Issue 12, 2010
From the journal:

New Journal of Chemistry

Template controlled synthesis of monometallic zerovalent metal nanoclusters inside cross-linked polymer frameworks: the effect of a single matrix on the size of different metal nanoparticles†‡

Paolo Centomo,*a   Patrizia Canton,b   Matteo Ferronic  and  Marco Zeccaa  

* Corresponding authors

a Dipartimendo di Scienze Chimiche, Università degli Studi di Padova, Via Marzolo 1, Padova, Italy
E-mail: paolo.centomo@unipd.it
Fax: +39 0498275223
Tel: +39 0498275206

b Dipartimento di Chimica Fisica, Università degli Studi Ca' Foscari di Venezia, Via Torino 155/b, 30170 Venezia-Mestre, Italy
E-mail: cantonpa@unive.it
Fax: +39 0412346747
Tel: +39 0412346790

c SENSOR, CNR-INFM, Brescia University, Via Valotti 9, Brescia, Italy
E-mail: matteo.ferroni@ing.unibs.it
Fax: + 39 0303715788
Tel: + 39 0303715749

Abstract

Starting from the gel-type, cross-linked copolymer co-poly-{(N,N-dimethethylacrylamide/4-vinylpyridine/N,N′-methylenebisacrylamide} (DV44) we prepared nanoclusters of several noble metals (Ru, Rh, Pd, Pt, Ag, Au) inside its polymer framework through the so-called “template-controlled synthesis” approach. This procedure involves the immobilization of the relevant metal centers inside the polymer framework, followed by their reduction to M0 nanoclusters (in our case, uptake from solutions of suitable precursors and reduction with aqueous solutions of NaBH4, respectively). In this way, a set of monometallic polymer supported nanoclusters (M/DV44, M = Ru, Rh, Pd, Pt, Ag, Au) were obtained. The experimental conditions were set so as to generally obtain a homogeneous radial distribution of the metal throughout the particles of the materials. The latter were characterized by means of transmission electron microscopy for the assessment of the metal nanocluster sizes. The diameter of the nanoclusters generated by reduction inside water-swollen DV44 were compared with the size of the nanopores of the water-swollen polymer framework that had previously been determined by means of inverse steric exclusion chromatography. The diameter of the prevailing pore fractions in water-swollen DV44 was 3.2–4.3 nm and the largest available pores observed had a diameter of 8.1 nm. Nanoclusters with diameters larger than this value were observed in no cases, and in all cases the average diameter of the nanoclusters never exceeded the diameter of the prevailing pore fraction. For Pd/DV44, Ag/DV44 and Au/DV44, the average nanocluster diameter compared very well with the diameter of the prevailing pore fraction.

Graphical abstract: Template controlled synthesis of monometallic zerovalent metal nanoclusters inside cross-linked polymer frameworks: the effect of a single matrix on the size of different metal nanoparticles

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Article information

DOI
https://doi.org/10.1039/B9NJ00648F
Article type
Paper
Submitted
09 Nov 2009
Accepted
27 Jul 2010
First published
20 Sep 2010

New J. Chem., 2010,34, 2956-2961

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Template controlled synthesis of monometallic zerovalent metal nanoclusters inside cross-linked polymer frameworks: the effect of a single matrix on the size of different metal nanoparticles

P. Centomo, P. Canton, M. Ferroni and M. Zecca, New J. Chem., 2010, 34, 2956 DOI: 10.1039/B9NJ00648F

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