Activity and stability of pyrolyzed iron ethylenediaminetetraacetic acid as cathode catalyst in microbial fuel cells

A low-cost and effective iron-chelated catalyst was developed as an electrocatalyst for the oxygen reduction reaction (ORR) in microbial fuel cells (MFCs). The catalyst was prepared by pyrolyzing carbon mixed iron-chelated ethylenediaminetetraacetic acid (PFeEDTA/C) in an argon atmosphere. Cyclic voltammetry measurements showed that PFeEDTA/C had a high catalytic activity for ORR. The MFC with a PFeEDTA/C cathode produced a maximum power density of 1122 mW/m², which was close to that with a Pt/C cathode (1166 mW/m²). The PFeEDTA/C was stable during an operation period of 31 days. Based on X-ray diffraction and X-ray photoelectron spectroscopy measurements, quaternary-N modified with iron might be the active site for the oxygen reduction reaction. The total cost of a PFeEDTA/C catalyst was much lower than that of a Pt catalyst. Thus, PFeEDTA/C can be a good alternative to Pt in MFC practical applications.     

Application of Co-naphthalocyanine (CoNPc) as alternative cathode catalyst and support structure for microbial fuel cells

Co-naphthalocyanine (CoNPc) was prepared by heat treatment for cathode catalysts to be used in microbial fuel cells (MFCs). Four different catalysts (Carbon black, NPc/C, CoNPc/C, Pt/C) were compared and characterized using XPS, EDAX and TEM. The electrochemical characteristics of oxygen reduction reaction (ORR) were compared by cyclic voltammetry (CV) and linear sweep voltammetry (LSV). The Co-macrocyclic complex improves the catalyst dispersion and oxygen reduction reaction of CoNPc/C. The maximum power of CoNPc/C was 64.7 mW/m² at 0.25 mA as compared with 81.3 mW/m² of Pt/C, 29.7 mW/m² of NPc/C and 9.3 mW/m² of carbon black when the cathodes were implemented in H-type MFCs. The steady state cell, cathode and anode potential of MFC with using CoNPc/C were comparable to those of Pt/C.     

Carbon nanotube supported MnO₂ catalysts for oxygen reduction reaction and their applications in microbial fuel cells

Three types of manganese dioxide, α-MnO(2), β-MnO(2), γ-MnO(2) were tested as alternative cathode catalysts for oxygen reduction reaction (ORR) in air-cathode microbial fuel cells (MFCs). Prepared by solution-based methods, the MnO(2) nanomaterials were comprehensively characterized, and their electrocatalytic activities in neutral electrolyte were investigated with the supporting material of carbon nanotubes (CNTs) by cyclic voltammetry (CV). The CV results showed that all MnO(2) species could catalyze ORR in neutral NaCl solution with different catalytic activities. β-MnO(2) had the highest catalytic activity due to its intrinsic structure and better interaction with CNTs. Three MnO(2) species were further used as cathode catalysts under optimized conditions in air-cathode cubic MFCs, in which mixed culture was inoculated as biocatalysts and domestic wastewater was used as the substrate in the anode chamber. It was also found that β-MnO(2) based MFC yielded the best performance with a power density of 97.8 mWm(-2) which was 64.1% that of the Pt-based MFC, and a lower internal resistance of 165 Ω. Furthermore, the COD removal efficiency of β-MnO(2) based MFC was estimated as 84.8%, higher than that of the Pt-based MFC. This study demonstrated that using β-MnO(2) on CNT support instead of Pt could potentially improve the feasibility of scaling up air-cathode MFCs for practical applications by lowering the material cost.     

