DOI: 10.1021/la0207522. Transition-Metal Nanocluster Stabilization Fundamental Studies: Hydrogen Phosphate as a Simple, Effective, Readily Available, Robust, and Previously Unappreciated Stabilizer for Well-Formed, Isolable, and Redissolvable Ir(0) and Other Transition-Metal Nanoclusters

Transition-Metal Nanocluster Stabilization Fundamental Studies: Hydrogen Phosphate as a Simple, Effective, Readily Available, Robust, and Previously Unappreciated Stabilizer for Well-Formed, Isolable, and Redissolvable Ir(0) and Other Transition-Metal Nanoclusters

10.1021/la0207522

Crossref journal-article

American Chemical Society (ACS)

Langmuir (316)

Bibliography

Ãzkar, S., & Finke, R. G. (2003). Transition-Metal Nanocluster Stabilization Fundamental Studies:â Hydrogen Phosphate as a Simple, Effective, Readily Available, Robust, and Previously Unappreciated Stabilizer for Well-Formed, Isolable, and Redissolvable Ir(0) and Other Transition-Metal Nanoclusters. Langmuir, 19(15), 6247â6260.

Authors 2

Saim Özkar (first)
Richard G. Finke (additional)

References 36 Referenced 66

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A SciFinder search of the literature yielded only two reports on the use of phosphate anion to stabilize (silver) colloids;a,bno prior study of phosphate to stabilize modern transition-metal(0) nanoclusters2has appeared. Moreover, none of the prior reports provides any idea that phosphate might be a more general stabilizer with an effectiveness comparable to that of citrate3-; there is also no idea in the prior literature that phosphate or hydrogen phosphate might be applicable to a broader range of metal(0) nanoclusters29as suggested by the results reported herein. Finally, it is even ambiguous which protonation state of phosphate is the actual stabilizer, as well as what the charge and formal oxidation state are on the surface metals, of the prior (Ag) nanocolloid work.a,b(a) Schneider, S.; Grau, H.; Halbig, P.; Freunscht, P.; Nickel, U.J. Raman Spectrosc.1996,27, 57. (b) Greaves, S. J.; Griffith, W. P.J. Raman Spectrosc.1988,19, 503. (c) Phosphate has also been used to stabilize (AgI)n, a historically important system in which double layer theory was tested: Hunter, R. J. InFoundationsof Colloidal Science; Oxford University Press: New York, 1987; Vol. 1, p 369; see also Van den Hul, H. J.; Lyklema, J.J. Colloid Sci.1967,23, 500. (d) One other paper reports the use of CoII3(PO4)2in colloid preparation as an integral component of higher-valent metal colloids, that is, materials that obviously are not HPO42-anion-stabilized metal(0) nanoclusters such as those made in the present work; see Ishikawa, T.; Matijevic, E.J. ColloidInterface Sci.1988,123, 122. (e) A recent paper adds Na3PO4to serve as a base in a Pd nanocluster-catalyzed Suzuki coupling reaction but focuses only on the polymer or dendrimer stabilizers present; an unrecognized stabilizing effect due to the phosphate, as well as stabilization due to the other anions present, are probable in that work: Li, Y.; El-Sayed, M. A.J. Phys. Chem. B2001,105, 8938. For phosphating metal surfaces, see also: (f) Rausch, W.The Phosphating of Metals; Finishing Publications Ltd. Teddington, Middlesex, England, 1990. (g) Yu, T.; Li, L.; Lin, C. T.J. Phys. Chem.1995,99, 7613. These authors note that “the chemical and physical fundamentals of the molecular level of metal phosphate formed at the coating interface have never been systematically studied”. They propose a PO-species to bind to the metal surface; our work in the present paper suggests, instead, PO3n-binding to the metal surface. (h) Kozlov, L. A.; Okulov, V. V. AVTOBAZ, Tolyatti, Russia.Gal'vanotekhnika i Obrabotka Poverkhnosti,1999,7(2), 27−32. (“Phosphating Theory and Practice”; in Russian; CAN 132:254222.) (i) Giles, T. R.Metal Finishing2001,99(9), 10−12, 14−16, 18−20. (“Pretreatment of Various Substrates Prior to Electrocoating”; Henkel Surface Technologies, Henkel Corp, Madison Heights, MI; CAN 135:306595.) (j) Schuemichen, H. Interfinish 92, Int. Congr. Surf. Finish,1992,2, 630−639. (“New Developments in the Field of Phosphating Metal Surfaces”; Publisher: Assoc. Bras. Trat. Superficie, Sao Paulo, Brazil; CAN 119: 165228.)
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(a) A rough estimate of the metal−metal distance for each of these metals atop their individual nanoclusters, taken as 2 times their bulk-metallic radius,29bis as follows: Fe (2.52 Å), Co (2.50 Å), Ni (2.50 Å), Ru (2.68 Å), Rh (2.68 Å), Pd (2.74 Å), Re (2.74 Å), Os (2.70 Å), and Pt (2.78 Å). A 1−4% contraction of these surface distances atop nanoclusters has precedent; see the references and discussion of this point provided elsewhere.5c(b) Wells, A. F.Structural Inorganic Chemistry; Clarendon Press: Oxford, U.K., 1975; p 1022. For example, the metallic radius of 12-coordinate, fcc-packed Ir is 1.36 Å, so that a first estimate of the Ir−Ir surface distance is twice this value or ca. 2.7 Å, and with even a 4% contraction within the 2.6−2.7 Å range cited in the text.
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Dates

