A hydrogen utilizing exoelectrogenic bacterium (
Geobacter sulfurreducens) was compared to both a nonhydrogen oxidizer (
Geobacter metallireducens) and a mixed consortium in order to compare the hydrogen production rates and hydrogen recoveries of pure and mixed cultures in microbial electrolysis cells (MECs). At an applied voltage of 0.7 V, both
G. sulfurreducens and the mixed culture generated similar current densities (ca. 160 A/m
3), resulting in hydrogen production rates of ca. 1.9 m
3 H
2/m
3/day, whereas
G. metallireducens exhibited lower current densities and production rates of 110 ± 7 A/m
3 and 1.3 ± 0.1 m
3 H
2/m
3/day, respectively. Before methane was detected in the mixed-culture MEC, the mixed consortium achieved the highest overall energy recovery (relative to both electricity and substrate energy inputs) of 82% ± 8% compared to
G. sulfurreducens (77% ± 2%) and
G. metallireducens (78% ± 5%), due to the higher coulombic efficiency of the mixed consortium. At an applied voltage of 0.4 V, methane production increased in the mixed-culture MEC and, as a result, the hydrogen recovery decreased and the overall energy recovery dropped to 38% ± 16% compared to 80% ± 5% for
G. sulfurreducens and 76% ± 0% for
G. metallireducens. Internal hydrogen recycling was confirmed since the mixed culture generated a stable current density of 31 ± 0 A/m
3 when fed hydrogen gas, whereas
G. sulfurreducens exhibited a steady decrease in current production. Community analysis suggested that
G. sulfurreducens was predominant in the mixed-culture MEC (72% of clones) despite its relative absence in the mixed-culture inoculum obtained from a microbial fuel cell reactor (2% of clones). These results demonstrate that
Geobacter species are capable of obtaining similar hydrogen production rates and energy recoveries as mixed cultures in an MEC and that high coulombic efficiencies in mixed culture MECs can be attributed in part to the recycling of hydrogen into current.Electrohydrogenesis is an efficient method for generating hydrogen gas from organic matter in reactors known as microbial electrolysis cells (MECs) (
17,
18,
26). MECs differ from air-cathode microbial fuel cells (MFCs) in that the cathode remains anaerobic, and voltage is added in order to generate hydrogen at the cathode. Under the biological conditions in MECs, hydrogen evolution is not a thermodynamically favorable reaction. However, combining the hydrogen formation reaction potential of −0.41 V at the cathode (
ECAT) with the anode potential (
EAN) typically obtained in MFCs with an
EAN of −0.30 V (1 g of acetate/liter) results in a minimum required voltage of only 0.14 V. Applied voltages (
EAP) of 0.2 V (0.45 kWh/m
3 H
2) or larger are needed in practice to produce measurable quantities of hydrogen, but this input is substantially less than the average of 2.3 V (5.1 kWh/m
3 H
2) required for water electrolysis (
13).Recent improvements in designs and materials have substantially improved hydrogen yields, production rates, and energy recoveries (
3,
18,
27-
29,
33). Hydrogen recoveries using typical dead-end fermentation end products such as acetate and butyrate have reached 80 to 100%, whereas other complex substrates such as glucose and cellulose have yielded recoveries of ca. 70% (
5). Production rates larger than 6 m
3 H
2/m
3/day have been obtained using MECs (
32), which are similar to an average rate of 2.5 m
3 H
2/m
3/day obtained for hydrogen production by biological fermentation (
10). Energy recoveries relative to the electrical energy input as high as 680% have already been shown (
5), and overall energy recoveries that include the energy of the substrate have reached 85% (
2,
5).Hydrogen losses can occur using a mixed culture in an MEC, reducing hydrogen yields, production rates, and recoveries (
3,
11,
16,
32). Hydrogen recoveries can drop significantly at lower applied voltages in membraneless MECs because of methanogenic consumption of hydrogen (
2,
8,
11,
34). Using a membraneless MEC, Call and Logan (
2) found that the overall hydrogen recovery of 90% at an
EAP of 0.6 V was reduced to 18% at an
EAP of 0.2 V and that methane concentrations increased from 0.9 to 28% in the product gas. Reducing solution pH can help inhibit methanogens, but a methane concentration of 22% was observed in a membrane free MEC at pH 5.8 (
11). When hydrogen is the intended product of an MEC, methane production is detrimental to the process. However, biologically produced methane is a renewable energy source, and membraneless MECs can be used to generate methane instead of hydrogen, although energy recoveries are lower (
8). Hydrogen can also be consumed by chemolithotrophic bacteria in mixed-culture MECs. These bacteria may transfer the associated electrons to a suitable electron acceptor, such as carbon dioxide, and in some cases, the anode. In the latter scenario, the electrons from hydrogen would be recycled internally, causing an increase in coulombic efficiency (
16). Hydrogen losses reduce hydrogen and energy recoveries, and alternative methods for generating methane-free and high hydrogen content gas are needed.Pure culture MECs are one method to avoid losses to methanogens, but production rates and efficiencies with pure cultures can be low compared to those with mixed cultures. Using a pure culture of
Shewanella oneidensis MR-1 and lactate, Hu et al. obtained a hydrogen production rate of 0.025 m
3 H
2/m
3/day at an
EAP of 0.6 V (
11). However, production rates at this same applied voltage using mixed cultures have reached 1 to 2 m
3 H
2/m
3/day (
2,
5). In MFCs,
S. oneidensis has produced low coulombic efficiencies (<10%) (
24,
25) and maximum current densities of ca. 50 mA/m
2 (
15) with lactate, compared to ca. 9,900 mA/m
2 (
9) for mixed cultures.Several
Geobacter species are commonly found in mixed culture MFCs, and tests with pure cultures of
Geobacter sulfurreducens have demonstrated power and current densities close to or equal to those achieved with mixed cultures. In an air cathode MFC,
G. sulfurreducens produced a lower power density (461 mW/m
2, 1.5 A/m
2) than a mixed culture (576 mW/m
2, 1.3 A/m
2) (
12). The reduced performance of
G. sulfurreducens in the air cathode MFC may have been due to oxygen intrusion across the cathode. Using an MFC with a ferricyanide cathode, Nevin et al. (
23) reported a power density of 1.9 W/m
2 (4.6 A/m
2) for
G. sulfurreducens compared to 1.6 W/m
2 (3.2 A/m
2) for a mixed consortium. When the authors placed the
G. sulfurreducens MFC in an anaerobic chamber, the coulombic efficiency improved from 55% to ca. 100%, confirming the importance of strictly anaerobic conditions for
G. sulfurreducens. This suggests that the anaerobic environment of MECs may provide excellent conditions for obtaining current densities comparable to those of mixed cultures with pure cultures of
Geobacter species, while at the same time eliminating methane gas production.In order to investigate the performance of
Geobacter species in MECs, we selected two
Geobacter species based on their differences in hydrogen utilization.
G. sulfurreducens was selected because it is capable of producing high current densities in MFCs, and it can utilize hydrogen.
G. metallireducens, which does not oxidize hydrogen, was examined to determine whether higher hydrogen recoveries were possible with a bacterium that cannot oxidize hydrogen. Both of these cultures were compared to a mixed culture under identical conditions in order to further examine the role of internal hydrogen recycling in MECs and to show that methane-free gas can be produced in MECs at rates comparable to those obtained with mixed cultures.
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