Simultaneous carbon and nitrogen removal using an oxic/anoxic-biocathode microbial fuel cells coupled system

A coupled microbial fuel cell (MFC) system comprising of an oxic-biocathode MFC (O-MFC) and an anoxic-biocathode MFC (A-MFC) was implemented for simultaneous removal of carbon and nitrogen from a synthetic wastewater. The chemical oxygen demand (COD) of the influent was mainly reduced at the anodes of the two MFCs; ammonium was oxidized to nitrate in the O-MFC’s cathode, and nitrate was electrochemically denitrified in the A-MFC’s cathode. The coupled MFC system reached power densities of 14 W/m³ net cathodic compartment (NCC) and 7.2 W/m³ NCC for the O-MFC and the A-MFC, respectively. In addition, the MFC system obtained a maximum COD, NH₄⁺-N and TN removal rate of 98.8%, 97.4% and 97.3%, respectively, at an A-MFC external resistance of 5 Ω, a recirculation ratio (recirculated flow to total influent flow) of 2:1, and an influent flow ratio (O-MFC anode flow to A-MFC anode flow) of 1:1.     

Factors affecting current production in microbial fuel cells using different industrial wastewaters

This study evaluated how different types of industrial wastewaters (bakery, brewery, paper and dairy) affect the performance of identical microbial fuel cells (MFCs); and the microbial composition and electrochemistry of MFC anodes. MFCs fed with paper wastewater produced the highest current density (125 ± 2 mA/m²) at least five times higher than dairy (25 ± 1 mA/m²), brewery and bakery wastewaters (10 ± 1 mA/m²). Such high current production was independent of substrate degradability. A comprehensive study was conducted to determine the factor driving current production when using the paper effluent. The microbial composition of anodic biofilms differed according to the type of wastewater used, and only MFC anodes fed with paper wastewater showed redox activity at −134 ± 5 mV vs NHE. Electrochemical analysis of this redox activity indicated that anodic bacteria produced a putative electron shuttling compound that increased the electron transfer rate through diffusion, and as a result the overall MFC performance.     

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.     

Scalable air cathode microbial fuel cells using glass fiber separators, plastic mesh supporters, and graphite fiber brush anodes

The combined use of brush anodes and glass fiber (GF1) separators, and plastic mesh supporters were used here for the first time to create a scalable microbial fuel cell architecture. Separators prevented short circuiting of closely-spaced electrodes, and cathode supporters were used to avoid water gaps between the separator and cathode that can reduce power production. The maximum power density with a separator and supporter and a single cathode was 75 ± 1 W/m³. Removing the separator decreased power by 8%. Adding a second cathode increased power to 154 ± 1 W/m³. Current was increased by connecting two MFCs connected in parallel. These results show that brush anodes, combined with a glass fiber separator and a plastic mesh supporter, produce a useful MFC architecture that is inherently scalable due to good insulation between the electrodes and a compact architecture.     

Air-cathode structure optimization in separator-coupled microbial fuel cells

Microbial fuel cells (MFC) with 30% wet-proofed air cathodes have previously been optimized to have 4 diffusion layers (DLs) in order to limit oxygen transfer into the anode chamber and optimize performance. Newer MFC designs that allow close electrode spacing have a separator that can also reduce oxygen transfer into the anode chamber, and there are many types of carbon wet-proofed materials available. Additional analysis of conditions that optimize performance is therefore needed for separator-coupled MFCs in terms of the number of DLs and the percent of wet proofing used for the cathode. The number of DLs on a 50% wet-proofed carbon cloth cathode significantly affected MFC performance, with the maximum power density decreasing from 1427 to 855 mW/m² for 1–4 DLs. A commonly used cathode (30% wet-proofed, 4 DLs) produced a maximum power density (988 mW/m²) that was 31% less than that produced by the 50% wet-proofed cathode (1 DL). It was shown that the cathode performance with different materials and numbers of DLs was directly related to conditions that increased oxygen transfer. The coulombic efficiency (CE) was more affected by the current density than the oxygen transfer coefficient for the cathode. MFCs with the 50% wet-proofed cathode (2 DLs) had a CE of >84% (6.8 A/m²), which was substantially larger than that previously obtained using carbon cloth air-cathodes lacking separators. These results demonstrate that MFCs constructed with separators should have the minimum number of DLs that prevent water leakage and maximize oxygen transfer to the cathode.     

