Ferrocene-decorated nanocrystalline cellulose with charge carrier mobility

S Eyley, Sara Shariki, Sara E C Dale, Simon Bending, Frank Marken, W Thielemans

Research output: Contribution to journalArticle

44 Citations (Scopus)

Abstract

Ferrocene-decorated cellulose nanowhiskers were prepared by the grafting of ethynylferrocene onto azide functionalized cotton-derived cellulose nanowhiskers using azide-alkyne cycloaddition. Successful surface modification and retention of the crystalline morphology of the nanocrystals was confirmed by elemental analysis, inductively coupled plasma-atomic emission spectroscopy, X-ray photoelectron spectroscopy, and X-ray diffraction. The coverage with ferrocenyl is high (approximately 1.14 × 10 -3 mol g -1 or 4.6 × 10 13 mol cm -2 corresponding to a specific area of 61 ̊ 2 per ferrocene). Cyclic voltammetry measurements of films formed by deposition of ferrocene-decorated nanowhiskers showed that this small spacing of redox centers along the nanowhisker surface allowed conduction hopping of electrons. The apparent diffusion coefficient for electron (or hole) hopping via Fe(III/II) surface sites is estimated as D app = 10 -19 m 2s -1 via impedance methods, a value significantly less than nonsolvated ferrocene polymers, which would be expected as the 1,2,3-triazole ring forms a rigid linker tethering the ferrocene to the nanowhisker surface. In part, this is believed to be also due to "bottleneck"? diffusion of charges across contact points where individual cellulose nanowhiskers contact each other. However, the charge-communication across the nanocrystal surface opens up the potential for use of cellulose nanocrystals as a charge percolation template for the preparation of conducting films via covalent surface modification (with applications similar to those using adsorbed conducting polymers), for use in bioelectrochemical devices to gently transfer and remove electrons without the need for a solution-soluble redox mediator, or for the fabrication of three-dimensional self-assembled conducting networks.
Original languageEnglish
Pages (from-to)6514-6519
Number of pages6
JournalLangmuir
Volume28
Issue number16
DOIs
Publication statusPublished - 2012

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Nanowhiskers
Carrier mobility
carrier mobility
Charge carriers
cellulose
Cellulose
charge carriers
Nanocrystals
nanocrystals
Azides
conduction
Surface treatment
Electrons
tethering
Atomic emission spectroscopy
Conductive films
Triazoles
electrons
Alkynes
Cycloaddition

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Ferrocene-decorated nanocrystalline cellulose with charge carrier mobility. / Eyley, S; Shariki, Sara; Dale, Sara E C; Bending, Simon; Marken, Frank; Thielemans, W.

In: Langmuir, Vol. 28, No. 16, 2012, p. 6514-6519.

Research output: Contribution to journalArticle

Eyley, S ; Shariki, Sara ; Dale, Sara E C ; Bending, Simon ; Marken, Frank ; Thielemans, W. / Ferrocene-decorated nanocrystalline cellulose with charge carrier mobility. In: Langmuir. 2012 ; Vol. 28, No. 16. pp. 6514-6519.
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