High hydrogen production rate of microbial electrolysis cell (MEC) with reduced electrode spacing

Practical applications of microbial electrolysis cells (MECs) require high hydrogen production rates and a compact reactor. These goals can be achieved by reducing electrode spacing but high surface area anodes are needed. The brush anode MEC with electrode spacing of 2 cm had a higher hydrogen production rate and energy efficiency than an MEC with a flat cathode and a 1-cm electrode spacing. The maximum hydrogen production rate with a 2 cm electrode spacing was 17.8 m(3)/m(3)d at an applied voltage of E(ap)=1 V. Reducing electrode spacing increased hydrogen production rates at the lower applied voltages, but not at the higher (>0.6 V) applied voltages. These results demonstrate that reducing electrode spacing can increase hydrogen production rate, but that the closest electrode spacing do not necessarily produce the highest possible hydrogen production rates.     

微生物电解池阳极生物膜功能菌群构建及群落特征分析

【目的】微生物电解电池(MEC)是近几年快速发展的利用电极呼吸微生物快速降解有机质,通过较小的辅助外加电压直接生成氢气的新工艺。MEC能够有效地富集高效率电子传递功能菌群,是未来工艺放大和快速启动的关键。【方法】采用不同驯化方法构建MEC电极微生物菌群,通过单链构象多肽性技术(Single-strand conformation poly-morphism,SSCP)快速检测分析启动后电子传递功能菌群特征。【结果】阳极生物膜接种MEC可以实现2 d的快速启动,库仑效率达到20%以上,7 d获得稳定产氢,氢气转化率达到30%,能量回收效率达到90%以上。通过SSCP群落分析发现,采用微生物燃料电池阳极生物膜构建的MEC主要电子传递功能相关的菌群包括Pseudomonas sp.、Flavobacterium sp.、Ochrobactrum sp.,而直接由产氢MEC阳极生物膜新启动的MEC功能菌群组成丰度更大,包括电子传递效能更高的Desulfovibrio、Pseudomonas和Shewanella成为主要优势电子传递菌群。通过稳定产氢运行,MEC阳极生物膜优势菌群中存在的较大比例的厌氧菌与电子传递辅助菌对体系的快速稳定运行十分重要。【结论】与MFC阳极生物膜相比,MEC生物膜作为启动菌源能够获得多样性更丰富的电极功能菌群,其库仑效率和产氢效率更具优势。     

Acetate enhances startup of a H₂-producing microbial biocathode

H(2) can be produced from organic matter with a microbial electrolysis cell (MEC). To decrease MEC capital costs, a cathode is needed that is made of low-cost material and produces H(2) at high rate. A microbial biocathode is a low-cost candidate, but suffers from a long startup and a low H(2) production rate. In this study, the effects of cathode potential and carbon source on microbial biocathode startup were investigated. Application of a more negative cathode potential did not decrease the startup time of the biocathode. If acetate instead of bicarbonate was used as carbon source, the biocathode started up more than two times faster. The faster startup was likely caused by a higher biomass yield for acetate than for bicarbonate, which was supported by thermodynamic calculations. To increase the H(2) production rate, a flow through biocathode fed with acetate was investigated. This biocathode produced 2.2 m(3) H(2) m(-3) reactor day(-1) at a cathode potential of -0.7 V versus NHE, which was seven times that of a parallel flow biocathode of a previous study.     

Enhancement of hydrogen production in a single chamber microbial electrolysis cell through anode arrangement optimization

Reducing the inner resistances is crucial for the enhancement of hydrogen generation in microbial electrolysis cells (MECs). This study demonstrates that the optimization of the anode arrangement is an effective strategy to reduce the system resistances. By changing the normal MEC configuration into a stacking mode, namely separately placing the contacted anodes from one side to both sides of cathode in parallel, the solution, biofilm and polarization resistances of MECs were greatly reduced, which was also confirmed with electrochemical impedance spectroscopy analysis. After the anode arrangement optimization, the current and hydrogen production rate (HPR) of MEC could be enhanced by 72% and 118%, reaching 621.3 ± 20.6 A/m³ and 5.56 m³/m³ d respectively, under 0.8 V applied voltage. A maximum current density of 1355 A/m³ with a HPR of 10.88 m³/m³ d can be achieved with 1.5 V applied voltage.     

