Research project proposal

1. Project title:
Improving the performance of microbial fuel cell by introduce Fe-AAPyr catalyst.
-Firoz Ahmed
2. Introduction:

Energy plays a pivotal role in our daily life. In this regard, energy demand increasing day by day.
Therefore, it is needed to produce energy in low cost and find out sustainable energy harvesting
technologies like renewable energy sources [1-4]. After the invention of fuel cell (FC) in 1838,
peoples started to use microbial fuel cells (MFCs) extensively all over the world because of its
continuous supply of electricity. In MFC, an electrochemical reaction takes place into hydrogen
and oxygen or another oxidizing agent to produce electricity [5]. In the very beginning of the
invention of FC, it was used in NASA for the production of electricity in satellites and space
capsules. In course of time FC used in fuel vehicle including Automobiles, buses, boats and even
in the submarines [6].
In Bangladesh, use of FC was started after many years later of its invention, because of low
economics country. But nowadays its use increasing inordinately here. Meanwhile, the commercial
energy stock of Bangladesh is very poor which will be not sufficient for future energy demand. In
this case, for mitigating this energy problem, it will be needed a new source of energy where MFC
can play a significant role [7]. A MFC work by converting chemical energy to electrical energy by
the help of electroactive catalyst at the anode [ 8]. Therefore, some limitations are raised from the
deeper study about MFC. In the acidic medium, Oxygen can be reduced to water towards 2x2e-
mechanism with an intermediate (peroxide). In alkaline medium, oxygen can ve reduced to
hydroxyl ion towards 2x2e- transfer mechanism in presence of HO2- and OH- as intermediate.
Second one can produce H2O or OH in case of acidic or alkaline media electrolyte by chemically
or electrochemically. Here chemical kinetics generally low. For enhancing kinetics of overall
reaction, additional catalysts are used. Different types of catalysts are available like biotic or
abiotic such as enzymatic and microbial respectively (9, 10). First one is unsuitable for MFCs
because of high cost and low durability. Second one is vest fitted as catalyst in FC which enhance
the chemical reaction besides its sustainability. Abiotic catalysts have two families named: i)
platinum-group metal (PGM), ii) platinum group metal free (PGM-free) [11]. PGM catalysts are
predominantly used in MFCs as the cathode materials [11,12]. This is because of the utilization of
the formation of the more mature fuel cell functioned in both acidic or alkaline FC. Besides this,
PGM catalysts are enable to directly exposed to wastewater activated sludge and other organics
which contains large amounts of cations and anions that interact directly with the catalyst active
centres, reducing dramatically the electrocatalytic activity [13].
Those limitations will be fixed if we introduce PGM catalysts as cathode materials for MFCs
applications. In spite of different carbonaceous materials like activated carbon, carbon nanotube
etc. Fe-AAPyr catalysts are regularly used because of its environmental friendly substance.
Therefore, carbonaceous materials are used as supporting catalyst materials and pyrolyzed PGM-
free catalysts are generally the most used for MFCs [14]. The expected motto of this work is to
introduce catalysts such as activated carbon and iron-amino antipyrine (Fe-AAPyr) placed on
graphene nanosheet separately and used these as alternative cathode catalyst materials to improve
MFCs performance.
3. Objectives of study:
The main objectives of the proposed research project are the following:
1. To examine the performance of catalyst materials as an alternative cathode in MFC.
2. To enhance the production of electric power.
3. To study the electrochemical behaviour of the fabricated cathodes.
4. To elucidate the effect of Fe-AAPyr incorporation to carbon nanosheet for improving
its electrocatalytic activity in terms of Oxygen Reduction Reaction (ORR).