Effects of ammonium concentration and charge exchange on ammonium recovery from high strength wastewater using a microbial fuel cell

Ammonium recovery using a two chamber microbial fuel cell (MFC) was investigated at high ammonium concentration. Increasing the ammonium concentration (from 0.07 to 4 g ammonium-nitrogen/L) by addition of ammonium chloride did not affect the performance of the MFC. The obtained current densities by DC-voltammetry were higher than 6 A/m² for both operated MFCs. Also continuous operation at lower external resistance (250 Ω) showed an increased current density (0.9 A/m²). Effective ammonium recovery can be achieved by migrational ion flux through the cation exchange membrane to the cathode chamber, driven by the electron production from degradation of organic substrate. The charge transport was proportional to the concentration of ions. Nonetheless, a concentration gradient will influence the charge transport. Furthermore, a charge exchange process can influence the charge transport and therefore the recovery of specific ions.     

Performance and microbial ecology of air-cathode microbial fuel cells with layered electrode assemblies

Microbial fuel cells (MFCs) can be built with layered electrode assemblies, where the anode, proton exchange membrane (PEM), and cathode are pressed into a single unit. We studied the performance and microbial community structure of MFCs with layered assemblies, addressing the effect of materials and oxygen crossover on the community structure. Four MFCs with layered assemblies were constructed using Nafion or Ultrex PEMs and a plain carbon cloth electrode or a cathode with an oxygen-resistant polytetrafluoroethylene diffusion layer. The MFC with Nafion PEM and cathode diffusion layer achieved the highest power density, 381 mW/m² (20 W/m³). The rates of oxygen diffusion from cathode to anode were three times higher in the MFCs with plain cathodes compared to those with diffusion-layer cathodes. Microsensor studies revealed little accumulation of oxygen within the anode cloth. However, the abundance of bacteria known to use oxygen as an electron acceptor, but not known to have exoelectrogenic activity, was greater in MFCs with plain cathodes. The MFCs with diffusion-layer cathodes had high abundance of exoelectrogenic bacteria within the genus Geobacter. This work suggests that cathode materials can significantly influence oxygen crossover and the relative abundance of exoelectrogenic bacteria on the anode, while PEM materials have little influence on anode community structure. Our results show that oxygen crossover can significantly decrease the performance of air-cathode MFCs with layered assemblies, and therefore limiting crossover may be of particular importance for these types of MFCs.     

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.     

Enhancement in current density and energy conversion efficiency of 3-dimensional MFC anodes using pre-enriched consortium and continuous supply of electron donors

Using a pre-enriched microbial consortium as the inoculum and continuous supply of carbon source, improvement in performance of a three-dimensional, flow-through MFC anode utilizing ferricyanide cathode was investigated. The power density increased from 170 W/m³ (1800 mW/m²) to 580 W/m³ (6130 mW/m²), when the carbon loading increased from 2.5 g/l-day to 50 g/l-day. The coulombic efficiency (CE) decreased from 90% to 23% with increasing carbon loading. The CEs are among the highest reported for glucose and lactate as the substrate with the maximum current density reaching 15.1 A/m². This suggests establishment of a very high performance exoelectrogenic microbial consortium at the anode. A maximum energy conversion efficiency of 54% was observed at a loading of 2.5 g/l-day. Biological characterization of the consortium showed presence of Burkholderiales and Rhodocyclales as the dominant members. Imaging of the biofilms revealed thinner biofilms compared to the inoculum MFC, but a 1.9-fold higher power density.     

Improved performance of membrane free single-chamber air-cathode microbial fuel cells with nitric acid and ethylenediamine surface modified activated carbon fiber felt anodes

Surface modifications of anode materials are important for enhancing power generation of microbial fuel cell (MFC). Membrane free single-chamber air-cathode MFCs, MFC-A and MFC-N, were constructed using activated carbon fiber felt (ACF) anodes treated by nitric acid and ethylenediamine (EDA), respectively. Experimental results showed that the start-up time to achieve the maximum voltages for the MFC-A and MFC-N was shortened by 45% and 51%, respectively as compared to that for MFC-AT equipped with an unmodified anode. Moreover, the power output of MFCs with modified anodes was significantly improved. In comparison with MFC-AT which had a maximum power density of 1304 mW/m², the MFC-N achieved a maximum power density of 1641 mW/m². The nitric acid-treated anode in MFC-A increased the power density by 58% reaching 2066 mW/m². XPS analysis of the treated and untreated anode materials indicated that the power enhancement was attributable to the changes of surface functional groups.     

