Developing 3D-Printable Cathode Electrode for Monolithically Printed Microbial Fuel Cells (MFCs).

Microbial Fuel Cells (MFCs) employ microbial electroactive species to convert chemical energy stored in organic matter, into electricity. The properties of MFCs have made the technology attractive for bioenergy production. However, a challenge to the mass production of MFCs is the time-consuming assembly process, which could perhaps be overcome using additive manufacturing (AM) processes. AM or 3D-printing has played an increasingly important role in advancing MFC technology, by substituting essential structural components with 3D-printed parts. This was precisely the line of work in the EVOBLISS project, which investigated materials that can be extruded from the EVOBOT platform for a monolithically printed MFC. The development of such inexpensive, eco-friendly, printable electrode material is described below. The electrode in examination (PTFE_FREE_AC), is a cathode made of alginate and activated carbon, and was tested against an off-the-shelf sintered carbon (AC_BLOCK) and a widely used activated carbon electrode (PTFE_AC). The results showed that the MFCs using PTFE_FREE_AC cathodes performed better compared to the PTFE_AC or AC_BLOCK, producing maximum power levels of 286 µW, 98 µW and 85 µW, respectively. In conclusion, this experiment demonstrated the development of an air-dried, extrudable (3D-printed) electrode material successfully incorporated in an MFC system and acting as a cathode electrode.

Recovery of chromium, copper and vanadium combined with electricity generation in two-chambered microbial fuel cells.

Microbial fuel cells (MFCs) offer a promising solution towards recovery and treatment of heavy metal pollutants. In this study, two-chambered MFCs were employed for recovery of chromium, copper and vanadium (Cr (VI), Cu (II) and V (V)). One g/L concentrations of K2Cr2O7, CuCl2 and NaVO3 served as catholytes, while a mixed culture was used as anolyte. Cr (VI), Cu (II) and V (V) were reduced biologically into less toxic forms of Cr (III), Cu and V (IV) respectively. Power density and cathodic efficiency were calculated for each of the catholytes. Cr (VI) gave the maximum power density and cathodic efficiency due to its high redox potential. Current produced depended on the concentration of the catholyte. Over a period of time, biological reduction of catholytes lead to decrease in the metal concentrations, which demonstrated the application of MFC technology towards heavy metal treatment and recovery in a reasonably cost-effective manner.

Long-term bio-power of ceramic microbial fuel cells in individual and stacked configurations.

In order to improve the potential of Microbial Fuel Cells (MFCs) as an applicable technology, the main challenge is to engineer practical systems for bioenergy production at larger scales and to test how the prototypes withstand the challenges occurring during the prolonged operation under constant feeding regime with real waste stream. This work presents the performance assessment of low-cost ceramic MFCs in the individual, stacked (modular) and modular cascade (3 modules) configurations during long term operation up to 19 months, utilising neat human urine as feedstock. During 1 year, the performance of the individual MFC units reached up to 1.56 mW (22.3 W/m3), exhibiting only 20% power loss on day 350 which was significantly smaller in comparison to conventional proton or cation exchange membranes. The stack module comprising 22 MFCs reached up to 21.4 mW (11.9 W/m3) showing power recovery to the initial output levels after 580 days, whereas the 3-module cascade reached up to 75 mW (13.9 W/m3) of power, showing 20% power loss on day 446. In terms of chemical oxygen demand (COD) removal, the 3-module cascade configuration achieved a cumulative reduction of >92%, which is higher than that observed in the single module (56%).

Rapid detection of biodegradable organic matter in polluted water with microbial fuel cell sensor: Method of partial coulombic yield.

