Journal of Electroanalytical Chemistry 757 (2015) 270–276

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Journal of Electroanalytical Chemistry

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Microbial fuel cell based on Ni-tetra sulfonated phthalocyanine cathodeand graphene modified bioanode

Joffrey Champavert a, Salma Ben Rejeb b, Christophe Innocent a,⁎, Maxime Pontié ba Institut Européen des Membranes, UMR 5635, ENSCM-UMII-CNRS, Place Eugène Bataillon, 34095 Montpellier, Franceb UNAM, Angers University, GEPEA, UMR CNRS 6144, 2Bd. Lavoisier, Angers 49045, France

⁎ Corresponding author.

http://dx.doi.org/10.1016/j.jelechem.2015.09.0121572-6657/© 2015 Elsevier B.V. All rights reserved.

a b s t r a c t

a r t i c l e i n f o

Article history:Received 25 March 2015Received in revised form 18 August 2015Accepted 7 September 2015Available online 12 September 2015

Keywords:Microbial Fuel CellReduced graphene oxidePoly-NiTSPcStainless steelCarbon felt

A Microbial Fuel Cell (MFC) has been constructed using stainless steel modified with reduced graphene oxide(rGO) by layer by layer (LbL) original method as the bioanode and carbon felt modified withpolyNi(II)tetrasulfophthalocyanine (poly-NiTSPc) as the cathode. In this work, an easy method is reported tofabricate a MFC with long time life using compost garden leachate as source of micro-organisms for theelectroactive biofilm. rGO permitted to obtain stable power density over a period of 40 days (24.8 mW/m2 inpresence of pure O2). The cathode presented in this paper allows to obtain a power density 7.5 times higherthan using a Pt cathode.

© 2015 Elsevier B.V. All rights reserved.

1. Introduction

Microbial fuel cells (MFCs) are electrochemical devices which con-vert chemical energy into electricity using micro-organisms as catalyst.Using organic waste for the formation of an electroactive biofilm aswellas a source of substrate is really promising due to the fact it will treatwastes and will harvest energy in the same time [1].

Since anode, as the electron acceptor for the electroactive bacteria,directly interacts with the microorganisms, the selection of high-performance anode materials is of crucial importance in the design ofan MFC [2–4].

Aside from all the other factors affecting the MFC performance,which include cell design, inoculum, substrate, proton exchangemateri-al and electrode surface areas… [5–11], the fabricationmaterials for theanode plays a profound role in influencing the power generation bydetermining the actual accessible area for bacteria to anchor and byaffecting the interfacial electron transfer resistance.

Therefore, a high-performance anode material is essential to im-prove the power outputs of MFCs [12]. However, the cathodic electrodeplays also an important role. Limitation of oxygen reduction can reducethe performance of MFC. Thus, MFC performance is mainly limited bythe cathode [13,14]. Recentworks have been focused on the biocathodefor enzymatic fuel cell [15,16] as well as for MFC [17,18].

In this paper, a graphene modified bioanode has been combinedwith a chemical poly-NiTSPc modified carbon felt cathode in the aim

to fabricate a MFC. Recently, graphene has been considered as theintriguing material, attracting strong scientific and technologicalinterest with great application potentials in various fields, such as lithi-um ion batteries [19], solar cells [20] and electrochemical super-capacitors [21], for its unique nanostructure and extraordinary proper-ties (high surface area [22], excellent conductivity [23], passivation ofbiocorrosion [24] outstanding mechanical strength [25] and extraordi-nary electrocatalytic activities, etc.). Stainless steel foam has beenselected due to its bio-corrosion resistance, its 3-D structure, its porosity(whichmay facilitate the anchor ofmicro-organism) and because itwassuitable for the LbL method contrary to carbon felt which would haveabsorb rGO and PEI instead of having a layer deposition. Also, stainlesssteel foam is a promising material electrode for microbial colonizationas report elsewhere [26]. Moreover, the mechanical resistance of stain-less steel foam is much higher than that of carbon felt. The influence ofsupply of oxygen at the cathode has been investigated as well as thelong time stability of this microbial fuel cell.

