photooxidation of tris in a photoelectrochemical biofuel cell
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Photooxidation of Tris in a Photoelectrochemical Biofuel Cell
Marcin S. FilipiakPiotr GreskowiakAdrianna ZloczewskaRobert LynchMartin Jönsson-Niedziolka
Institute of Physical ChemistryPolish Academy of SciencesWarsaw, Poland
Martin Jönsson-Niedziólka, martinj@ichf.edu.pl
Institute of Physical Chemistry PAS, Warsaw Poland
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Outline
• Photoelectrochemical biofuel cells
• Our system and preparation of TiO2 NT electrodes
• Some difficulties
• Tris(hydroxymethyl)aminomethane oxidation
• Conclusions
Institute of Physical Chemistry PAS, Warsaw Poland
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Yang, J. et al., J. Power Sources 248, 660–667 (2014).
Photoelectrochemical Biofuel Cell
Institute of Physical Chemistry PAS, Warsaw Poland
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Brune, A. et al., Langmuir 20, 8366–71 (2004).
TiO2 anode with 5-(4-carboxyphenyl)-10,15,20-tris(4-methylphenyl)porphyrin. Anode compartment with 0.25 M Tris at pH 8 (adjusted with HCl) that contained 0.1 M KCl as a supporting electrolyte.4.0 mM NADH, 0.10 M glucose, and 0.5 units/mL GDH under an argon atmosphere.Three electrode setup.
Photoelectrochemical Biofuel Cell
Institute of Physical Chemistry PAS, Warsaw Poland
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TiO2 nanotube anode and air-breathing biocathode
Institute of Physical Chemistry PAS, Warsaw Poland
Zloczewska, A. & Jönsson-Niedziolka, M., J. Power Sources 228, 104–111 (2013).
66Institute of Physical Chemistry PAS, Warsaw Poland
Anodisation of TiO2 nanotubes (TNTs)
• Electropolished titanium sheet • 0.75% HF solution in ethylene glycol,• H2O content - 9.985% v/v• 100 V• 1 h• after anodization – 3 h of 450°C annealing
J. M. Macák et al., Angew. Chem. Int. Ed. (2005) 44 (14), p. 2100–2102
77Institute of Physical Chemistry PAS, Warsaw Poland
0.6% v/v HF
1.0% v/v HF
88Institute of Physical Chemistry PAS, Warsaw Poland
Setup
photoanode
TiO2 NT
biocathodeTORAY|
(BOD+SWCNT-PTSA+MTMOS)
Nafion membrane
0.1 M phosphate buffer pH 8
0.1 M phosphate
buffer pH 4.8
99Institute of Physical Chemistry PAS, Warsaw Poland
Zloczewska, A., PhD Thesis (2013).
Some strange results
Black – Sensitised TNTs; 4 mM NADH, 15 Units GDH dm−3 and 1 M glucose
Grey – bare TNTs in buffer.
Diamonds grown for 4 hours, triangles 1 h.
1010Institute of Physical Chemistry PAS, Warsaw Poland
What‘s going on?
Illumination
Glucose is adsorbing UV.- removing all the biostuff – glucose sensorNot suitable porphyrin Large background currents in
enzyme experiments
Han, L., et al., Chem. Commun. 48, 6103–5 (2012).
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Large background current
Institute of Physical Chemistry PAS, Warsaw Poland
(a)glucose (b)glucose, but no sensitizer, GDH and
NADH (c) no glucose(d)in the dark.Yang, J. et al., J. Power Sources 222, 344–350 (2013).
Han, L., et al., Chem. Commun. 48, 6103–5 (2012).
1212Institute of Physical Chemistry PAS, Warsaw Poland
Tris photoelectrocatalysis on TNT
1313Institute of Physical Chemistry PAS, Warsaw Poland
Tris photoelectrocatalysis on TNT
Tris is photo-oxidised by hydroxyl radical attack
Diesen, V. & Jonsson, M., J. Adv. Oxid. Technol. 15, 392–398 (2012).
Langmuir-Hinshelwood model
KLH = 295 M-1
1414Institute of Physical Chemistry PAS, Warsaw Poland
Photoelectrochemical biofuel cell
0.0 0.3 0.6 0.9 1.2 1.50
100
200
300
400
500486 A/cm
2
1.36 V
1.07 V
366 A/cm2
j /
A/c
m2
E vs. Ag/AgCl / V
0.25 M TRIS
buffer
2 M MeOH
0.0 0.3 0.6 0.9 1.2 1.50
50
100
150
200
250
138.31 W/cm2
(0.61 V)
222.5 W/cm2 (0.73 V)
P / W
/cm
2
E vs. Ag/AgCl / V
buffer
0.25 M TRIS
2 M MeOH
Very similar characteristics to published PECBFC with enzymatic regeneration system.
1515Institute of Physical Chemistry PAS, Warsaw Poland
Conclusions
• Tris can be efficiently photoelecrooxidized on the titania
based electrode
• We made a TNT based PECBFC with decent
performance.
• Tris can act as a quite efficient fuel in
photoelectrochemical biofuel cell, but maybe it's not the
best idea
• Main conclusion – be careful with your buffers, they are
not always nice inert backgrounds.
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Dr Ada ZloczewskaDr Robert LynchUniversity of Limerick
Marcin Filipiak
1616Institute of Physical Chemistry PAS, Warsaw Poland
Martin Jönsson-Niedziólka, martinj@ichf.edu.pl, www.charge-transfer.pl
Thank you for your attention
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