W 2-step kinetic model, papers that also contain a detailed discussion of the limitations of the F\u2212W kinetic model (see also elsewhere for a general discussion of the limitations of models in science(38)) all types:"
    },
    {
      "key": "ref37/cit37a",
      "doi-asserted-by": "crossref",
      "first-page": "2413",
      "DOI": "10.1021/bi701899y",
      "volume": "47",
      "author": "Morris A. M.",
      "year": "2008",
      "journal-title": "Biochemistry"
    },
    {
      "key": "ref37/cit37b",
      "doi-asserted-by": "crossref",
      "first-page": "10790",
      "DOI": "10.1021/bi800726m",
      "volume": "47",
      "author": "Watzky M. A.",
      "year": "2008",
      "journal-title": "Biochemistry"
    },
    {
      "key": "ref37/cit37c",
      "doi-asserted-by": "crossref",
      "first-page": "9",
      "DOI": "10.1016/j.bpc.2008.11.003",
      "volume": "140",
      "author": "Morris A. M.",
      "year": "2009",
      "journal-title": "Biophys. Chem."
    },
    {
      "key": "ref38/cit38",
      "first-page": ", submitted",
      "author": "Finney E. E.",
      "journal-title": "Chem. Mater."
    },
    {
      "key": "ref39/cit39",
      "doi-asserted-by": "crossref",
      "first-page": "10301",
      "DOI": "10.1021/ja021436c",
      "volume": "125",
      "author": "Widegren J. A.",
      "year": "2003",
      "journal-title": "J. Am. Chem. Soc."
    }
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