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Langmuir. 2006 Oct 24;22(22):9357-67.

A test of the transition-metal nanocluster formation and stabilization ability of the most common polymeric stabilizer, poly(vinylpyrrolidone), as well as four other polymeric protectants.

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Colorado State University, Fort Collins, Colorado 80523, USA.


Following an introduction to the nanocluster stabilization literature and DLVO (Derjaugin-Landau-Verwey-Overbeek) theory of colloidal stability, the most common steric stabilizer of transition-metal nanoclusters, poly(vinylpyrrolidone) (PVP), has been examined for its efficacy in the formation, stabilization, and subsequent catalytic activity of prototype, test case Ir(0)n nanoclusters. First, the five criteria established previously for ranking nanocluster protectants for their nanocluster formation and stabilization ability were evaluated for 1 monomer equiv of 10000 average molecular weight (MWav) PVP in the absence, and then presence, of the traditionally weakly coordinating anion BF4- as well as the absence and presence of the strongly coordinating, superior anionic stabilizer P2W15Nb3O62(9-), all in propylene carbonate solvent. It is found that neither 1 equiv of BF4- in propylene carbonate nor 1 monomer equiv of (undried) PVP alone allows for isolable and redissolvable nanoclusters without bulk Ir(0)n metal formation. Careful predrying of the PVP, and by implication other polymers, is shown to be necessary for the formation and stabilization of the nanoclusters. Next, 40 monomer equiv of 10000 MWav PVP and 1 equiv of BF4- in propylene carbonate are shown to allow isolable, redissolvable nanoclusters. Control experiments reveal little difference on nanocluster stabilization by 3500 or 55000 (i.e., vs 10,000) MWav PVP, but yield interesting effects on nanocluster nucleation by the 3500 MWav PVP, as well as by the polymer poly(bis(ethoxy)phosphazene) (PBEP). Four other key polymers reported in the literature to be nanocluster stabilizers are tested by the five criteria method for their efficacy in the formation and stabilization of Ir0n nanoclusters (now in acetone due to the polymers' solubility) and in comparison to each other, specifically, poly(methyl methacrylate) (PMMA), poly(styrene) (PS), poly(methylhydrosilane) (PMHS), and PBEP. Only 40 monomer equiv dried PMMA allows isolable and redissolvable nanoclusters in acetone. Control/reference point experiments show that the electrostatic stabilizer P2W15Nb3O62(9-) is superior to each of the five polymeric stabilizers studied herein in both acetone and propylene carbonate, at least for the test case of Ir(0)n nanoclusters. Further controls show that 40 monomer equiv of PVP added to P2W15Nb3O(62)9--stabilized nanoclusters has no discernible effect on the five criteria other than to reduce by approximately 50% the nanocluster catalytic activity and total catalytic lifetime for cyclohexene hydrogenation. The main finding of this work is that DLVO theory as applied to nanocluster stabilization is fully supported; that is, surface-bound anions in high dielectric constant solvents provide superior stabilization. The importance of even traditionally weakly coordinating anions such as BF4- in nanocluster stabilization is a second, important finding of this work. The fact that HPO4(2-) has been shown to be a simple, cheap, commercially available, thermally robust, and 31P-NMR-handle-containing analogue of the more esoteric P2W15Nb3O62(9-) stabilizer is also discussed in the 14 total Conclusions from this first study ranking polymeric stabilizers of modern transition-metal nanoclusters.

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