Relating MEC population dynamics to anode performance from DGGE and electrical data

The microbial electrolysis cell (MEC) is a promising system for H₂ production, but little is known about the active microbial population in MEC systems. Therefore, the microbial community of five different MEC graphite felt anodes was analyzed using denaturing gradient gel electrophoresis (DGGE) profiling. The results showed that the bacterial population was very diverse and there were substantial differences between microorganisms in anolyte and anode samples. The archaeal population in the anolyte and at the anodes, and between the different MEC anodes, was very similar. SEM and FISH imaging showed that Archaea were mainly present in the spaces between the electrode fibers and Bacteria were present at the fiber surface, which suggested that Bacteria were the main microorganisms involved in MEC electrochemical activity. Redundancy analysis (RDA) and QR factorization-based estimation (QRE) were used to link the composition of the bacterial community to electrochemical performance of the MEC. The operational mode of the MECs and their consequent effects on current density and anode resistance on the populations were significant. The results showed that the community composition was most strongly correlated with current density. The DGGE band mostly correlated with current represented a Clostridium sticklandii strain, suggesting that this species had a major role in current from acetate generation at the MEC anodes. The combination of RDA and QRE seemed especially promising for obtaining an insight into the part of the microbial population actively involved in electrode interaction in the MEC.     

Insights in the anode chamber influences on cathodic bioelectromethanogenesis – systematic comparison of anode materials and anolytes

Cathode and catholyte are usually optimized to improve microbial electrosynthesis process, whereas the anodic counter reaction was not systematically investigated and optimized for these applications yet. Nevertheless, the anolyte and especially the anode material can limit the cathodic bioelectrochemical process. This paper compares for the first time the performance of different anode materials as counter electrodes for a cathodic bioelectrochemical process, the bioelectromethanogenesis. It was observed that depending on the anode material the cathodic methane production varies from 0.96 µmol/d with a carbon fabric anode to 25.44 µmol/d with a carbon felt anode of the same geometrical surface area. The used anolyte also affected the methane production rate at the cathode. Especially, the pH of the anolyte showed an impact on the system; an anolyte with pH 5 produced up to 2.0 times more methane compared to one with pH 8.5. The proton availability is discussed as one reason for this effect. Although some of the measured effects cannot be explained completely so far this study advises researchers to strongly consider the anode impact during process development and optimization of a cathodic bioelectrochemical synthesis process.     

Enhancing substrate utilization and power production of a microbial fuel cell with nitrogen-doped carbon aerogel as cathode catalyst

Objectives

Catalytic efficiency of a nitrogen-doped, mesoporous carbon aerogel cathode catalyst was investigated in a two-chambered microbial fuel cell (MFC) applying graphite felt as base material for cathode and anode, utilizing peptone as carbon source.

Results

This mesoporous carbon aerogel containing catalyst layer on the cathode increased the maximum power density normalized to the anode volume to 2.7 times higher compared to the maximum power density obtained applying graphite felt cathode without the catalyst layer. At high (2 and 3) cathode/anode volume ratios, maximum power density exceeded 40 W m^?3. At the same time, current density and specific substrate utilization rate increased by 58% resulting in 31.9 A m^?3 and 18.8 g COD m^?3 h^?1, respectively (normalized to anode volume). Besides the increase of the power and the rate of biodegradation, the investigated catalyst decreased the internal resistance from the range of 450–600 to 350–370 Ω.

Conclusions

Although Pt/C catalyst proved to be more efficient, a considerable decrease in the material costs might be achieved by substituting it with nitrogen-doped carbon aerogel in MFCs. Such cathode still displays enhanced catalytic effect.

     

Integrated hydrogen production process from cellulose by combining dark fermentation, microbial fuel cells, and a microbial electrolysis cell

Hydrogen gas production from cellulose was investigated using an integrated hydrogen production process consisting of a dark fermentation reactor and microbial fuel cells (MFCs) as power sources for a microbial electrolysis cell (MEC). Two MFCs (each 25 mL) connected in series to an MEC (72 mL) produced a maximum of 0.43 V using fermentation effluent as a feed, achieving a hydrogen production rate from the MEC of 0.48 m³ H₂/m³/d (based on the MEC volume), and a yield of 33.2 mmol H₂/g COD removed in the MEC. The overall hydrogen production for the integrated system (fermentation, MFC and MEC) was increased by 41% compared with fermentation alone to 14.3 mmol H₂/g cellulose, with a total hydrogen production rate of 0.24 m³ H₂/m³/d and an overall energy recovery efficiency of 23% (based on cellulose removed) without the need for any external electrical energy input.     

