微生物燃料电池在毒性物质检测中的应用

微生物燃料电池(Microbial fuel cell,MFC)利用微生物整体作为催化剂催化底物将化学能直接转化为电能,是一种极具应用前景的生物电化学技术。微生物在阳极氧化还原有机物产生电子并传递给阳极,电子通过外电路传递至阴极后将电子释放给阴极中的氧化剂,从而产生电流。当有毒物质进入MFC,微生物活性降低,电子传递量变少,电流降低,而电流的产生与微生物活性呈线性关系,据此可检测样品的毒性。本文主要介绍了微生物燃料电池在毒性物质抗生素、重金属离子、有机污染物、酸等方面的研究,并分析了微生物燃料电池存在的问题及未来研究方向,以期不久的将来微生物燃料电池能付之使用。     

石墨烯-多壁碳纳米管复合材料协同刃天青修饰阳极对微生物燃料电池性能的影响

【目的】利用石墨烯与多壁碳纳米管复合材料协同刃天青修饰微生物燃料电池(Microbial fuel cell,MFC)阳极,提高MFC的运行性能。【方法】以碳布为基底,采用滴涂法分别制备了刃天青/碳布(R/CC)、刃天青+石墨烯/碳布(R+GNS/CC)、刃天青+多壁碳纳米管/碳布(R+MWCNT/CC)、刃天青+石墨烯+多壁碳纳米管/碳布(R+GNS+MWCNT/CC)四种阳极材料。【结果】在降解高氯酸盐的过程中,与刃天青/碳布(最高输出电压54 m V)相比,刃天青+石墨烯/碳布、刃天青+多壁碳纳米管/碳布和刃天青+石墨烯+多壁碳纳米管/碳布阳极MFC最高输出电压分别为87、145、275 m V,分别提高了61.11%、168.52%、409.26%;高氯酸盐的还原速率也分别提高了59.1%、89.7%、147.3%。4种阳极的电化学交流阻抗(EIS)和塔菲尔(Tafel)测试发现,与刃天青/碳布阳极相比,刃天青+石墨烯/碳布、刃天青+多壁碳纳米管/碳布阳极活化内阻减小,电极反应速率提高,但刃天青+石墨烯+多壁碳纳米管/碳布阳极的活化内阻更小,电极反应速率更快,同时4种阳极附着微生物胞外聚合物(EPS)分析表明,修饰过的阳极附着微生物数量增加,多糖减少,R+GNS+MWCNT/CC阳极变化最大,更有利于微生物传递电子。【结论】石墨烯、多壁碳纳米管复合材料协同刃天青修饰MFC阳极可以减小活化内阻从而加快电子传递,进而提高MFC的性能。     

一株土壤产电菌Clostridium sporogenes的分离及其产电性能

【目的】从土壤中分离获得产电菌纯菌株SE6,鉴定其种类并分析其产电性能。【方法】通过厌氧培养分离得到纯菌株,根据其形态、生理生化性质及16S r RNA基因测序分析确定其种属。以该菌株作为产电菌接种源,液体LB培养基和铁氰化钾溶液分别作为阳极液和阴极液,构建双室微生物燃料电池(Microbial fuel cells,MFCs),研究其产电能力;根据交流阻抗图谱,分析MFCs的内阻。应用循环伏安测试确定该菌株的胞外电子传递方式。并利用扫描电镜对阳极表面产电菌形态进行观察。【结果】菌株SE6的16S r RNA基因序列与Clostridium sporogenes有100%同源性,结合其形态特征和生理生化特性,确定其属于梭菌属(Clostridium)。SE6接种到MFCs中可以获得44.42 m W/m~2的最大功率密度。MFCs的阳极内阻、阴极内阻和欧姆内阻分别为(1488±193)Ω/cm~2、(0.92±0.01)Ω/cm~2和(20.69±1.76)Ω/cm~2。其循环伏安图谱显示体系中存在电化学活性物质且峰值电流随扫速升高线性增大。扫描电镜观察到阳极表面聚集附着着长度约1μm的杆菌。【结论】本研究成功从土壤中分离出具有一定产电能力的菌株C.sporogenes SE6,可直接将电子传递至阳极,其产电过程阻抗较大。     