The quantification of biodegradable organic matter (BOM) in polluted water plays an essential role for biodegradation-based processing of wastewater and management of water environment. Compared with the traditional detection of five-day biochemical oxygen demand (BOD5), microbial fuel cell (MFC) sensors have shown an advantage for rapid and more accurate BOM assessment in several hours using coulombic yield of MFC as the signal. In this study, we propose a new calculation method that relies on the partial coulombic yield (P-CY) to further shorten the duration of the measurement. The P-CY is the cumulative coulomb at the point at which the voltage acquisition reaches a maximum voltage drop rate. The detection results with the standard GGA solution (a mixture of glucose and glutamic acid) show an enhanced linear relationship ranging from 37.5 mg L-1 to 375 mg L-1 in comparison to conventional methods. Notably, the response time for P-CY is remarkably shortened (0.99 ± 0.18-18.08 ± 0.58 h). The cutoff point for P-CY has more stable electrochemical characteristics, which enhances the accuracy of BOM detection. Furthermore, the validity of our determination of the cutoff point for P-CY is demonstrated by a mathematical model based on the Michaelis-Menten equation. Thus, the P-CY method is viable for the rapid detection of BOM in polluted water.

Functional group surface modifications for enhancing the formation and performance of exoelectrogenic biofilms on the anode of a bioelectrochemical system.

Various new energy technologies have been developed to reduce reliance on fossil fuels. The bioelectrochemical system (BES), an integrated microbial-electrochemical energy conversion process, is projected to be a sustainable and environmentally friendly energy technology. However, low power density is still one of the main limiting factors restricting the practical application of BESs. To enhance power output, functional group modification on anode surfaces has been primarily developed to improve the bioelectrochemical performances of BESs in terms of startup, power density, chemical oxygen demand (COD) removal and coulombic efficiency (CE). This modification could change the anode surface characteristics: roughness, hydrophobicity, biocompatibility, chemical bonding and electrochemically active surface area. This will facilitate bacterial adhesion, biofilm formation and extracellular electron transfer (EET). Additionally, some antibacterial functional groups are applied on air cathodes in order to suppress aerobic biofilms and enhance cathodic oxygen reduction reactions (ORRs). Various modification strategies such as: soaking, heat treatment and plasma modification have been reported to introduce functional groups typically as O-, N- and S-containing groups. In this review, the effects of anode functional groups on electroactive bacteria through the whole biofilm formation process are summarized. In addition, the application of those modification technologies to improve bioelectricity generation, resource recovery, bioelectrochemical analysis and the production of value-added chemicals and biofuels is also discussed. Accordingly, this review aims to help scientists select the most appropriate functional groups and up-to-date methods to improve biofilm formation.

Improved performance of microbial fuel cells using a gradient porous air cathode: An experiment and simulation study.

High carbon catalyst loadings are commonly used for the catalyst layer (CL) in air-cathodes to obtain a performance comparable with that using platinum. This results in a much thicker CL, which severely limits mass transfer. In this study, we developed a porosity-gradient CL to passively enhance mass transfer in the air-cathode of microbial fuel cells (MFCs) for the first time. Computational results demonstrated that a cathode CL with increasing porosity (CL-IP) and decreasing porosity (CL-DP) from the water to the air-facing side exhibited improved transport of oxygen and OH-, respectively, alleviating concentration overpotentials in the CL. Experimental results also showed that an MFC that included a cathode with CL-IP achieved a maximum power density of 1781 ±â€¯92 mW m-2, which was higher than that achieved with CL-DP and a homogeneous CL (1614 ±â€¯72 and 1183 ±â€¯205 mW m-2).

Nano-Fe3C@PGC as a novel low-cost anode electrocatalyst for superior performance microbial fuel cells.