4. Rationale of the study:

First FC were invented in the year 1838 which was used in only NASA space program during this
time (Wikipedia). In course of time, the use of MFC increasing day by day. The efficient system
of electricity production makes this cell an undissected part of our lives in the field of energy. In
this row, Bangladesh is also explored the field of use of MFC. Nowadays advanced study is
ongoing through all over the world, Bangladesh is not outside of this study but It has some lacking
standby. Still, there are some problems in terms of energy production which makes the people
encourage to use gasoline engine. Therefore, I approach to do research to introduce a catalyst in
MFCs which will increase the rate of electrochemical reaction into the cell and require less amount
of fuels but give higher amount of energy compared to ordinary MFCs. As Bangladesh is a
developed country so, economic side is must be take into account that, is it economically feasible
or not? So, Efficiency must be increased to produce energy and here PGM catalyst can do it. On
the other hand, gasoline engine, some other ordinary fuel cell, hydrogen production cell is
generally not environment-friendly where MFCs does not affect environment badly. In summary,
some catalysts like PGM, Fe-AAPyr separately introduced into MFCs as an alternative cathode
catalyst to improve the performance of the MFCs which will be lower the cost of the energy
production. This is the most needed criteria for the country like Bangladesh which will be
economically feasible and environment-friendly.

5. Methodology:

5.1 Materials Aminoantipyrne (Fe-AApyr), Silica, organic precursor, Air breathing cathode,
activated carvon (AC), Hydrofluoric acid (HF), Eppendorf tubes, Nafion solution, Isopropanol,
Buffer solution, Micro-tip ultrasonic prove, Glassy carbon disk, Sweep voltammograms (LSVs)
etc.

5.2 Preparation of catalyst Fe-AAPyr Sacrificial Support Method is most practiced method for
the synthesis of Fe-AAPyr (59). At first Fe-AAPyr and Iron nitrite will be grinding in a ball-mill
with silica until getting fine powder. The gained powder will be pyrolyzed under Ultrapure N2 gas
at 950 centigrade for 40mins. The flow rate will be fixed at 100mLmin per min. After completing
this action, the mixture will be cooled down in 25°C under atmospheric temperature in a furnace.
Here HF will be used for the removal of silica from the catalyst and catalyst will be washed with
DI water for acquiring neutral PH. Then the catalyst dried at a temperature of 90°C in muffle
furnace.

5.3 Characterization of Fe-AAPyr Fe-AAPyr are strongly heterogeneous due to the existence of
different sizes of pores including micropores, mesopores and micropores. Surface and structural
properties of the Fe-AAPyr and activated carbons will be studied directly by employing various
techniques. Scanning electron microscope (SEM) will be employed to identify the surface
morphology. The specific surface area and the porosity of the as-synthesized samples will be
characterized by N2 sorption analysis. The chemical functionality of prepared Fe-AAPyr will be
qualitatively identified by Fourier transforms infrared (FTIR) spectrophotometer.

5.4 Electrode Preparation Anode electrodes made up of two carbon brushes with 3cm in diameter
and 3cm in height. Cathode will be fabricated in a circular pellet type structure by using metallic
pellet which will dye under the pressure of 3mT applied for 5min using hydraulic press [8]. A
mixture of Activated carbon (AC), carbon black (CB) and polytetrafluoroethylene (PTFE) will be
taken into a blender for mixing in a ratio of 7:1:2 respectively. This mixture will mix with 30gm
of catalyst and made into air breathing cathodes respectively. Then cathode and anode will be
ready for use.