Power output and columbic efficiencies from biofilms of Geobacter sulfurreducens comparable to mixed community microbial fuel cells

It has been previously noted that mixed communities typically produce more power in microbial fuel cells than pure cultures. If true, this has important implications for the design of microbial fuel cells and for studying the process of electron transfer on anode biofilms. To further evaluate this, Geobacter sulfurreducens was grown with acetate as fuel in a continuous flow 'ministack' system in which the carbon cloth anode and cathode were positioned in close proximity, and the cation-selective membrane surface area was maximized in order to overcome some of the electrochemical limitations that were inherent in fuel cells previously employed for the study of pure cultures. Reducing the size of the anode in order to eliminate cathode limitation resulted in maximum current and power densities per m(2) of anode surface of 4.56 A m(-2) and 1.88 W m(-2) respectively. Electron recovery as current from acetate oxidation was c. 100% when oxygen diffusion into the system was minimized. This performance is comparable to the highest levels previously reported for mixed communities in similar microbial fuel cells and slightly higher than the power output of an anaerobic sludge inoculum in the same ministack system. Minimizing the volume of the anode chamber yielded a volumetric power density of 2.15 kW m(-3), which is the highest power density per volume yet reported for a microbial fuel cell. Geobacter sulfurreducens formed relatively uniform biofilms 3-18 mum thick on the carbon cloth anodes. When graphite sticks served as the anode, the current density (3.10 A m(-2)) was somewhat less than with the carbon cloth anodes, but the biofilms were thicker (c. 50 mum) with a more complex pillar and channel structure. These results suggest that the previously observed disparity in power production in pure and mixed culture microbial fuel cell systems can be attributed more to differences in the fuel cell designs than to any inherent superior capability of mixed cultures to produce more power than pure cultures.     

Two-phase partitioning bioreactors in environmental biotechnology

Operation of microbial electrolysis cells (MECs) without an ion exchange membrane could help to lower the construction costs while lowering the ohmic cell resistance and improving MEC conversion rates by minimizing the pH gradient between anode and cathode. In this research, we demonstrate that membraneless MECs with plain graphite can be operated for methane production without pH adjustment and that the ohmic cell resistance could be lowered with approximately 50% by removing the cation exchange membrane. As a result, the current production increased from 66 ± 2 to 156 ± 1 A m⁻³ MEC by removing the membrane with an applied voltage of −0.8 V. Methane was the main energetic product despite continuous operation under carbonate-limited and slightly acidified conditions (pH 6.1–6.2). Our results suggest that continuous production of hydrogen in membraneless MECs will be challenging since methane production might not be avoided easily. The electrical energy invested was not always completely recovered under the form of an energy-rich biogas; however, our results indicate that membraneless MECs might be a viable polishing step for the treatment of the effluent of anaerobic digesters as methane was produced under low organic loading conditions and at room temperature. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Petroleum desulfurization byDesulfovibrio desulfuricans M6 using electrochemically supplied reducing equivalent

Summary Desulfovibrio desulfuricans M6 selected for its ability to degrade dibenzothiophene was cultured in an electrochemical cell system. The ratio of carbon dioxide production to that of hydrogen sulfide was 2.13 in the control culture, whilst the ratios of the cultures made in the cathode compartment and the anode compartment were 1.54 and 3.13, respectively. WhenD. desulfurican M6 was incubated in a sulfate-free medium C with Kuwait crude oil and methyl viologen as an electron mediator in the cathode compartment, the sulfur content of crude oil was decreased with the production of hydrogen sulfide.     

利用微生物电解池处理牛奶废水过程中产电菌落与产氢性能之间的关系

【目的】 研究微生物电解池(Microbial electrolysis cell, MEC)利用复杂有机物作为底物的运行特性, 对其在废水处理中的应用有着重要的意义。【方法】 以模拟牛奶废水为基质, 通过构建MEC反应器来考察在不同外加电压条件下产电菌群的性能。【结果】 当外加电压升高到1.2 V时, 最大电流密度可达到261 A/m3, 产氢速率可达0.048 m3 H2/m3 d, 分别比外加电压为0.4 V的情形提高了467%和700%。外加电压为1.2 V时, 系统对COD和蛋白质去除率可分别达59%和74%, 其中COD去除较之0.4 V的情形提高了22.5%。PCR-DGGE的分子生物学分析结果表明, 阳极生物膜中以Geobacter sp.作为优势菌, 说明在利用大分子有机物作为基质时产电菌与非产电菌的协同作用更为明显。【结论】 MEC能够利用牛奶废水作为燃料, 在实现高效降解的同时以产氢的形式进行能量产出, 这为MEC的实际应用提供了研究思路。     

Analysis of the microbial community of the biocathode of a hydrogen-producing microbial electrolysis cell