We report a novel anode electrocatalyst, iron carbide nanoparticles dispersed in porous graphitized carbon (Nano-Fe3C@PGC), which is synthesized by facile approach involving a direct pyrolysis of ferrous gluconate and a following removal of free iron, but provides microbial fuel cells with superior performances. The physical characterizations confirm the unique configuration of iron carbide nanoparticles with porous graphitized carbon. Electrochemical measurements demonstrate that the as-synthesized Nano-Fe3C@PGC exhibits an outstanding electrocatalytic activity toward the charge transfer between bacteria and anode. Equipped with Nano-Fe3C@PGC, the microbial fuel cells based on a mixed bacterium culture yields a power density of 1856 mW m-2. The resulting excellent performance is attributed to the large electrochemical active area and the high electronic conductivity that porous graphitized carbon provides and the enriched electrochemically active microorganisms and enhanced activity towards the redox reactions in microorganisms by Fe3C nanoparticles.

Methanogenesis suppression in microbial fuel cell by aluminium dosing.

Reduction in power production due to loss of substrate to methanogens makes methanogenesis a serious performance limitation in microbial fuel cell (MFC). Aluminium (Al) due to its antibacterial properties easily affects the methanogens, which have a thinner cell membrane and slower growth rate. The effect of Al in suppressing methanogens was thus studied by adding 5 mg/L of aluminium sulphate in anolyte of the treated MFC (MFCT). Reduced COD removal efficiency of 86.11 ±â€¯1.3% was observed in MFCT which was lower than that observed (96.25 ±â€¯1.7%) in the control MFC (MFCC) operated without Al addition. An average volumetric power density of 1.84 ±â€¯0.40 W/m3 was observed in MFCT whereas the average volumetric power density observed in MFCC was 1.54 ±â€¯0.46 W/m3. An internal resistance of 195â€¯Ω was observed in MFCT, which was significantly lower than 349 Ω, as observed in MFCC. The coulombic efficiency (CE) of MFCT was found to be 2.5 times higher than the CE of MFCC. This improved performance of MFCT denoted better biocatalytic activity and electron transfer capability of anodic biofilm of MFCT than MFCC. Higher current generation during electrochemical analysis showed better electron discharge at the anode and lesser electron loss at the interface of electrode and electrolyte.

Low-cost nanowired α-MnO2/C as an ORR catalyst in air-cathode microbial fuel cell.

In this work, low cost α-MnO2 nanowires and α-MnO2 nanowires supported on carbon Vulcan (α-MnO2/C) have been synthesized via a simple and facile hydrothermal method for application in microbial fuel cells. The prepared samples have been characterized by X-ray diffraction (XRD), Raman spectroscopy and field emission scanning electron microscopy (FE-SEM). Electrocatalytic activities of the samples have been evaluated by means of cyclic voltammetry (CV), linear sweep voltammetry (LSV) and electrochemical impedance spectroscopy (EIS) in a neutral phosphate buffer solution. EIS was performed at different potentials to gain further insight into the kinetic properties of α-MnO2/C. Both catalysts were used in air cathode microbial fuel cells to achieve power densities of 180 and 111 mWm-2 for α-MnO2/C and pristine α-MnO2 nanowires, respectively. α-MnO2/C functions as a good and economical alternative for Pt free catalysts in practical MFC applications, as shown by the findings of stability test and voltage generation cycles in long-term operation of MFC.

Fabrication of highly effective hybrid biofuel cell based on integral colloidal platinum and bilirubin oxidase on gold support.

A hybrid biofuel cell (HBFC) is explored as a low-cost alternative to abiotic and enzymatic biofuel cells. Here the HBFC provides an enzymeless approach for the fabrication of the anodic electrode while employing an enzymatic approach for the fabrication of the cathodic electrode to develop energy harvesting platform to power bioelectronic devices. The anode employed 250 µm braided gold wire modified with colloidal platinum (Au-co-Pt) and bilirubin oxidase (BODx) modified gold coated Buckypaper (BP-Au-BODx) cathode. The functionalization of the gold coated multi-walled carbon nanotube (MWCNT) structures of the BP electrodes is achieved by 3-mercaptopropionic acid surface modification to possess negatively charged carboxylic groups and subsequently followed by EDC/Sulfo-NHS (1-Ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride and N-Hydroxysulfosuccinimide) crosslinking with BODx. The integration of the BODx and gold coated MWCNTs is evaluated for bioelectrocatalytic activity. The Au-co-Pt and BP-Au-BODx exhibited excellent electrocatalytic activity towards glucose oxidation with a linear dynamic range up to 20 mM glucose and molecular oxygen reduction, respectively. The HBFC demonstrated excellent performance with the largest open circuit voltages of 0.735 V and power density of 46.31 µW/cm2 in 3 mM glucose. In addition, the HBFC operating on 3 mM glucose exhibited excellent uninterrupted operational stability while continuously powering a small electronic device. These results provide great opportunities for implementing this simple but efficient HBFC to harvest the biochemical energy of target fuel(s) in diverse medical and environmental applications.

