Electrochemistry Communications 9 (2007) 17301734 www.elsevier.

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Lead dioxide as an alternative catalyst to platinum in microbial fuel cells

Jerey M. Morris a, Song Jin
a

a,b,*

, Jiaquan Wang b, Chengzhu Zhu b, Michael A. Urynowicz

Western Research Institute, 365 North 9th Street, Laramie, WY 82072, USA b Hefei University of Technology, Hefei, Anhui 230009, PR China c University of Wyoming, Laramie, WY 82071, USA

Received 9 March 2007; received in revised form 29 March 2007; accepted 31 March 2007 Available online 12 April 2007

Abstract Lead dioxide (PbO2) was compared to platinum (Pt) as a cathode catalyst in a double-cell microbial fuel cell (MFC) utilizing glucose as a substrate in the anode chamber. Four types of cathodes were tested in this study including two PbO2 cathodes fabricated using a titanium base with butanol or Naon binders and PbO2 paste, one Pt/carbon cathode fabricated using a titanium base with a carbonPt paste, and a commercially available Pt/carbon cathode made from carbon paper with Pt on one side. The power density and polarization curves were compared for each cathode and cost estimates were calculated. Results indicate the PbO2 cathodes produced between 2 and 4 more power than the Pt cathodes. Furthermore, the PbO2 cathodes produced between 2 and 17 more power per initial fabrication or purchase cost than the Pt cathodes. This study suggests that cathode designs that incorporate PbO2 instead of Pt could possibly improve the feasibility of scaling up MFC designs for real world applications by improving power generation and lowering production cost. 2007 Elsevier B.V. All rights reserved.
Keywords: Alternative energy; Catalyst; Cathode; Lead dioxide; Microbial fuel cells

1. Introduction A microbial fuel cell (MFC) is a device that generates electrical power by harnessing the oxidizing potential of anaerobic bacteria through an external circuit. In MFCs, bacteria utilize a solid-state terminal electron acceptor (anode) and electrons ow through an external circuit to a cathode where oxygen is reduced to water and electrons are consumed, thus, generating power. Maximum power production in an MFC is inuenced by many factors including cell design, microbial species, microbial activity, substrate composition and concentration, and temperature [16]. One of the most important factors inuencing power production is the cathode catalyst, which drives oxygen
* Corresponding author. Address: Western Research Institute, 365 North 9th Street, Laramie, WY 82072, USA. Tel.: +1 307 721 2404; fax: +1 307 721 2256. E-mail address: sjin@uwyo.edu (S. Jin).

reduction and, therefore, directly inuences the electrical current produced in the external circuit. The most commonly used and one of the most eective catalysts is platinum (Pt) [7]. Although power production is much higher when using Pt or other materials such as cobalt tetramethylphenylporphyrin (CoTTMP) as catalysts in MFCs [8] as compared to not using a catalyst, the cost of using these materials may be prohibitive to scaling up MFC designs for large applications such as municipal wastewater treatment. Therefore, there is a need for catalyst materials that perform at a comparable level to Pt but cost substantially less [7]. We hypothesized that lead dioxide (PbO2) could adequately replace Pt as a catalyst on the cathode given the successful substitution of PbO2 for Pt on anodes in many electrochemical applications (e.g., [9,10]). The purpose of this experiment was to compare the performance of Pt to PbO2 as a catalyst material on the cathode in an MFC device. To avoid signal interference due to galvanic reactions and system disturbance due to opening working cells,

1388-2481/$ - see front matter 2007 Elsevier B.V. All rights reserved. doi:10.1016/j.elecom.2007.03.028

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a double-cell MFC was established to compare the performance of PbO2 and Pt as cathode catalysts. 2. Experimental
RSB