5.5 Cathode polarization curve and MFCs polarization curve

In this study, the prepared cathodes screwed to a lateral hole of the MFC and filled with 0.1M
buffer solution of potassium phosphate with 7.5 pH to carry out the linear sweep voltammetry
(LSV) measurements (96,97). The cathode will keep in contact with electrolyte for a whole night.
LSV will be running in a fixed scan rate of 0.2 mV per second from open circuit potential to -0.4V
with the working electrode cathode. Titanium wire (> 2m in length) as counter electrode and
Ag/AgCl (3M KCl) as the reference electrode. Here air breathing cathodes were run for each
catalyst investigated. For Bacterial feed solution sodium acetate solution will be used along with
activated sludge. The solution which is prepared before will switched in 50:50 K-PV and keep
with 3mL siduyn acetate (stock of 100g/L). Source of activated sludge will be collecting from
some ordinary source. Into the switched solution, the anodes are moved into the new MFCs and
the overall system will have left in open circuit voltage(OCV) for at least 3h before running the
overall polarization curve. The polarization curve will be running from OCV to 0V with scanning
rate 0.2mV/s. Then the triplicates of different MFCs will be investigated which run for each
catalyst. The individual potentials of cathode and anode will be measured separately during the
preparation of polarization curve using another potentiometer channel. The amount of surface area
(2.858 cm2) of cathode will be exposed into the solution. All the calculations will have referred to
the geometric cathode are exposed to the electrolyte.
6.Expected outcomes:
- MFC can turn on ten LED lamps and one digital clock for the duration of 2 days. Therefore,
it mitigates some electricity deficiency.
- Two conference paper and one journal paper.

7.References

1. P. Pandey, V.N. Shinde, R.L. Deopurkar, S.P. Kale, S.A. Patil, D. Pant, Recent advances
in the use of different substrates in microbial fuel cells toward wastewater treatment and
simultaneous energy recovery, Appl. Energy 168 (2016) 706.
2. S. Bajracharya, S. Srikanth, G. Mohanakrishna, R. Zacharia, D.P. Strik, D. Pant,
Biotransformation of carbon dioxide in bioelectrochemical systems: state of the art and
future prospects, J. Power Sources 365 (2017) 256.
3. A. Rinaldi, B. Mecheri, V. Garavaglia, S. Licoccia, P. Di Nardo, E. Traversa, Engineering
materials and biology to boost performance of microbial fuel cells: a critical review,
Energy Environ. Sci. 1 (2008) 417.
4. C. Santoro, C. Arbizzani, B. Erable, I. Ieropoulos, Microbial fuel cells: from fundamentals
to applications. A review, J. Power Sources 356 (2017) 225.
5. R.S. Khurmi, R.S. Sedha, Material Science, 5th edition, New Delhi, India, 2014.
6. en.wikipedia.org, 31 March, 2018.
7. M.S. Mridha, A.H. Khan, M.A.W. Miah, Bangladesh atomic energy commission research
news, Atomic Energy Centre, P.O. Box 164, Ramna, Dhaka-1000, Bangladesh.
8. K. Mounika, H. Sergi, K. Sadia, S. Alexey, S. Carlo, I. Ioannis, A. Plamen, Enhancement
of microbial fuel cell performance by introducing a nanocomposite cathode catalyst, Elec.
Acta 265 (2018) 56-64.
9. B. Erable, D. Feron, A. Bergel, Microbial catalysis of the oxygen reduction reaction for
microbial fuel cell: a review, ChemSusChem 5 (2012) 975.
10. K. Kinoshita, Carbon: Electrochemical and Physicochemical Properties, John Wiley Sons,
New York, NY, 1988.
11. W. Yang, K.Y. Kim, P.E. Saikaly, B.E. Logan, The impact of new cathode materials
relative to baseline performance of microbial fuel cells all with the same architecture and
solution chemistry, Energy Environ, Sci. 10 (2017) 1025.
12. C. Arbizzani, S. Beninati, E. Manferrari, F. Soavi, M. Mastrangostino, Electrodeposited
PtRu on cryogel carbon-Nafion supports for DMFC anodes, J. Power Sources 161 (2006)
826.
13. C. Santoro, A. Derov, C.W. Narvaez Villiarrubia, S. Stariha, S. Babanova, K. Artyushkova,
A.J. Schuler, P.Atanassov, High catalytic activity and pollutants resistivity using Fe-
AAPyr cathode catalyst for microbial fuel cell application, Sci. Rep. 5 (2015) 16596.
14. C. Santoro, S. Rojas-Carbonell, R. Awais, R. Gokhale, M. Kodali, A. Serov, K.
Artyushkova, P. Atanassov, Influence of platinum group metal-free catalyst synthesis on
microbial fuel cell performance, J. Power Sources 375 (2018) 11.