Architectural adaptations of microbial fuel cells.

Conventional wastewater treatment consumes a large amount of money worldwide for removal of pollutants prior to its discharge into water body or facilitating reuse. Decreasing energy expenditure during wastewater treatment and rather recovering some value-added products while treating wastewater is an important goal for researchers. Microbial fuel cells (MFCs) are representative bioelectrochemical systems, which offer energy-efficient wastewater treatment. MFCs convert chemical energy of organic matter into electrical energy by using biocatalytic activities. Although MFCs are not truly commercialized, they have potential to make energy-gaining wastewater treatment technologies and represent their capabilities successfully. Over the last decade, MFCs have developed remarkably in almost every dimension including wastewater treatment capabilities, power output, and cost optimization; however, its architectural design is an important consideration for scaling up. Here, we review various architectural advancements and technology up-gradation MFCs have experienced during its journey, to take this technology step forward for commercialization.

Bread-derived 3D macroporous carbon foams as high performance free-standing anode in microbial fuel cells.

Microbial fuel cells (MFCs) are a promising clean energy source to directly convert waste chemicals to available electric power. However, the practical application of MFCs needs the increased power density, enhanced energy conversion efficiency and reduced electrode material cost. In this study, three-dimensional (3D) macroporous N, P and S co-doped carbon foams (NPS-CFs) were prepared by direct pyrolysis of the commercial bread and employed as free-standing anodes in MFCs. As-obtained NPS-CFs have a large specific surface area (295.07 m2 g-1), high N, P and S doping level, and excellent electrical conductivity. A maximum areal power density of 3134 mW m-2 and current density of 7.56 A m-2 are generated by the MFCs equipped with as-obtained NPS-CF anodes, which is 2.57- and 2.63-fold that of the plain carbon cloth anodes (areal power density of 1218 mW m-2 and current density of 2.87 A m-2), respectively. Such improvement is explored to mainly originate from two respects: the good biocompatibility of NPS-CFs favors the bacterial adhesion and enrichment of electroactive Geobacter species on the electrode surface, while the high conductivity and improved bacteria-electrode interaction efficiently promote the extracellular electron transfer (EET) between the bacteria and the anode. This study provides a low-cost and sustainable way to fabricate high power MFCs for practical applications.

Enhancing Electricity Generation Using a Laccase-Based Microbial Fuel Cell with Yeast Galactomyces reessii on the Cathode.

The fungi associated with termites secrete enzymes such as laccase (multi-copper oxidase) that can degrade extracellular wood matrix. Laccase uses molecular oxygen as an electron acceptor to catalyze the degradation of organic compounds. Owing to its ability to transfer electrons from the cathodic electrode to molecular oxygen, laccase has the potential to be a biocatalyst on the surface of the cathodic electrode of a microbial fuel cell (MFC). In this study, a two-chamber MFC using the laccase-producing fungus Galactomyces reessii was investigated. The fungus cultured on coconut coir was placed in the cathode chamber, while an anaerobic microbial community was maintained in the anode chamber fed by industrial rubber wastewater and supplemented by sulfate and a pH buffer. The laccase-based biocathode MFC (lbMFC) produced the maximum open circuit voltage of 250 mV, output voltage of 145 mV (with a 1,000 Ω resistor), power density of 59 mW/m2, and current density of 278 mA/m2, and a 70% increase in half-cell potential. This study demonstrated the capability of laccase-producing yeast Galactomyces reessii as a biocatalyst on the cathode of the two-chamber lbMFC.