2.1. Cathode fabrication Four dierent cathodes were tested in these experiments. The rst two cathodes were made by smearing a PbO2paste (0.65 g PbO2; Fisher Scientic, S75147) mixed with 0.5 ml of either 1-butanol (SigmaAldrich, 360465) or Naon peruorinated ion-exchange resin (Naon; SigmaAldrich, 274704) on both sides of a 16-cm2 piece of 0.02-inch thick titanium (Ti) sheeting (McMasterCarr, 9051K37). These two cathodes are referred to hereafter as PbO2/Ti (butanol) and PbO2/Ti (Naon). The third cathode was made by smearing a carbonPt paste on both sides of a 16-cm2 piece of Ti (as with the rst two cathodes). The paste for this cathode was made with 0.08 g of Vulcan XC72 carbon black with 10% Pt (E-TEK Division, C1-10 with 10% HP Pt) and 0.5 ml of Naon resulting in 0.25 mg Pt/ cm2 of cathode. This cathode is referred to hereafter as PtC/Ti (Naon). These cathodes were allowed to air dry overnight, after applying the respective paste mixtures. The fourth cathode was a 16-cm2 piece of a commercially available phosphoric acid fuel cell electrode on toray carbon paper (E-TEK Division, A3STDSI, 0.35 mg Pt/cm2), which had Pt on one side only (referred to hereafter as commercial cathode). 2.2. Bacterial culture and growth media 2.4. Cathode performance The MFC was inoculated with a mixed bacterial culture indigenous to the local municipal wastewater treatment plant in Laramie, WY, USA. The anode and cathode chambers of the double-cell MFC were lled with a phosphate buer media [11] that had been boiled for 30 min and gassed with nitrogen. The anode chamber contained 500 mg glucose/L as a substrate. 2.3. Microbial fuel cell design A double-cell MFC (Fig. 1) was constructed using two 450-ml glass jars with a silicone-coated lid on the anode chamber and no lid on the cathode chamber. The cathode chamber was lled with 450 ml of sterile phosphate buer with no substrate. A carbon-cloth anode (5 10 cm; ETEK Division, B-1/B, no wet-proong) was placed inside the anode chamber and one edge was draped over the edge of the chamber with the lid threaded over the anode so that part of the anode was outside of the chamber for external circuit attachment. The two chambers were connected with a 45-cm proton bridge. This bridge was made using 0.5inch inner-diameter vinyl tubing, which was lled with a warm mixture containing 3.75 M KCl (SigmaAldrich, P3911) and 3% non-nutrient agar (by weight; Difco Laboratories, 0140-01) in deionized water [11] that was allowed The rst three cathodes with a Ti base were only submerged halfway; therefore, only 16 cm2 of the 32-cm2 cathode (double-sided) was used. The commercial cathode was submerged fully (except for the point of contact with the alligator clip) because this cathode only had Pt coating on one side, therefore, the same catalytic surface area (16 cm2) was submerged for all cathodes. Maximum power generation was determined for each cathode by measuring voltage across a series of dierent resistances with a multimeter. The external resistance was varied from 50,000 X to 50 X and then back up to 50,000 X using a resistor substitution box (Model RS-500, Elenco Electronics Inc., Wheeling, IL, USA). Voltage readings were allowed to stabilize for approximately 1 min between each reading and power density and polarization curves were generated for each cathode using the average value measured at each resistance (n = 2) [7]. Data was collected for all cathodes on the same MFC within 1.5 h in the following order: PbO2/Ti (Naon), PtC/Ti (Nafion), PbO2/Ti (butanol), and commercial cathode. 2.5. Cathode cost estimates General cost estimates were made for each of the three Ti-based cathodes based on the retail cost of the materials
Anode Cathode

Fig. 1. Schematic drawing of a double-cell microbial fuel cell with a sealed anode chamber and an open cathode chamber. A carbon-cloth anode (dashed line) was connected to a resistor substitution box (RSB), which was connected to various cathodes that were being tested (hatched box). To avoid galvanic reactions the anode and cathode were connected to the RSB externally and these connection points were not submerged in the phosphate buer solution (dotted area) in each chamber. The anode and cathode chambers were also connected with a proton bridge (dotted line).

to cool and solidify in the tube. The bridge was inserted through a hole in the lid of the anode chamber and sealed with silicone to maintain anaerobic conditions. The anode was connected externally to the cathode with a 20-gauge copper wire attached to stainless steel alligator clips on each end. The alligator clips attached to the cathode and anode did not come into contact with the solution in each chamber at any time. This design enabled us to quickly switch between dierent cathode types without disturbing the system so that each cathode could be compared on the same MFC within minutes.