Type	When
Created	22 years, 1 month ago (July 15, 2003, 1:17 a.m.)
Deposited	2 years, 6 months ago (March 5, 2023, 4:46 p.m.)
Indexed	2 weeks, 1 day ago (Aug. 23, 2025, 12:59 a.m.)
Issued	22 years, 2 months ago (June 25, 2003)
Published	22 years, 2 months ago (June 25, 2003)
Published Online	22 years, 2 months ago (June 25, 2003)
Published Print	22 years, 2 months ago (July 1, 2003)

Funders 0

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BibTeX

@article{_zkar_2003, title={Transition-Metal Nanocluster Stabilization Fundamental Studies: Hydrogen Phosphate as a Simple, Effective, Readily Available, Robust, and Previously Unappreciated Stabilizer for Well-Formed, Isolable, and Redissolvable Ir(0) and Other Transition-Metal Nanoclusters}, volume={19}, ISSN={1520-5827}, url={http://dx.doi.org/10.1021/la0207522}, DOI={10.1021/la0207522}, number={15}, journal={Langmuir}, publisher={American Chemical Society (ACS)}, author={Özkar, Saim and Finke, Richard G.}, year={2003}, month=jun, pages={6247–6260} }

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      "unstructured": "(a) A rough estimate of the metal\u2212metal distance for each of these metals atop their individual nanoclusters, taken as 2 times their bulk-metallic radius,29bis as follows:\u2009 Fe (2.52 \u00c5), Co (2.50 \u00c5), Ni (2.50 \u00c5), Ru (2.68 \u00c5), Rh (2.68 \u00c5), Pd (2.74 \u00c5), Re (2.74 \u00c5), Os (2.70 \u00c5), and Pt (2.78 \u00c5). A 1\u22124% contraction of these surface distances atop nanoclusters has precedent; see the references and discussion of this point provided elsewhere.5c(b) Wells, A. F.Structural Inorganic Chemistry; Clarendon Press:\u2009 Oxford, U.K., 1975; p 1022. For example, the metallic radius of 12-coordinate, fcc-packed Ir is 1.36 \u00c5, so that a first estimate of the Ir\u2212Ir surface distance is twice this value or ca. 2.7 \u00c5, and with even a 4% contraction within the 2.6\u22122.7 \u00c5 range cited in the text."
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