Exfoliated molybdenum di-sulfide (MoS2) electrode for hydrogen production in microbial electrolysis cell.

The most widely reported catalyst in microbial electrochemical cells (MEC) cathodes is platinum (Pt). The disadvantages of Pt include its high cost and sensitivity to various molecules. In this research an exfoliated molybdenum di-sulfide (MoS2-EF) catalyst was synthesized. The size of the obtained particles was 200 ±â€¯50 nm, 50-fold smaller than the pristine MoS2 catalyst. The MoS2-EF Raman spectrum displays the E12g and A1g peaks at 373 cm-1 and 399 cm-1. Electrochemical characterization by linear sweep voltammetry (LSV) of a rotating disc electrode RDE showed that the current density of Pt in 0.5 M H2SO4 was 3.3 times higher than MoS2-EF. However, in phosphate buffer (pH-7) electrolyte this ratio diminished to 1.9. The polarization curve of Pt, MoS2-EF and the pristine MoS2 electrodes, at -1.3 V in MEC configuration in abiotic conditions exhibit current densities of 17.46, 12.67 and 3.09 mA cm-2, respectively. Hydrogen evolution rates in the same MEC with a Geobacter sulfurreducens anode and Pt, MoS2-EF and the pristine MoS2 cathodes were 0.106, 0.133 and 0.083 m3 d-1 m-3, respectively. The results in this study show that MoS2-EF led to highly purified hydrogen and that this catalyst can serve as an electrochemical active and cost-effective alternative to Pt.

Binder materials for the cathodes applied to self-stratifying membraneless microbial fuel cell.

The recently developed self-stratifying membraneless microbial fuel cell (SSM-MFC) has been shown as a promising concept for urine treatment. The first prototypes employed cathodes made of activated carbon (AC) and polytetrafluoroethylene (PTFE) mixture. Here, we explored the possibility to substitute PTFE with either polyvinyl-alcohol (PVA) or PlastiDip (CPD; i.e. synthetic rubber) as binder for AC-based cathode in SSM-MFC. Sintered activated carbon (SAC) was also tested due to its ease of manufacturing and the fact that no stainless steel collector is needed. Results indicate that the SSM-MFC having PTFE cathodes were the most powerful measuring 1617 µW (11 W·m-3 or 101 mW·m-2). SSM-MFC with PVA and CPD as binders were producing on average the same level of power (1226 ±â€¯90 µW), which was 24% less than the SSM-MFC having PTFE-based cathodes. When balancing the power by the cost and environmental impact, results clearly show that PVA was the best alternative. Power wise, the SAC cathodes were shown being the less performing (≈1070 µW). Nonetheless, the lower power of SAC was balanced by its inexpensiveness. Overall results indicate that (i) PTFE is yet the best binder to employ, and (ii) SAC and PVA-based cathodes are promising alternatives that would benefit from further improvements.

Polyvinylidene fluoride effects on the electrocatalytic properties of air cathodes in microbial fuel cells.

The use of polyvinylidene fluoride (PVDF) as a binder was investigated in order to prepare the active carbon catalyst and carbon black diffusion layers of a microbial fuel cell cathode. Compared with other binders, PVDF performed competitively as it did not require a lengthy curing time and high curing temperature. Results of XRD characterization showed that the typical ß-PVDF was enhanced as PVDF content ratio increased. SEM results indicated that the catalyst layer easily peeled off due to the low binder concentration of binder, but the high binder content was deemed undesirable because the large amount of non-conductive PVDF interrupted the percolation path. The optimum binder concentration was double checked using Tafel and EIS tests. Results indicated that the cathode with 10% PVDF is the optimum operated concentration. The cathode can obtain 180mV of cathode potential and the smallest total impedance of 2500Ω, which are consistent with the SEM analysis. Moreover, the cathode with 10% PVDF concentration produced a maximum power density of 1600mWm-2, suggesting that PVDF can compete with other traditional binders.