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Table 1 Cost of materials used to build various cathodes for performance comparison in a double-cell microbial fuel cell Material PbO2 (powder) CPt (powder) 1-Butanol (liquid) Naon (liquid) 0.020-in. Ti sheet
a b c d

Quantity 100 g 5g 1.0 L 0.1 L 0.56 m2

Cost ($) 8.75 89.30 39.20 295.00 214.29

Distributor Fisher Scientica E-TEKb Sigmac Sigma McMasterCarrd

Catalog # S75147 C1-10 360465 274704 9051K37

Amount used per cm2 20.3 mg 2.5 mg 15.6 ll 15.6 ll 0.5 cm2 (double-sided)

Cost ($)/ cm2 0.0018 0.0447 0.0006 0.0460 0.0102

Fisher Scientic International, www.shersci.com. E-TEK Division, www.etek-inc.com. SigmaAldrich, www.sigma-aldrich.com. McMasterCarr, www.mcmaster.com.

Power density (mW/m2 cathode)

used to manufacture each cathode (Table 1). The cost of the commercial cathode was simply the retail cost, which was $1.46/cm2 (a 900-cm2 sheet = $1310.09). 3. Results 3.1. Cathode performance The PbO2/Ti (butanol) and PbO2/Ti (Naon) cathodes generated nearly equal power (77 and 78 mW/m2 cathode, respectively), which was 1.73.9 more power than the PtC/Ti (Naon) or commercial cathodes, respectively (Table 2). The PbO2/Ti (butanol) and PbO2/Ti (Naon) cathodes also had similar optimal external resistances (2000 X; Table 2), evident from their power density curves (Fig. 2a), and they had similar values of internal resistance (1963 X and 1804 X, respectively; Table 2) calculated from their polarization curves (Fig. 2b). 3.2. Cathode cost estimates The total cost of materials used to manufacture the double-sided, 16-cm2 PbO2/Ti (butanol), PbO2/Ti (Naon), and PtC/Ti (Naon) cathodes was $0.40, $1.85, and $3.23, respectively but only half of the electrode was submerged, therefore, the cost of the eective surface area for each of these cathodes was only $0.20, $0.93, and $1.61, respectively. The cost for the 16-cm2 commercial cathode was $23.36. To get a sense of the relative cost of power generation using the dierent types of cathodes, the power produced using each cathode was normalized

a
80 60 40 20 0 0.00 1.0 0.8 0.6 0.4 0.2 0.0 0.00

0.01

0.02

0.03

0.04

b
Cell voltage (V)

0.01

0.02
2

0.03

0.04

Current density (mA/cm cathode)

Fig. 2. Power density (a) and polarization (b) curves for various cathodes described in the text including: PbO2/Ti (butanol; s), PbO2/Ti (Naon; }), PtC/Ti (Naon; n), and a commercial cathode (h). These curves were generated by measuring cell potential across various resistances ranging from 50 X to 50,000 X (current was calculated using V = I R).

Table 2 Relative performance of various cathodes in a double-cell microbial fuel cell Cathode material PbO2/Ti (butanol) PbO2/Ti (Naon) PtC/Ti (Naon) Commercial cathodea
a b

Optimal external resistance (X) 2000 2000 3000 2000

Calculated internal resistance (X) 1963 1804 2040 2214

Maximum power (mW/m2 cathode) 77 78 45 20

Power per cost of cathode materials (lW/$) 612.0 134.0 45.0 1.4b

E-TEK Division, A3STDSI, 0.35 mg Pt/cm2, www.etek-inc.com. Calculation based on retail cost and not just the cost of materials.