Effects of sulfide on microbial fuel cells with platinum and nitrogen-doped carbon powder cathodes

Because of the advantages of low cost, good electrical conductivity and high oxidation resistance, nitrogen-doped carbon (NDC) materials have a potential to replace noble metals in microbial fuel cells (MFCs) for wastewater treatment. In spite of a large volume of studies on NDC materials as catalysts for oxygen reduction reaction, the influence of sulfide on NDC materials has not yet been explicitly reported so far. In this communication, nitrogen-doped carbon powders (NDCP) were prepared by treating carbon powders in nitric acid under reflux condition. Sodium sulfide (Na(2)S) was added to the cathodic electrolyte to compare its effects on platinum (Pt) and NDCP cathodes. Cell voltages, power density and cathodic potentials were monitored without and with Na(2)S and after Na(2)S was removed. The maximum cell voltage of the MFCs with Pt cathode decreased by 10% in the presence of Na(2)S that did not change the performance of the MFC with NDCP cathode, and the maximum power density of the MFC with NDCP cathode was even 11.3% higher than that with Pt cathode (222.5 ± 8 mW m(-2) vs. 199.7 ± 4 mW m(-2)).     

A microfluidic microbial fuel cell fabricated by soft lithography

Here we report a new microfluidic microbial fuel cell (MFC) platform built by soft-lithography techniques. The MFC design includes a unique sub-5 μL polydimethylsiloxane soft chamber featuring carbon cloth electrodes and microfluidic delivery of electrolytes. Bioelectricity was generated using Shewanella oneidensis MR-1 cultivated on either complex organic substrates or lactate-based minimal medium. These micro-MFCs exhibited fast start-ups, reproducible current generation, and enhanced power densities up to 62.5 W m⁻³ that represents the best result for sub-100 μL MFCs. Systematic comparisons of custom-made MFC reactors having different chamber sizes indicate volumetric power density is inversely correlated with chamber size in our systems: i.e., the smaller the chamber, the higher the power density is achieved.     

Enhanced Cathodic Oxygen Reduction and Power Production of Microbial Fuel Cell Based on Noble‐Metal‐Free Electrocatalyst Derived from Metal‐Organic Frameworks

Microbial fuel cell (MFC) can generate electricity from organic substances based on anodic electrochemically active microorganisms and cathodic oxygen reduction reaction (ORR), thus exhibiting promising potential for harvesting electric energy from organic wastewater. The ORR performance is crucial to both power production efficiency and overall cost of MFC. A new type of metal‐organic‐framework‐derived electrocatalysts containing cobalt and nitrogen‐doped carbon (CoNC) is developed, which is effective to enhance activity, selectivity, and stability toward four‐electron ORR in pH‐neutral electrolyte. When glucose is used as the substrate, the maximum power density of 1665 mW m^?2 is achieved for the optimized CoNC pyrolyzed at 900 °C, which is 39.8% higher than that of 1191 mW m^?2 for commercial Pt/C catalyst in the single‐chamber MFC. The improved performance of CoNC catalyst can be attributed to large surface area, microporous nature, and the involvement of nitrogen‐coordinated cobalt species. These properties enable the efficient ORR by increasing the active sites and enhancing mass transfer of oxygen and protons at “water‐flooding” three‐phase boundary where ORR occurs. This work provides a proof‐of‐concept demonstration of a noble‐metal‐free high‐efficiency and cost‐effective ORR electrocatalyst for effective recovery of electricity from biomass materials and organic wastewater in MFC.     

