Surface Immobilisation of Transition Metal Substituted Krebs Type Polyoxometalates, [X 2 W 20 M 2 O 70 (H 2 O) 6 ] n-(X = Bi or Sb, M = Co 2+ or Cu 2+ ), by the Layer by Layer Technique

Murphy, Aidan Fagan and McCormac, Timothy (2011) Surface Immobilisation of Transition Metal Substituted Krebs Type Polyoxometalates, [X 2 W 20 M 2 O 70 (H 2 O) 6 ] n-(X = Bi or Sb, M = Co 2+ or Cu 2+ ), by the Layer by Layer Technique. Electrochimica Acta .

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Abstract

A series of transition metal (i.e. Cu 2+ and Co 2+ ) substituted Krebs type Polyoxometalates (POMs), of the general formula [X 2 W 20 M 2 O 70 (H 2 O) 6 ] n- , X = Sb or Bi, M = Co(II) or Cu(II), have been successfully immobilised onto carbon electrode surfaces through the employment of the layer-by-layer (LBL) technique. This involved the construction of alternating anionic POM, [X 2 W 20 M 2 O 70 (H 2 O) 6 ] n- , layers and the cationic metallodendrimer, Ru(II)-metallodendrimer as the cationic layers, in addition to a [poly(diallyldimethylammonium chloride)] PDDA base layer. Stable multielectron redox couples associated with the W-O framework, for the Krebs type POMs, and the Ru(III/II) for the metallodendrimer, were clearly observed upon layer construction and redox switching within the pH domain of 2 to 6.5. The constructed multilayer assemblies exhibited pH dependent redox activity and thin layer behaviour up to 100 mV s -1 . The porosity and permeability of the individual multilayer assemblies towards an anionic probe was determined by AC impedance and cyclic voltammetry. The surface morphology of each multilayer was also determined by Atomic Force Microscopy (AFM). Keywords:

Item Type:	Article
Uncontrolled Keywords:	Polyoxometalate; Krebs; Immobilisation; Layer by Layer (LBL);
Subjects:	Science
Research Centres:	Electrochemistry Research Group
Depositing User:	Concepta Woods
Date Deposited:	01 Dec 2011 14:42
Last Modified:	11 Nov 2014 16:10
URI:	https://eprints.dkit.ie/id/eprint/72

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