2. Experimental

2.1. Chemicals and materials

Graphene oxide (GO) was synthesized from graphite by a modifiedHummers method suspended in MilliQ water [27,28]. Hydrazine andammonia solution (purchased from Fluka) were used to chemicallyreduce GO [29]. rGO obtained had a concentration of 0.25 mg/mL. A 1mg/mL solution of poly(ethyleneimine) (PEI, Aldrich) was prepared inan aqueous solution of 0.5 M NaCl (Fluka).

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Fig. 1. (A) Fabrication's scheme of the anode using LbLmethod, (B) SEM images of blank SSF, (C) SEM images of SSF/(PEI/rGO)5, (D) SEM images of the biofilmon the SSF/(PEI/rGO)5 anodeand (E) SEM images of SSF/(PEI/rGO)5/Biofilm.

271J. Champavert et al. / Journal of Electroanalytical Chemistry 757 (2015) 270–276

Compost garden leachate was made with 1 L of commercial gardencompost (Botanic, France) and 1 L of 60 mM potassium chloride(Fluka). The mixture was stirred for 48 h and was grossly filtered witha sieve in order to remove all solid compost. Potassium acetate (Fulka)was added to the solution previously filtered to obtain a concentration

Fig. 2. Scheme of the two compartments MFC set up.

of 20 mM in the leachate medium. Potassium acetate is thus used asfuel for the fuel cell [30].

Untreated Nafion 117® (Dupont USA) was used as proton exchangemembrane separator between the two compartments of the biofuel cell.

Stainless steel foams (ASI 316) with a surface area of 10 cm2 wereused for experiments.

Pt disc electrode with a surface area of 0.78 cm2 was used forexperiments

Also, all results have been normalized by the geometric surface areaof electrodes in order to compare them.

2.2. Electrochemical measurements

All electrochemical experiments were performed on a SP-50 fromBiologic (France) in a three-electrodes set up, including a working elec-trode, a graphite counter electrode and either an Ag/AgCl (saturatedKCl) or SCE reference electrode. An external resistance (1 kΩ) betweenthe anode and the cathode was used to determine the power outputduring the discharge of the MFC. Data were recorded every 30 minduring the beginning of the discharge until stabilization of the systemand then it was recorded once a day. All experiments were run atroom temperature.

2.3. Field emission gun scanning electron microscopy (FESEM) andScanning electron microscopy (SEM) experiments

The FESEM equipment used is a JSM-6301F from JEOL (AngersUniversity, France). Before analysis, all samples were washed with

Fig. 3. Cyclic voltammograms (scan rate 0.1 V·s−1) of (a) carbon felt in 0.1 M NaOH+ 2 mM NiTSPc (70 cycles) and (b) C/poly-NiTSPc in 0.1 M NaOH (1 cycle).

272 J. Champavert et al. / Journal of Electroanalytical Chemistry 757 (2015) 270–276

ultra-pure water to remove excess of salts deposited. Carbon feltsamples were desiccated and glued to a carbon support. The sampleswere then attached to steel discs with double side-scotch tape andthen covered of an ultra-thin layer of Pt/Pd (4 nm) using an evaporatingtechnique. Beam energywas very low for FESEM analysis (under 3 keV).

The SEM used is a S4800 FEG — HR from Hitachi (MontpellierUniversity, France). Before analysis, all samples were washed withultra-pure water and attached to steel discs with double side-scotchcarbon tape. Then, samples were coated with a thin layer of Pt/Pd(4 nm) using an evaporating technique. Samples with biofilms werepre-treated in order to stabilize bacteria attached to the anode. Sample(cut from the anode) was immersed in 4% glutaraldehyde (Sigma)solution for 4 h. It was then rinsed with de-ionized water for 3 times,followed by dehydration with increasing concentration of ethanol(20%, 40%, 60%, 80% and 98%) for 10 min each times and further rinsedin isoamyl acetate twice (10 min each time). Sample was then dried atCO2-critical point for 3 h [31].

Fig. 4. Current density (J) at−0.8 V vs. SCE versus cycle's number of poly-NiTSPc electro-deposition in 0.1 M KNO3 solution saturated with atmospheric O2.