“共轭聚合物-产电菌”复合生物电极构建及其在微生物燃料电池中的应用

微生物燃料电池(Microbial fuel cell,MFC)作为一种生物电化学装置,在可再生能源生产和废水处理方面的巨大潜力已引起广泛关注。然而MFC面临输出功率低、欧姆内阻高以及启动时间长等问题,极大限制了其在实际工程中的应用。MFC中阳极是微生物附着的载体,对电子的产生及传递起着关键作用,开发优质的生物电极已发展成为改善MFC性能的有效途径。共轭聚合物具有成本低、电导率高、化学稳定性及生物相容性好等优点,利用共轭聚合物修饰生物电极结构,可以实现大比表面积、缩短电荷转移路径,从而实现高效生物电化学性能。同时,纳米级共轭聚合物包覆细菌,可以使细菌产生的电子有效地传递到电极。文中综述了最近报道的共轭聚合物在MFC中的应用,重点介绍了共轭聚合物修饰的MFC阳极,系统分析了共轭聚合物的优点及局限性,以及这些高效复合生物电极如何解决MFC应用中存在的低输出功率、高欧姆内阻及长启动时间等问题。     

微生物燃料电池内阻及其影响因素分析

微生物燃料电池(MFC)是一种通过微生物的催化作用将有机物中的化学能直接转化为电能的生物反应装置,研究表明内阻是限制微生物燃料电池产能的重要因素。本文对目前国内外有关微生物燃料电池内阻的研究成果进行了总结,系统介绍了微生物燃料电池内阻定义、构成和常用的微生物燃料电池内阻测定方法,重点分析了反应器、产电底物、产电微生物和操作条件等对微生物燃料电池内阻的影响,并结合已有的研究结果提出了降低内阻、提高微生物燃料电池产电性能的可行性方法。     

微生物燃料电池中阳极产电微生物的研究进展

微生物燃料电池（MFC）是利用阳极产电微生物为催化剂降解有机废物直接将化学能转化为电能的装置。在MFC系统中,产电微生物是影响产电性能的核心要素之一。介绍了MFC中产电微生物的最新研究现状,详细讨论了产电微生物的种类、产电机理和产电能力．为产电微生物的富集、驯化、改造和多种菌种优化组合提供思路。     

pH值对微生物燃料电池处理生物废弃物的影响

以生物废弃物为底物,采用双室微生物燃料电池对生物废弃物进行处理,研究阳极液初始pH值对生物废弃物CODcr、TOC去除率的影响,以及对微生物燃料电池产电性能影响。实验结果表明,当阳极液pH值为6时,CODcr去除率达72.1%,TOC的去除率达44.5%,其输出电压最大为1.27 V,平均电压797 mV,最大功率密度达到136.6 mW/m2。     

微生物电极的研制及其阴、阳极反应的研究

本文描述了一个用于微生物浓度快速测定的燃料电池型的微生物电极的构造及其基本工作原理。分别用恒电流阴极极化法和旋转圆盘电极恒电位阳极极化法研究了微生物电极的阴极反应和阳极反应,用分光光度法研究了微生物对染料(硫堇)的还原动力学。结果表明;以K₃Fe(CN)₆-K₄ Fe(CN)₆,的饱和溶滚为阴极液,在微生物电极的正常工作电流下,阴极电位基本上不发生极化,阳极反应受扩散控制,微生物对染料(硫堇)的还原动力学符合米氏型方程 溶解氧,微生物的浓度以及微生物对染料的还原能力对染料的还原动力学具有较大的影响。     

好氧-厌氧混合污泥启动微生物燃料电池产电性能及微生物群落动态特征

【目的】为探讨好氧-厌氧混合污泥启动微生物燃料电池(Microbial fuel cell,MFC)产电性能以及MFC对微生物群落的选择作用,【方法】以乳酸为底物,应用不依赖于培养的微生物分子生物学技术解析单室MFC启动过程中微生物群落的组成和结构动态学特征。【结果】结果表明,MFC经过3个周期启动成功,最高输出电压230 m V。当MFC外电阻为1656Ω时,最大功率密度11.15 W/m3,电池运行稳定。混合污泥启动MFC以后,阳极生物膜微生物群落结构同种泥差异较大,且多样性降低。生物膜中微生物类群按丰度依次为β-变形菌纲(Betaproteobacteria)24.90%、拟杆菌门(Bacteroidetes)21.30%、厚壁菌门(Firmicutes)9.70%、γ-变形菌纲(Gammaproteobacteria)8.50%、δ-变形菌纲(Deltaproteobacteria)7.90%、绿弯菌门(Chloroflexi)4.20%以及α-变形菌纲(Alphaproteobacteria)3.60%。有利于生物膜形成与稳定的动胶菌属(Zoogloea)和不动杆菌属(Acinetobacter)序列丰度分别占生物膜群落的5.00%和3.90%,与MFC产电能力直接相关的地杆菌属(Geobacter)序列由混合污泥中的0.60%上升至阳极生物膜中的2.60%。【结论】本研究表明,MFC阳极生物膜在驯化过程中对污泥中的微生物进行淘汰和选择,最终驯化形成了有利于生物膜形成与稳定、有机物厌氧发酵与产电的微生物菌群。     

