j. w. dickinson, c.boxall, f. andrieux engineering department, lancaster university, lancaster, la1...
TRANSCRIPT
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J. W. Dickinson, C.Boxall, F. AndrieuxEngineering Department, Lancaster University, Lancaster, LA1 4YW, U.K
2nd year PhD
The Development of the Graphene Based Micro-optical Ring Electrode:
Application as a Photo-electrochemical Sensor for Actinide
Detection
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Contents
1. PROJECT BACKGROUND
2. FABRICATION OF THE GRAPHENE BASED-MICRO OPTICAL RING ELECTRODE (GB-MORE)
3. EXPERIMENTAL/ RESULTS
4. APPLICATIONS
5. ACKNOWLEDGEMENTS
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• The development of the Graphene Based Micro-Optical Ring Electrode (GB-MORE) as a photo-electrochemical sensor for:
• Selective
• Quantitative
measurements of actinide species in a range of nuclear processed waste streams.
• Actinides show good electrochemistry on carbon based electrodes which show
durability when being operated in highly corrosive conditions [Kwon, 2009;
Wang, 1995].
This project is aimed at:
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• Small size allows measurement in small volumes
• Possibility of calibration less use [Szabo, 1987]
Microelectrode Advantages
Convergent analyte diffusion field associated with micro-ring electrodes results in:
• Enhanced material flux
• Rapid attainment of the steady state • Short response time
Easy to construct and low costs
↓
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Carbon based electrode materials include:
• Glassy carbon
• Graphite
• Graphene
Why Graphene?
A single graphene layer has a thickness of ~0.355nm [Ni, 2007]
Graphene exhibits ballistic electron mobility resulting in super conducting electrical properities.
A high density of defect states on graphene flakes provide a loci for promoting electron transfer.
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Fabrication of the Electrode
• Synthesis of Graphite Oxide
• Layer Preparation
• Reduction of GO
• Electrode construction
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Top-Down formation of single layer graphite oxide from bulk graphite powder.
1. Bulk graphite
2. The oxidative procedure incorporates oxygen functionalities between the carbon layers forcing them apart
3. Heavy sonication in solution separates these layers forming single layers of GO
1.2. 3.
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Formation of GO layer on a pre- treated substrate
OH
O
O
O
OC
OH
CC
OOO
OO
OO
OH
O
CO
HO O
OHOH
OHOH
OH
O
O
O
OO
O OO
O
O
The oxidation procedure incorporates:
• lactol
• anhydrides
• quinone
• hydroxl
Above: GO layer with oxygen groups
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Graphite oxide flake →
Chemical and Thermal Reduction:
•Reduction By chemical treatment using hydrazine vapour and thermal
annealing
• Removes a majority of the oxygen functionalities and produce a conducting
layer.
3-Aminopropyltriethoxysilane →
Quartz substrate →
Reduced/conducting top side
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The Synthesis of Graphite Oxide (GO) via a Modified
Hummers Method.Recovered product is subsequently washed with a total 0f 40L of dilute acid solutions
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Collected Filter Cake of Washed Graphite Oxide
• Solutions of GO are made from the
dried material and heavily sonicated to
delaminate the layers of graphite oxide.
• 0.1- 10wt% solution loadings
• TGA analysis
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Bottom-up formation of homogenous GO layers
• Dip coating of pre-prepared quartz
substrates using GO solutions
•These solutions can now be:
- Evaporation cast
- Spin coated
- Dip coated
• Multiple dip coats can be used to increase
layer thickness
Above: Dip coated GO on quartz
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Left/ Above: Tapping mode AFM image of the reduced GO surface topography
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Treated 200µm fibre optic dip coated into GO solution followed by hydrazine
then thermal reduction treatment
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15
monochromd
light
light connector
gold layer
optical glue
ball lens
optical fibre
optical disc
electrochemical ring
Connection of MORE to Light Source
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Xenon Lampwith
mono-chromator
Earthed Faraday Cage
N2
MORE
Pt wire
SCE
Autolab with PGSTAT 10
Personal Computer
Light Coupler
Light Guide
Photo-Electrochemistry: Apparatus used
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Cyclic Voltammetric Analysis of GB-MORE using K3Fe(CN)63+:
Dark experiment
Eθ of K 3Fe(CN)63-/4- is 0.119V vs SCE [Bard, 2001].
Fe (II) → Fe (III)
Fe (II) ← Fe (III)
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Ru(bipy)32
+
h
The Ruthenium/Iron, Sensitiser Scavenger System: Light experiment
Ru(bipy)32+
*
Fe3+
Fe2+Ru(bipy)3
3+
e-
Photo current arise due to: Photo-physical, Chemical, Electrochemical reaction
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Measurement of a Photocurrent at the GB- MORE: the Ru(II)/Fe(III) System
Photo transient change in current; E=480mV, [Ru(bipy)32+] 10mM, [Fe3+]
5mM, pH=2, white light on and off
Light onLight on
Light offLight off
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Spectral response of Ru(II)/Fe(III) at GB-MOREVariation of steady state photocurrent as a function of irradiation wavelength
at the MORE. pH=2
Ru(bipy)32+
λmax = 453.2nm
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Effect on the Steady State Photocurrent as a Function of the Concentration in Ru(bipy)3
2+
Solution: [Fe(III)]=5mM, [Ru(bipy)32+]: as x-axis,
pH=2, E=480mV, Using white light
2
( ) ( )2 2 1
( )2 1
[ ] [ ][ ]
II IIIs ph
IIIk o
nFD I Ru a k Fei b a
k X k k Fe
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SV
o
kkk
erceptintslope 1
1
2
1( )
2 2( )
2 1
[ ]11
[ ]
IIs ph o
IIIk
nFD I Ru a kb a
i k X k Fe
Literature Stern Volmer quencher constant = 0.9 m 3 mol-1 [Lin & Sutin, 1976]
Effect on the Photocurrent as a Function of the Concentration in Iron(III)
Solution: [Ru(bipy)32+]= 10mM, [Fe(III)]= as x-axis,
pH=2, E=480mV, Using white light
KSV= 0.7m3 mol-1
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Conclusion
Graphene Based Micro- Optical Ring Electrodes have been
successfully fabricated with inner/ outer ring ratios >0.99.
Highly reversible electrochemistry has been observed in the
absence of any illuminating wavelength.
Very promising results have been obtained towards meeting the
aim of this project during photo-electrochemical experiments.
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Applications of the GB-MORE
• As a sensor for monitoring photo active species
• As a calibration less sensor
• selective
• quantitative
• actinide species in a range of nuclear processed waste streams
• Ability to differentiate between two or more actinide species
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UO22+ + hv → * UO2
2+
Further Work:
• To investigate dark electrochemistry of the uranyl ion on GB-MOREs
• To investigate the photo-electrochemistry of the uranyl ion using ethanol as
quencher in acidified aqueous media using the GB-MORE [Nagaishi, 2002]
• Study the results obtained using theoretical architecture [Andrieux, 2006]
• Look at further selectivity of GB-MORE in other species.
• Provided that the λmax of given actinide species is sufficiently separated
differentiation between two or more species in solution should be possible.
*UO22+/ UO2
+ = (E0=2.7V)
λmax = 420nm-460nm
*PuO22+/ Pu4+ (E0=4.56V)
λmax = 350nm
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Acknowledgements
University of Lancaster
Professor Colin Boxall
Dr Fabrice Andrieux