2.4. Modification and preparation of the anode

Stainless steel foamwasmodified with rGO by a LbL method [32]. Inorder to adsorb the rGO (negatively charged) onto the surface of theelectrode, it is important to form a positive layer on its surface. Thefirst layerwasmadewith the adsorption of PEI (positively chargedpoly-mer) on the surface by soaking the electrode in a solution of PEI (1mg/mL) for 15 min. The electrode was then washed with distilledwater and dried with nitrogen. Thereafter, the electrode was dippedinto the solution of rGO for 15 min too, cleaned with distilled waterand dried with nitrogen. This process was repeated 5 times in the aimof making 5 bilayers of (PEI/rGO). This electrode is thus named SSF/(PEI/rGO)5 as shown in Fig. 1.

The growth of an electroactive biofilm was followed bychronoamperometry with a potentiostat (SP 50 Biologic-France). In athree electrodes system, the working electrode (SSF/(PEI/rGO)5 orSSF) was immersed into a solution composed of compost gardenleachate and sodium acetate (1:1). The potential applied to the counterelectrode (graphite) was -0.246 V vs Ag/AgCl [26] andwas applied for aperiod of 20 days.

2.5. Cathode elaboration

Carbon felt cathodewas first electrochemically pretreated under thefollowing conditions: cyclic voltammetry between 0.0 and 1.2 V vs SCEin 0.1 M NaOH during 10 cycles (scan rate 0.1 V/s). The carbon felt pre-treatment is essential to attain a good reproducibility of the poly-NiTSPcfilm deposition because on one side it helps to eliminate initial impuri-ties and on the other side it prepares the carbon surface to graft oxygento the surface which is very essential to do O–Ni–O bridges. The electro-chemical deposition of poly-NiTSPc was achieved in 0.1 M NaOH and2 mM NiTSPc aqueous solution by repeated potential scans between20 and 140 times, between 0.0 and 1.2 V vs SCE (scan rate 0.1 V/s), inorder to optimize the poly-NiTSPc deposition.

2.6. Microbial fuel cell set up

The MFC set up is divided into two compartments. One is dedicatedto the anode and the other one is for the cathode. Compartments are

Fig. 5. Current-potential curves (scan rate 0.1 V·s−1) of both tested carbon felt cathodes, unmodified and modified poly-NiTSPc 70 cycles (in 0.1 M KNO3 solution saturated with atmo-spheric O2).

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separeted by a Nafion 117© membrane which allows protons to gothrough it from the anodic to the cathodic chamber. On one hand, theanode is immersed into a mixture of compost garden's leachate withsodium acetate (20 mM). On the other hand, the cathode is immersedin a solution of KNO3 0.1 M and either air or oxygen is provided intothe chamber. An external resistance of 1 kΩ is connected to theelectrodes [33] in order to shuttle electrons from the anode to thecathode. A voltameter,with a high enter impedance (10MΩ), is pluggedin parallel to observe the evolution of the voltage (Fig. 2).

3. Results and discussion

3.1. Cyclic voltammetry of poly-NiTSPc elaboration: the elaboration of anovel cathode dedicated to O2 reduction

Cyclic voltammetry deposition of poly-NiTSPc film on the pre-treated carbon felt cathode is shown in Fig. 3. Cyclic voltammetry ofthe modified electrode showed typical electrochemical redox peaks ofpoly-NiTSPc at 0.2 and 0.75 V vs SCE (Fig. 3b) proving the presence ofthe film on the carbon felt surface.

The apparent surface coverage of the film electrode by thetetrasulfonated nickel phthalocyanine can be calculated from the cyclicvoltammogram of the film after transfer of the film, through carefulrinsing, to a fresh alkaline solution containing no monomer. The calcu-lation is based on the charge under the oxidative peak observed at0.75 V/SCE using Faraday's law.

Fig. 6. SEM images of (left) bare carbon f

The effect of the number of poly-NiTSPc electrodeposition cycle'snumber on the oxygen reduction reaction was studied to optimizefirst the cathode performance. It is expected in modifying carbon feltsurface to increase the intensity of oxygen reduction reaction, leadingto an increase in fuel cell performances. The study of catalytic oxygenreduction has been carried out by chronoamperometry at −0.8 V/SCEto allow the comparisonof different electrodematerials. Fig. 4 illustratesthe evolution of the current density obtained at −0.8 V/SCE with thenumber of poly-NiTSPc cycles of electro-deposition.