微生物燃料电池利用乳酸产电性能与微生物群落分布特征

【目的】为探讨以乳酸为基质的微生物燃料电池(Microbial fuel cell,MFC)产电性能以及微生物群落在阳极膜、悬浮液、阳极沉淀污泥中的分布特征,【方法】试验建立了双室MFC,以乳酸为阳极主要碳源,研究了反应器的启动过程及产电效能,同时以电镜和PCR-变性梯度凝胶电泳(Denaturing gradient gelelectrophoresis,DGGE)技术解析了微生物群落的空间分布特征。【结果】结果表明,反应器启动第7天时外电压达到0.56 V,当外阻为80Ω时,电流密度为415 mA/m2,MFC的功率密度达到最大值82 mW/m2。电镜观察发现大量杆菌附着在阳极表面,结合较为紧密;DGGE图谱显示阳极膜表面微生物与种泥最为相似,与阳极悬浮液、底部沉淀污泥中的主要菌群一致,条带序列与睾丸酮丛毛单胞菌(Comamonas testosteroni)和布氏弓形菌(Arcobacter butzleri)等最为相似。【结论】本研究表明以乳酸为基质MFC可产生较高的功率密度,阳极附着的优势菌与接种污泥来源密切相关。     

Investigating microbial fuel cell bioanode performance under different cathode conditions

A compact, three‐in‐one, flow‐through, porous, electrode design with minimal electrode spacing and minimal dead volume was implemented to develop a microbial fuel cell (MFC) with improved anode performance. A biofilm‐dominated anode consortium enriched under a multimode, continuous‐flow regime was used. The increase in the power density of the MFC was investigated by changing the cathode (type, as well as catholyte strength) to determine whether anode was limiting. The power density obtained with an air‐breathing cathode was 56 W/m³ of net anode volume (590 mW/m²) and 203 W/m³ (2160 mW/m²) with a 50‐mM ferricyanide‐based cathode. Increasing the ferricyanide concentration and ionic strength further increased the power density, reaching 304 W/m³ (3220 mW/m², with 200 mM ferricyanide and 200 mM buffer concentration). The increasing trend in the power density indicated that the anode was not limiting and that higher power densities could be obtained using cathodes capable of higher rates of oxidation. The internal solution resistance for the MFC was 5–6 Ω, which supported the improved performance of the anode design. A new parameter defined as the ratio of projected surface area to total anode volume is suggested as a design parameter to relate volumetric and area‐based power densities and to enable comparison of various MFC configurations. Published 2009 American Institute of Chemical Engineers Biotechnol. Prog., 2009     

Effects of the Pt loading side and cathode-biofilm on the performance of a membrane-less and single-chamber microbial fuel cell

In order to analyze the effect of cathode's Pt loading side on the performance of single-chamber microbial fuel cells (MFCs), power generation of a bamboo charcoal membrane-less air-cathode MFC was examined. The maximum power outputs obtained were 0.144 and 1.16 mW, while the maximum voltage outputs were 0.400 and 0.500 V (external resistance was 500 Omega), respectively, when the Pt loading side facing to the air and to the anode chamber solution; after a long time of operation with the side of cathode loaded Pt facing to anode chamber solution, a biofilm was developed on the inner side of cathode. With the formation of this biofilm, the power outputs of MFC increased first, and then decreased to 0.8 mW; oxidation-reduction potentials (ORP) dropped first, and then achieved the level of stability. Coulombic efficiency (CE) increased at a certain extent. In addition, the impact of cathode-biofilm on the loss of water in anode chamber solution was determined.     