The microbial electrolysis cell (MEC) is a promising system for hydrogen production. Still, expensive catalysts such as platinum are needed for efficient hydrogen evolution at the cathode. Recently, the possibility to use a biocathode as an alternative for platinum was shown. The microorganisms involved in hydrogen evolution in such systems are not yet identified. We analyzed the microbial community of a mixed culture biocathode that was enriched in an MEC bioanode. This biocathode produced 1.1 A m⁻² and 0.63 m³ H₂ m⁻³ cathode liquid volume per day. The bacterial population consisted of 46% Proteobacteria, 25% Firmicutes, 17% Bacteroidetes, and 12% related to other phyla. The dominant ribotype belonged to the species Desulfovibrio vulgaris. The second major ribotype cluster constituted a novel taxonomic group at the genus level, clustering within uncultured Firmicutes. The third cluster belonged to uncultured Bacteroidetes and grouped in a taxonomic group from which only clones were described before; most of these clones originated from soil samples. The identified novel taxonomic groups developed under environmentally unusual conditions, and this may point to properties that have not been considered before. A pure culture of Desulfovibrio strain G11 inoculated in a cathode of an MEC led to a current development from 0.17 to 0.76 A m⁻² in 9 days, and hydrogen gas formation was observed. On the basis of the known characteristics of Desulfovibrio spp., including its ability to produce hydrogen, we propose a mechanism for hydrogen evolution through Desulfovibrio spp. in a biocathode system.     

Expression of serotonin derivative synthetic genes on a single self-processing polypeptide and the production of serotonin derivatives in microbes

Soils are rich in organics, particularly those that support growth of plants. These organics are possible sources of sustainable energy, and a microbial fuel cell (MFC) system can potentially be used for this purpose. Here, we report the application of an MFC system to electricity generation in a rice paddy field. In our system, graphite felt electrodes were used; an anode was set in the rice rhizosphere, and a cathode was in the flooded water above the rhizosphere. It was observed that electricity generation (as high as 6 mW/m², normalized to the anode projection area) was sunlight dependent and exhibited circadian oscillation. Artificial shading of rice plants in the daytime inhibited the electricity generation. In the rhizosphere, rice roots penetrated the anode graphite felt where specific bacterial populations occurred. Supplementation to the anode region with acetate (one of the major root-exhausted organic compounds) enhanced the electricity generation in the dark. These results suggest that the paddy-field electricity-generation system was an ecological solar cell in which the plant photosynthesis was coupled to the microbial conversion of organics to electricity.     

Long-term performance of a plant microbial fuel cell with Spartina anglica

The plant microbial fuel cell is a sustainable and renewable way of electricity production. The plant is integrated in the anode of the microbial fuel cell which consists of a bed of graphite granules. In the anode, organic compounds deposited by plant roots are oxidized by electrochemically active bacteria. In this research, salt marsh species Spartina anglica generated current for up to 119 days in a plant microbial fuel cell. Maximum power production was 100 mW m⁻² geometric anode area, highest reported power output for a plant microbial fuel cell. Cathode overpotential was the main potential loss in the period of oxygen reduction due to slow oxygen reduction kinetics at the cathode. Ferricyanide reduction improved the kinetics at the cathode and increased current generation with a maximum of 254%. In the period of ferricyanide reduction, the main potential loss was transport loss. This research shows potential application of microbial fuel cell technology in salt marshes for bio-energy production with the plant microbial fuel cell.     

Characterization of microbial communities during anode biofilm reformation in a two-chambered microbial electrolysis cell (MEC)

GeoChip (II) and single strand conformation polymorphism (SSCP) were used to characterize anode microbial communities of a microbial electrolysis cell (MEC). Biofilm communities, enriched in a two-chamber MEC (R1, 0.6 V applied) having a coulombic efficiency (CE) of 35±4% and a hydrogen yield (Y(H?))of 31±3%, were used as the inoculum for a new reactor (R2). After three months R2 achieved stable performance with CE=38±4% and (Y(H?)). Few changes in the predominant populations were observed from R1 to R2. Unlike sludge inoculation process in R1 in the beginning, little further elimination was aroused by community competitions in anode biofilm reformation in R2. Functional genes detection of biofilm indicated that cytochrome genes enriched soon in new reactor R2, and four genera (Desulfovibrio, Rhodopseudomonas, Shewanella and Geobacter) were likely to contribute to exoelectrogenic activity. This work also implied that symbiosis of microbial communities (exoelectrogens and others) contribute to system performance and stability.     