A maximum in the current density is observed for 70 cycles ofelectrochemical deposition, as illustrated in Fig. 4. The nickel-basedcomplex film thickness can be estimated by taking into account thecalculation of the electrode surface coverage, based on the chargeunder the oxidative or reductive peaks observed at 0.4 V/SCE, and theshape and size of the phthalocyanine macrocycle. In our consideredcase, NiTSPc-based films optimized cathode were prepared either by70 potential scans. This leads to the deposition of 6.1 × 10−8 mol/cm2,this corresponds approximately to a film thickness of 884 nm, as report-ed elsewhere [34–37].

Further experiments have demonstrated a good storage stability ofpoly-NiTSPc film at room temperature during 6 months (results notreported).

Also the poly-NiTSPc film enhances electron transfer between O2and the electrode surface, thus displaying a hypothetic electrocatalyticeffect. For more than 70 cycles the intensity at −0.8 V/SCE decreasedwith a minimum observed for 140 cycles. This evolution suggests

elt and (right) carbon/ poly-NiTSPc.

Fig. 7. Cyclic voltammetry of both electrodes (blank andmodified) without and with bio-film realized in a solution of acetate (20 mM) and KCl (60 mM) at 50 mV/s vs Ag/AgCl.

Fig. 9. Evolution of the current density and the power output of the MFC vs time (thearrow indicates an addition of acetate).

274 J. Champavert et al. / Journal of Electroanalytical Chemistry 757 (2015) 270–276

improved kinetics with increase in polymer thickness but the film po-rosity (nanoporosity suspected) became sufficiently low to limit O2 dif-fusion after 100 cycles.

Considering Fig. 5, the ORR intensity increases two times comparingunmodified carbon felt and modified C/p-NiTSPc, we hypothesis anevolution of a two-electrons mechanism to a 4 electrons but nonedisplacement of the OCP shows the absence of electrocatalytic effect.Furthermore, as illustrated in Fig. 6, poly-NITSPc is covering the fibersof the carbon felt increasing the geometrical surface exposed to O2reduction and this geometrical effect could explain the increase in thereduction current density observed.

The electrodeposition process must be homogeneous on the surfaceand the cycling method is the good way to achieve this aim. Thus, thefilm structure is imposed by the stacking of the complex layers via theinterconnecting oxo-bridges, and does not depend on the electrochem-ical deposition procedure (cyclic voltammetry or controlled potentialelectrolysis). Ureta-Zanatu et al. [38] reported that poly-NiTSPc filmelaborated and cycling in NaOH is in the form of β-Ni(OH)2 very similarto that in nickel hydroxide. A large part of the carbon fibers showmatteraggregates deposit (see Fig. 6b), supposed to be β-Ni(OH)2 clusters andvery recent works developed these previous results, see Ref. [39] andreferences therein.

Fig. 8. (A) Current density evolution of the electrodewith a resistance of 1 kΩ between theworking electrode (either SSF/(PEI/rGO)5 or SSF) and counter electrode. The addition ofacetate is reported through the red arrows. (B) Scheme of the set up.

3.2. Cyclic voltammetry of the anode without biofilm

Blank SSF and SSF/(PEI/rGO)5 electrodes were both characterized bycyclic voltammetry in a solution of acetate (20 mM) and KCl (60 mM)before and after the growth of the biofilm. As shown in Fig. 7, voltam-mograms of the SSF/(PEI/rGO)5 electrode revealed a larger currentresponses compared to the SSF blank electrode in the potential scanrange of−1.0 V to+0.6 V. The increase in the electron transfer efficien-cy can be attributed to the synergic properties of rGO. In addition, thesame behavior is observed with the biofilm onto the surface ofelectrodes. A current increase is observed for both electrodes whenthe biofilm is formed although the current is higher for the modifiedelectrode. The oxidation potential is shifted to the right (higher poten-tial) which shows the acetate oxidation by the biofilm.