Increasing power generation for scaling up single-chamber air cathode microbial fuel cells

Scaling up microbial fuel cells (MFCs) requires a better understanding the importance of the different factors such as electrode surface area and reactor geometry relative to solution conditions such as conductivity and substrate concentration. It is shown here that the substrate concentration has significant effect on anode but not cathode performance, while the solution conductivity has a significant effect on the cathode but not the anode. The cathode surface area is always important for increasing power. Doubling the cathode size can increase power by 62% with domestic wastewater, but doubling the anode size increases power by 12%. Volumetric power density was shown to be a linear function of cathode specific surface area (ratio of cathode surface area to reactor volume), but the impact of cathode size on power generation depended on the substrate strength (COD) and conductivity. These results demonstrate the cathode specific surface area is the most critical factor for scaling-up MFCs to obtain high power densities.     

Simultaneous degradation of refractory contaminants in both the anode and cathode chambers of the microbial fuel cell

In this study, the microbial fuel cell (MFC) was combined with the Fenton-like technology to simultaneously generate electricity and degrade refractory contaminants in both anode and cathode chambers. The maximum power density achieved was 15.9 W/m³ at an initial pH of 3.0 in the MFC. In the anode chamber, approximately 100% of furfural and 96% COD were removed at the end of a cycle. In the cathode chamber, the Fenton-like reaction with FeVO₄ as a catalyst enhanced the removal of AO7 and COD. The removal rates of AO7 and COD reached 89% and 81%, respectively. The optimal pH value and FeVO₄ dosage toward degrading AO7 were about 3.0 and 0.8 g, respectively. Furthermore, a two-way catalyst mechanism of FeVO₄ and the contaminant degradation pathway in the MFC were explored.     

Impact of initial biofilm growth on the anode impedance of microbial fuel cells

Electrochemical impedance spectroscopy (EIS) was used to study the behavior of a microbial fuel cell (MFC) during initial biofilm growth in an acetate-fed, two-chamber MFC system with ferricyanide in the cathode. EIS experiments were performed both on the full cell (between cathode and anode) as well as on individual electrodes. The Nyquist plots of the EIS data were fitted with an equivalent electrical circuit to estimate the contributions of various intrinsic resistances to the overall internal MFC impedance. During initial development of the anode biofilm, the anode polarization resistance was found to decrease by over 70% at open circuit and by over 45% at 27 microA/cm(2), and a simultaneous increase in power density by about 120% was observed. The exchange current density for the bio-electrochemical reaction on the anode was estimated to be in the range of 40-60 nA/cm(2) for an immature biofilm after 5 days of closed circuit operation, which increased to around 182 nA/cm(2) after more than 3 weeks of operation and stable performance in an identical parallel system. The polarization resistance of the anode was 30-40 times higher than that of the ferricyanide cathode for the conditions tested, even with an established biofilm. For a two-chamber MFC system with a Nafion 117 membrane and an inter-electrode spacing of 15 cm, the membrane and electrolyte solution dominate the ohmic resistance and contribute to over 95% of the MFC internal impedance. Detailed EIS analyses provide new insights into the dominant kinetic resistance of the anode bio-electrochemical reaction and its influence on the overall power output of the MFC system, even in the high internal resistance system used in this study. These results suggest that new strategies to address this kinetic constraint of the anode bio-electrochemical reactions are needed to complement the reduction of ohmic resistance in modern designs.     

Analysis of ammonia loss mechanisms in microbial fuel cells treating animal wastewater

Ammonia losses during swine wastewater treatment were examined using single- and two-chambered microbial fuel cells (MFCs). Ammonia removal was 60% over 5 days for a single-chamber MFC with the cathode exposed to air (air-cathode), versus 69% over 13 days from the anode chamber in a two-chamber MFC with a ferricyanide catholyte. In both types of systems, ammonia losses were accelerated with electricity generation. For the air-cathode system, our results suggest that nitrogen losses during electricity generation were increased due to ammonia volatilization with conversion of ammonium ion to the more volatile ammonia species as a result of an elevated pH near the cathode (where protons are consumed). This loss mechanism was supported by abiotic tests (applied voltage of 1.1 V). In a two-chamber MFC, nitrogen losses were primarily due to ammonium ion diffusion through the membrane connecting the anode and cathode chambers. This loss was higher with electricity generation as the rate of ammonium transport was increased by charge transfer across the membrane. Ammonia was not found to be used as a substrate for electricity generation, as intermittent ammonia injections did not produce power. The ammonia-oxidizing bacterium Nitrosomonas europaea was found on the cathode electrode of the single-chamber system, supporting evidence of biological nitrification, but anaerobic ammonia-oxidizing bacteria were not detected by molecular analyses. It is concluded that ammonia losses from the anode chamber were driven primarily by physical-chemical factors that are increased with electricity generation, although some losses may occur through biological nitrification and denitrification.     