Treatment of biodiesel production wastes with simultaneous electricity generation using a single-chamber microbial fuel cell

Biodiesel production through transesterification of lipids generates large quantity of biodiesel waste (BW) containing mainly glycerin. BW can be treated in various ways including distillation to produce glycerin, use as substrate for fermentative propanediol production and discharge as wastes. This study examined microbial fuel cells (MFCs) to treat BW with simultaneous electricity generation. The maximum power density using BW was 487 ± 28 mW/m² cathode (1.5 A/m² cathode) with 50 mM phosphate buffer solution (PBS) as the electrolyte, which was comparable with 533 ± 14 mW/m² cathode obtained from MFCs fed with glycerin medium (COD 1400 mg/L). The power density increased from 778 ± 67 mW/m² cathode using carbon cloth to 1310 ± 15 mW/m² cathode using carbon brush as anode in 200 mM PBS electrolyte. The power density was further increased to 2110 ± 68 mW/m² cathode using the heat-treated carbon brush anode. Coulombic efficiencies (CEs) increased from 8.8 ± 0.6% with carbon cloth anode to 10.4 ± 0.9% and 18.7 ± 0.9% with carbon brush anode and heat-treated carbon brush anode, respectively.     

Enhanced butanol production in a microbial electrolysis cell by <Emphasis Type="Italic">Clostridium beijerinckii</Emphasis> IB4

Reducing power such as NADH is an essential factor for acetone/butanol/ethanol (ABE) fermentation using Clostridium spp. The objective of this study was to increase available NADH in Clostridium beijerinckii IB4 by a microbial electrolysis cell (MEC) with an electron carrier to enhance butanol production. First of all, a MEC was performed without electron carrier to study the function of cathodic potential applying. Then, various electron carriers were tested, and neutral red (NR)-amended cultures showed an increase of butanol concentration. Optimal NR concentration (0.1 mM) was used to add in a MEC. Electricity stimulated the cell growth obviously and dramatically diminished the fermentation time from 40 to 28 h. NR and electrically reduced NR improved the final butanol concentration and inhibited the acetone generation. In the MEC with NR, the butanol concentration, yield, proportion and productivity were increased by 12.2, 17.4, 7.2 and 60.3 %, respectively. To further understand the mechanisms of NR, cathodic potential applying and electrically reduced NR, NADH and NAD⁺ levels, ATP levels and hydrogen production were determined. NR and electrically reduced NR also improved ATP levels and the ratio of NADH/NAD⁺, whereas they decreased hydrogen production. Thus, the MEC is an efficient method for enhancing the butanol production.     

Upgrading of straw hydrolysate for production of hydrogen and phenols in a microbial electrolysis cell (MEC)

In a microbial electrolysis cell (MEC), hydrolysate produced by hydrothermal treatment of wheat straw was used for hydrogen production during selective recovery of phenols. The average H₂ production rate was 0.61 m³ H₂/m³ MEC·day and equivalent to a rate of 0.40 kg COD/m³ MEC·day. The microbial community in the anode biofilm was adapted by establishment of xylose-degrading bacteria of the Bacteriodetes phylum (16%) and Geobacter sulfurreducens (49%). During the process, 61% of the chemical oxygen demand was removed as hydrogen at 64% yield. The total energy production yield was 78% considering the energy content in the consumed compounds and the cell voltage of 0.7 V. The highest hydrogen production was equivalent to 0.8 kg COD/m³ MEC·day and was obtained at pH 7–8 and 25°C. Accumulation of 53% w/v phenolic compounds in the liquor was obtained by stepwise addition of the hydrolysate during simultaneous production of hydrogen from consumption of 95% for the hemicellulose and 100% of the fatty acids. Final calculations showed that hydrolysate produced from 1 kg wheat straw was upgraded by means of the MEC to 22 g hydrogen (266 L), 8 g xylan, and 9 g polyphenolics for potential utilization in biobased materials.     

Anode microbial communities produced by changing from microbial fuel cell to microbial electrolysis cell operation using two different wastewaters

Conditions in microbial fuel cells (MFCs) differ from those in microbial electrolysis cells (MECs) due to the intrusion of oxygen through the cathode and the release of H₂ gas into solution. Based on 16S rRNA gene clone libraries, anode communities in reactors fed acetic acid decreased in species richness and diversity, and increased in numbers of Geobacter sulfurreducens, when reactors were shifted from MFCs to MECs. With a complex source of organic matter (potato wastewater), the proportion of Geobacteraceae remained constant when MFCs were converted into MECs, but the percentage of clones belonging to G. sulfurreducens decreased and the percentage of G. metallireducens clones increased. A dairy manure wastewater-fed MFC produced little power, and had more diverse microbial communities, but did not generate current in an MEC. These results show changes in Geobacter species in response to the MEC environment and that higher species diversity is not correlated with current.