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by the cost of the eective surface area of each, which was 16 cm2. The PbO2/Ti (butanol) cathode produced the most power per dollar (612 lW/$) followed by the PbO2/Ti (Naon; 134 lW/$), PtC/Ti (Naon; 45 lW/$), and the commercial cathode (1.4 lW/$). 4. Discussion The MFC design used in this study was not intended to maximize power generation as it is well known that singlecell MFCs with air cathodes can produce as much as 1020 more power (e.g., [5]) than the 78 mW/m2 attained during this study using double-cell MFCs with aqueous cathodes; however, our double-cell design allowed us to compare various cathode materials on a working MFC under the same conditions within a very short time frame. The reason PbO2 was tested as a substitute for Pt was primarily due to cost; we did not expect the PbO2 cathodes to out-perform the Pt cathodes. Interestingly, using PbO2 as a catalyst rather than Pt on the same base material (Ti) produced 1.7 more power and cost approximately half as much per unit power. Furthermore, the PbO2 cathodes produced 3.9 more power than the commercial Pt cathode. It is dicult to compare the cost per unit power between the Ti-based cathodes we manufactured and the commercial Pt cathode because we do not know the cost of materials for this product. Although the power measurements are straightforward, the cost estimates are conservative when considering that the cost for materials for the PtC/Ti (Naon) cathode was 1.7 higher than the PbO2/Ti (Naon) cathode and 8 higher than the PbO2/Ti (butanol) cathode. Furthermore, the overall costs of producing these cathodes could possibly be reduced by using stainless steel instead of Ti, a dierent binding solution or process other than expensive Naon, and producing cathodes in larger quantities to decrease labor costs. The one factor that cannot be significantly reduced is the cost of the Pt catalyst versus the PbO2 catalyst. In fact, the amount of Pt catalyst powder used on the PtC/Ti (Naon) cathode cost 25 more than the amount of PbO2 powder used on the PbO2/Ti cathodes even though we used 8 more PbO2 powder per cathode than Pt powder. One promising catalyst that was not tested was CoTMPP, which can produce power densities similar to Pt-catalyst cathodes. Cheng et al. [8] demonstrated that CoTMPP-catalyst cathodes (0.6 mg CoTMPP/cm2) produced 88% as much power as the Pt-catalyst cathodes (0.5 mg Pt/cm2). This is signicant because, like PbO2, CoTMPP is substantially less expensive than Pt. However, at this loading rate (0.6 mg CoTMPP/cm2), the CoTMPP would still cost >6 more per cm2 ($20.26/g, Acros Organics, 405340050) than PbO2, even though we used 34 PbO2/ cm2 on our Ti-based cathodes. Finally, it has not yet been determined if decreasing the loading rate of PbO2 signicantly aects power generation, if not, the cost of using this material could drop even lower.

The long-term stability of PbO2 as a cathode catalyst in an MFC compared to Pt is not yet known. However, anodes made with various base materials (e.g., graphite, Ti, stainless steel) that have been chemically or electrochemically coated with PbO2 have been successfully employed in the electrochemical preparation and oxidation of chemicals such as chlorates and perchlorates [12], chromium(III) [9], and in the chemical oxidation of wastewater [10,13] instead of more expensive Pt-coated electrodes. This is very reassuring because the environment in many electrochemical cells is very corrosive and much harsher than any environment these electrodes would likely encounter in an MFC application. 5. Conclusions The purpose of this project was only to compare PbO2 and Pt as catalysts in an MFC and the results of this investigation have subsequently demonstrated the superior performance of PbO2 as a catalyst and highlighted the potential value of this material in commercial MFC applications. However, due to the potential for Pb leaching from the PbO2 cathodes, various other methods and binders are currently being tested to stabilize this material on the cathode and prevent dissolution of Pb into cathode chamber solutions. Considering the superior power generation and lower cost of the PbO2 cathode, it appears that this technology could potentially improve the feasibility of scaling up current MFC designs for eld applications such as municipal wastewater treatment and bioremediation of contaminated groundwater. Acknowledgements The authors thank Huang Min (Hefei University of Technology, China) for assistance in developing the method to fabricate lead dioxide cathodes. Financial support for this research was provided by the United States Department of Energy (DoE) through WRIs Cooperative Agreement No. DE-FC26-98FT40322 with DoE. Any opinions, ndings, conclusions, or recommendations expressed herein are those solely of the authors. References
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