3.3. Power output of the anode in one compartment

The SSF/(PEI/rGO)5 electrode was set up in a one compartment cell(compost garden leachate and acetate, 1:1, Fig. 8) with a graphiteelectrode connected to a resistor of 1 kΩ [33] in a two electrode system.The goal of this experiment was to observe the evolution of the currentfor a long period in order to know the stability and the lifetime of this

Fig. 10. Comparison of power density output between the phthalocyanine electrode andthe Pt electrode.

Fig. 11. Bar chart showing the evolution of power output in presence of O2 or without.

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electrode. When the current obtained decreased, acetate was added toprovide fuel to the electrode (mentioned by the arrow on the Fig. 8).

It is shown on the Fig. 8 that the SSF electrode is not able to producecurrent anymore after a period of 18 days even with addition of acetate.Conversely, SSF/(PEI/rGO)5 is still producing current for 30 days.Moreover, the current density observed with SSF/(PEI/rGO)5 is twicehigher than for the SSF electrode. The power obtained after a period of30 days was therefore 21.6 mW/m2. rGO modification is then able totransfer more electron from the electroactive biofilm to the electrodesurface [40] and presents also a better stability and time life than theelectrode without any modifications. This electrode was thereaftercoupled with a Ni-phthalocyanine electrode in a complete MFC.

3.4. Power output of the MFC with membrane

Using a Nafion 117© membrane between the two compartments, aMFCwas built using a phthalocyanine carbon cloth electrode as cathodeand the SSF/(PEI/rGO)5 electrode as anode. The two electrodes wereconnected with a resistance of 1 kΩ in order to follow the evolution ofthe power produce in the time. The reduction of the oxygen occurredat the cathode which consequently implies oxygen supply at thecathodic chamber. This was provided with either ambient air or O2.The evolution of the current density at ambient air is reported in Fig. 9for a period of 40 days.

It is shown that in a first place, there is a large decrease of the currentproduced by the MFC. After the addition of acetate, the current increaseuntil a maximum which is then followed by a slight decrease untilstabilization at around 50 mA/m2.

During the previous experiment, the cathodewas replaced twice (atday 5 and day 21) with an electrode of platinum which is commonlyused for the reduction of O2. It appears (Fig. 10) that the power densityobtained with the phthalocyanine electrode was about 7.5 higher thanwith Platinum electrode in both case (day 5 and day 21).

The supply of oxygen has also been explored by using pure O2instead of ambient air (Fig. 11).

In the presence of O2, the power density output is much higher thanwithout, which is expected. Also, it is shown that the Ni-NiTSPcelectrode catalyzes the oxygen reduction better than Pt at ambient air.The power density values are drastically higher (2.5 times). In bothcase, the stability is conserved after 21 days demonstrating the efficien-cy of this novel MFC.

4. Conclusion

The present work showed for the first time the efficiency of poly-NiTSPc electrodeposited film as a new catalyst for the oxygen reductionreaction in biofuel cell. Furthermore, using rGO modification on the

anode, allowed a better stability of the biofilm due to the morphologymodification at the surface of the anode. Long time stability of both elec-trodes strengthens the idea of investigated in these electrodesmaterialsfor the realization of a larger sizeMFCs. Indeed, this novelMFC provideda power output of 24.8 mW/m2 in presence of pure O2 at the cathodeand 7.2 mW/m2 at ambient air after a period of 40 days.

Acknowledgments

The authors wish to thank IEMMontpellier University for SEM anal-ysis, particularly Didier Cot, and also Cyriaque Bardet, a master studentin Angers University for his precious help.

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Microbial fuel cell based on Ni-tetra sulfonated phthalocyanine cathode and graphene modified bioanode1. Introduction2. Experimental2.1. Chemicals and materials2.2. Electrochemical measurements2.3. Field emission gun scanning electron microscopy (FESEM) and Scanning electron microscopy (SEM) experiments2.4. Modification and preparation of the anode2.5. Cathode elaboration2.6. Microbial fuel cell set up

3. Results and discussion3.1. Cyclic voltammetry of poly-NiTSPc elaboration: the elaboration of a novel cathode dedicated to O2 reduction3.2. Cyclic voltammetry of the anode without biofilm3.3. Power output of the anode in one compartment3.4. Power output of the MFC with membrane

4. ConclusionAcknowledgmentsReferences