Simultaneous Congo red decolorization and electricity generation in air-cathode single-chamber microbial fuel cell with different microfiltration, ultrafiltration and proton exchange membranes

Different microfiltration membrane (MFM), proton exchange membrane (PEM) and ultrafiltration membranes (UFMs) with different molecular cutoff weights of 1 K (UFM-1K), 5 K (UFM-5K) and 10 K (UFM-10K) were incorporated into air-cathode single-chamber microbial fuel cells (MFCs) which were explored for simultaneous azo dye decolorization and electricity generation to investigate the effect of membrane on the performance of the MFC. Batch test results showed that the MFC with an UFM-1K produced the highest power density of 324 mW/m² coupled with an enhanced coulombic efficiency compared to MFM. The MFC with UMF-10K achieved the fastest decolorization rate (4.77 mg/L h), followed by MFM (3.61 mg/L h), UFM-5K (2.38 mg/L h), UFM-1K (2.02 mg/L h) and PEM (1.72 mg/L h). These results demonstrated the possibility of using various membranes in the system described here, and showed that UFM-1K was the best one based on the consideration of both cost and performance.     

<Emphasis Type="Italic">Pseudomonas seleniipraecipitatus</Emphasis> sp. nov.: A Selenite Reducing γ-<Emphasis Type="Italic">Proteobacteria</Emphasis> Isolated from Soil

Microbial fuel cells (MFCs) are a technology that provides electrical energy from the microbial oxidation of organic compounds. Most MFCs use oxygen as the oxidant in the cathode chamber. This study examined the formation in culture of an unidentified bacterial oxidant and investigated the performance of this oxidant in a two-chambered MFC with a proton exchange membrane and an uncoated carbon cathode. DNA, FAME profile and characterization studies identified the microorganism that produced the oxidant as Burkholderia cenocepacia. The oxidant was produced by log phase cells, oxidized the dye 2,2′-azino-bis(3-ethylbenzthiazoline-6-sulphonic acid) (ABTS), had a mass below 1 kD, was heat stable (121°C) and was soluble in ethanol. In a MFC with a 1000 Ω load and ABTS as a mediator, the oxidizer increased cell voltage 11 times higher than atmospheric oxygen and 2.9 times higher than that observed with ferricyanide in the cathode chamber. No increase in cell voltage was observed when no mediator was present. Organisms that produce and release oxidizers into the media may prove useful as bio-cathodes by improving the electrical output of MFCs.     

Pre-acclimation of a wastewater inoculum to cellulose in an aqueous-cathode MEC improves power generation in air-cathode MFCs

Cellulose has been used in two-chamber microbial fuel cells (MFCs), but power densities were low. Higher power densities can be achieved in air-cathode MFCs using an inoculum from a two-chamber, aqueous-cathode microbial electrolysis cell (MEC). Air-cathode MFCs with this inoculum produced maximum power densities of 1070 mW m⁻² (cathode surface area) in single-chamber and 880 mW m⁻² in two-chamber MFCs. Coulombic efficiencies ranged from 25% to 50%, and COD removals were 50-70% based on total cellulose removals of 60-80%. Decreasing the reactor volume from 26 to 14 mL (while maintaining constant electrode spacing) decreased power output by 66% (from 526 to 180 mW m⁻²) due to a reduction in total mass of cellulose added. These results demonstrate that air-cathode MFCs can produce high power densities with cellulose following proper acclimation of the inoculum, and that organic loading rates are important for maximizing power densities from particulate substrates.     

Optimization of a Pt-free cathode suitable for practical applications of microbial fuel cells

Microbial fuel cells (MFCs) are considered as a promising way for the direct extraction of biochemical energy from biomass into electricity. However, scaling up the process for practical applications and mainly for wastewater treatment is an issue because there is a necessity to get rid of unsustainable platinum (Pt) catalyst. In this study, we developed a low-cost cathode for a MFC making use of sputter-deposited cobalt (Co) as the catalyst and different types of cathode architecture were tested in a single-chambered air-cathode MFC. By sputtering the catalyst on the air-side of the cathode, increased contact with ambient oxygen significantly resulted in higher electricity generation. This outcome was different from previous studies using conventionally-coated Pt cathodes, which was due to the different technology used.