Volume 19, Issue 28 p. 9381-9387
Full Paper

Synthesis of Nanocomposites from Pd0 and a Hyper-Cross-Linked Functional Resin Obtained from a Conventional Gel-Type Precursor

Dr. Karel Jeřábek

Corresponding Author

Dr. Karel Jeřábek

Institute of Chemical Process Fundamentals, Academy of Sciences of the Czech Republic, Rozvojova 2/135, CZ-16502 Prague 6-Suchdol, Czech Republic, Fax: (+420) 220-920-661

Karel Jeřábek, Institute of Chemical Process Fundamentals, Academy of Sciences of the Czech Republic, Rozvojova 2/135, CZ-16502 Prague 6-Suchdol, Czech Republic, Fax: (+420) 220-920-661

Marco Zecca, Dipartimento di Scienze Chimiche, Università degli Studi di Padova, Via Marzolo 1, 35131 Padova (Italy), Fax: (+39) 049-827-5050

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Prof. Marco Zecca

Corresponding Author

Prof. Marco Zecca

Dipartimento di Scienze Chimiche, Università degli Studi di Padova, Via Marzolo 1, 35131 Padova (Italy), Fax: (+39) 049-827-5050

Karel Jeřábek, Institute of Chemical Process Fundamentals, Academy of Sciences of the Czech Republic, Rozvojova 2/135, CZ-16502 Prague 6-Suchdol, Czech Republic, Fax: (+420) 220-920-661

Marco Zecca, Dipartimento di Scienze Chimiche, Università degli Studi di Padova, Via Marzolo 1, 35131 Padova (Italy), Fax: (+39) 049-827-5050

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Dr. Paolo Centomo

Dr. Paolo Centomo

Dipartimento di Scienze Chimiche, Università degli Studi di Padova, Via Marzolo 1, 35131 Padova (Italy), Fax: (+39) 049-827-5050

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Federico Marchionda

Federico Marchionda

Dipartimento di Scienze Chimiche, Università degli Studi di Padova, Via Marzolo 1, 35131 Padova (Italy), Fax: (+39) 049-827-5050

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Dr. Luca Peruzzo

Dr. Luca Peruzzo

Istituto di Geoscienze e Georisorse – Sezione di Padova, Consiglio Nazionale delle Ricerche, Via Matteotti 30, 35137 Padova (Italy)

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Dr. Patrizia Canton

Dr. Patrizia Canton

Dipartimento di Scienze Molecolari e Nanosistemi, Università Ca' Foscari di Venezia via Torino 155/b, I-30170 Venezia-Mestre (Italy)

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Dr. Enrico Negro

Dr. Enrico Negro

Dipartimento di Scienze Chimiche, Università degli Studi di Padova, Via Marzolo 1, 35131 Padova (Italy), Fax: (+39) 049-827-5050

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Prof. Vito Di Noto

Prof. Vito Di Noto

Dipartimento di Scienze Chimiche, Università degli Studi di Padova, Via Marzolo 1, 35131 Padova (Italy), Fax: (+39) 049-827-5050

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Prof. Benedetto Corain

Prof. Benedetto Corain

Dipartimento di Scienze Chimiche, Università degli Studi di Padova, Via Marzolo 1, 35131 Padova (Italy), Fax: (+39) 049-827-5050

Istituto di Scienze e Tecnologie Molecolari – Sezione di Padova, Consiglio Nazionale delle Ricerche, Via Marzolo 1, 35131 Padova (Italy)

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First published: 31 May 2013
Citations: 9

Graphical Abstract

Templating palladium with a permanently microporous resin: A sulfonated hyper-cross-linked resin has been used for the first time as the support for nanostructured palladium. TEM analysis (see figure) showed that the resin effectively acts as an exo-template that controls the size of the metal nanoparticles generated within its permanent pore system.

Abstract

Hyper-cross-linked resins stemming from a gel-type poly-chloromethylated poly(styrene-co-divinylbenzene) resin (GT) have been investigated by a multi-methodological approach based on elemental analysis, scanning electron microscopy, X-ray microanalysis, and solvent absorption. The hyper-cross-linking of the parent resin was accomplished by Friedel–Crafts alkylation of the phenyl rings of the resins with the chloromethyl groups. This produced a permanent pore system comprising both micropores (<2.0 nm in diameter) and mesopores (2.2 nm). The chloromethyl groups that did not react in the hyper-cross-linking step were transformed into methylmercaptan groups and the latter were then converted into sulfonic groups by oxidation with hydrogen peroxide. By this procedure the extensive permanent porosity of the parent unsulfonated hyper-cross-linked polymer (HGT) was retained by the sulfonated polymer (HGTS). The final exchange capacity of HGTS was determined to be 0.36 mmol g−1. HGTS was easily metalated with PdII and the subsequent reduction of the metal centers with either aqueous sodium borohydride, formaldehyde, or dihydrogen produced three Pd0/HGTS nanocomposites. The metal nanoparticles had diameters in the 1–6 nm range for all the nanocomposites, as determined by TEM, but with somewhat different distributions. When formaldehyde was used, more than 90 % of the nanoparticles were less than 3 nm and their radial distribution throughout the polymer beads was quite homogeneous. These findings show that with this reducing agent the metal nanoparticles are generated within the pore system of the polymer matrix, hence their size is controlled by the dimensions of the pores of the polymeric support.