PubMed · 16263496
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David C Holzman. 2005. Microbe power!. https://doi.org/10.1289/ehp.113-a754
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The performance of oxygen reduction catalysts (platinum, pyrolyzed iron(ll) phthalocyanine (pyr-FePc) and cobalt tetramethoxyphenylporphyrin (pyr-CoTMPP)) is discussed in light of their application in microbial fuel cells. It is demonstrated that the physical and chemical environment in microbial fuel cells severely affects the thermodynamics and the kinetics of the electrocatalytic oxygen reduction. The neutral pH in combination with low buffer capacities and low ionic concentrations strongly affect the cathode performance and limit the fuel cell power output. Thus, the limiting current density in galvanodyanamic polarization experiments decreases from 1.5 mA cm(-2) to 0.6 mA cm(-2) (pH 3.3, E(cathode) = 0 V) when the buffer concentration is decreased from 500 to 50 mM. The cathode limitations are superposed by the increasing internal resistance of the MFC that substantially contributes to the decrease of power output. For example, the maximum power output of a model MFC decreased by 35%, from 2.3 to 1.5 mW, whereas the difference between the electrode potentials (deltaE = E(anode) - E(cathode)) decreased only by 10%. The increase of the catalyst load of pyr-FePc from 0.25 to 2 mg cm(-2) increased the cathodic current density from 0.4 to 0.97 mA cm(-2) (pH 7, 50 mM phosphate buffer). The increase of the load of such inexpensive catalyst thus represents a suitable means to improve the cathode performance in microbial fuel cells. Due to the low concentration of protons in MFCs in comparison to relatively high alkali cation levels (ratio C(Na+,K+)/C(H+) = 5 x E5 in pH 7, 50 mM phosphate buffer) the transfer of alkali ions through the proton exchange membrane plays a major role in the charge-balancing ion flux from the anodic into the cathodic compartment. This leads to the formation of pH gradients between the anode and the cathode compartment.
There is a need for alternative catalysts for oxygen reduction in the cathodic compartment of a microbial fuel cell (MFC). In this study, we show that a bipolar membrane combined with ferric iron reduction on a graphite electrode is an efficient cathode system in MFCs. A flat plate MFC with graphite felt electrodes, a volume of 1.2 L and a projected surface area of 290 cm2 was operated in continuous mode. Ferric iron was reduced to ferrous iron in the cathodic compartment according to Fe(3+) + e(-) --> Fe2+ (E0 = +0.77 V vs NHE, normal hydrogen electrode). This reversible electron transfer reaction considerably reduced the cathode overpotential. The low catholyte pH required to keep ferric iron soluble was maintained by using a bipolar membrane instead of the commonly used cation exchange membrane. For the MFC with cathodic ferric iron reduction, the maximum power density was 0.86 W/m2 at a current density of 4.5 A/m2. The Coulombic efficiency and energy recovery were 80-95% and 18-29% respectively.
A miniature-microbial fuel cell (mini-MFC, chamber volume: 1.2 mL) was used to monitor biofilm development from a pure culture of Shewanella oneidensis DSP10 on graphite felt (GF) under minimal nutrient conditions. ESEM evidence of biofilm formation on GF is supported by substantial power density (per device cross-section) from the mini-MFC when using an acellular minimal media anolyte (1500 mW/m2). These experiments demonstrate that power density per volume for a biofilm flow reactor MFC should be calculated using the anode chamber volume alone (250W/m3), rather than with the full anolyte volume. Two oxygen reduction cathodes (uncoated GF or a Pt/vulcanized carbon coating on GF) were also compared to a cathode using uncoated GF and a 50mM ferricyanide catholyte solution. The Pt/C-GF (2-4% Pt by mass) electrodes with liquid cultures of DSP10 produced one order of magnitude larger power density (150W/m3) than bare graphite felt (12W/m3) in this design. These advances are some of the required modifications to enable the mini-MFC to be used in real-time, long-term environmental power generating situations.