Bioelectricity generation enhancement in a dual chamber microbial fuel cell under cathodic enzyme catalyzed dye decolorization

Enzymatic decolorization of reactive blue 221 (RB221) using laccase was investigated in a dual-chamber microbial fuel cell (MFC). Suspended laccase was used in the cathode chamber in the absence of any mediators in order to decolorize RB221 and also improve oxygen reduction reaction in the cathode. Molasses was utilized as low cost and high strength energy source in the anode chamber. The capability of MFC for simultaneous molasses and dye removal was investigated. A decolorization efficiency of 87% was achieved in the cathode chamber and 84% COD removal for molasses was observed in the anode chamber. Laccase could catalyze the removal of RB221 and had positive effect on MFC performance as well. Maximum power density increased about 30% when enzymatic decolorization was performed in the cathode chamber.     

Integrated organic and nitrogen removal with electricity generation in a tubular dual-cathode microbial fuel cell

This study presented a dual-cathode microbial fuel cell (MFC) that was designed to accomplish nitrification in its outer cathode and denitrification in the inner cathode. The MFC was continuously operated for more than 150 days and achieved organic removal of 85–99% in the anode, depending on the initial organic loading rates. More than 96% of the ammonium was removed, while the total nitrogen removal was between 66.7 and 89.6%, largely affected by the remaining nitrate in the effluent of the inner cathode. The coulombic efficiency suggested that the nitrate was primarily removed by bioelectrochemcial denitrification in the inner cathode, especially at the low nitrogen loading rates. However, a higher nitrogen loading rate encouraged nitrate migration through the anion exchange membrane, thereby being removed by conventional denitrification. The preliminary energy analysis suggested that the energy production in the dual-cathode MFC could potentially support its pumping system. To achieve an energy-neutral system, aeration must be omitted in the future design and passive oxygen supply should be considered with a proper design of the outer cathode. Those results demonstrated the feasibility of using a tubular dual-cathode MFC to remove both organics and nitrogen while producing electricity.     

A comparison of air and hydrogen peroxide oxygenated microbial fuel cell reactors

In this study, a two-compartment continuous flow microbial fuel cell (MFC) reactor was used to compare the efficiencies of cathode oxygenation by air and by hydrogen peroxide. The MFC reactor had neither a proton-selective membrane nor an electron transfer mediator. At startup, the cathodic compartment was continuously aerated and the anodic compartment was fed with a glucose solution. An increase of electrical power generation from 0.008 to 7.2 mW m(-2) of anode surface with a steady-state potential of 215-225 mV was observed within a period of 12 days. The performance of the air-oxygenated MFC reactor progressively declined over time because of biofilm proliferation in the cathodic compartment. Oxygenation of the cathodic compartment using 300 mL d(-1) of 0.3% hydrogen peroxide solution resulted in a power density of up to 22 mW m(-2) (68.2 mA m(-2)) of anode surface at a potential of 340-350 mV. The use of H2O2 for oxygenation was found to improve the long-term stability of the MFC reactor.     

Electrical behavior of a natural polyelectrolyte hydrogel: chitosan/carboxymethylcellulose hydrogel

An amphoteric hydrogel film was prepared by solution blending of two natural polyelectrolytes, chitosan and carboxymethylcellulose, and cross-linking with glutaraldehyde. The bending of the film in an electric field was studied in different electrolyte solutions. Because of its amphoteric nature, the hydrogel can bend toward either anode or cathode depending on the pH of the solution. Other factors such as ionic strength and electric field strength also influence the electromechanical behavior of the hydrogels. The equilibrium bending angle of the hydrogel was found to reach a maximum at about 90 degrees in pH = 6 Britton-Robinson buffer solution with an ionic strength of 0.2 M. The sensitivity of the films over a wide range of pH and the good reversibility of this natural amphoteric electric-sensitive hydrogel suggest its future use in microsensor and actuator applications, especially in the biomedical field.