Highly efficient charge transfer in Co/Co2P Schottky junctions embedded in nitrogen-doped porous carbon for enhancing bioelectricity generation.

Exploration of noble-metal free catalysts with high oxygen reduction reaction (ORR) activity and durability as alternatives for platinum/carbon (Pt/C) in microbial fuel cells (MFCs) remains a great challenge. This study reports the preparation of nitrogen-doped cobalt/cobalt phosphide/carbon (Co/Co2P/NC) catalysts via an in situ simultaneous doping/reduction method by using residual cornstalks as carbon source. Effects of carbonization temperature on structural characteristics and catalytic activity of Co/Co2P/NC catalysts are investigated. Co/Co2P/NC-850 with regular network structure obtains the maximum power density of 972 ± 5mWm-2, which is higher than that of Pt/C (808 ± 5mWm-2). The highest Coulombic efficiency (23.1%) and the lowest charge transfer resistance (0.93Ω) are also obtained by Co/Co2P/NC (850°C). ORR catalyzed by Co/Co2P/NC-850 is mainly via 4e- reduction pathway. The better durability of Co/Co2P/NC (850°C) is detected from long-term operation of MFCs. The promising catalytic activity for ORR is attributed to the introduction of Co/Co2P nanoparticles/Schottky junctions and N species in porous carbon skeleton, which are served as active sites to trap and consume electrons. Biomass-derived carbon with good electrical conductivity can provide large specific surface area and abundant interconnected holes, which contribute to efficient permeation and transport of O2. The synergistic effects between porous structure and sufficient active sites can energetically boost catalytic activity to improve ORR efficiency. These Co/Co2P/NC catalysts with durable power outputs are expected to have more extensive applications in MFCs.

Optimum spacing between electrodes in an air-cathode single chamber microbial fuel cell with a low-cost polypropylene separator.

The performance of a single chamber microbial fuel cell (MFC) with a low-cost polypropylene separator was investigated at various electrode interspaces in a separator electrode assembly (SEA). The lag period was shortened (3.74-0.17 days) and voltage generation was enhanced (0.2-0.5 V) as electrode spacing was increased from 0 to 9 mm. Power density was increased from 220 to 370 mW/m2 with increased spacing. The highest power density of 488 mW/m2 was obtained in polarization analysis with 6 mm. The oxygen mass transfer coefficients with 0 mm (K o = 3.69 × 10-5 cm/s) electrode spacing were 3.8 times higher than with 9 mm (K o = 0.96 × 10-5 cm/s) spacing. Columbic efficiency (CE) was increased from 5 to 32% due to less oxygen diffusion with increase in electrode spacing, but on contrary the ohmic resistance (R oh) was increased from 2 to 4 Ω. In a long-term operation (200 days), a gradual decrease in cathode potentials was observed in all electrode spacing as the main limiting factor of stable MFC performance.

Ultralight Cut-Paper-Based Self-Charging Power Unit for Self-Powered Portable Electronic and Medical Systems.

The development of lightweight, superportable, and sustainable power sources has become an urgent need for most modern personal electronics. Here, we report a cut-paper-based self-charging power unit (PC-SCPU) that is capable of simultaneously harvesting and storing energy from body movement by combining a paper-based triboelectric nanogenerator (TENG) and a supercapacitor (SC), respectively. Utilizing the paper as the substrate with an assembled cut-paper architecture, an ultralight rhombic-shaped TENG is achieved with highly specific mass/volume charge output (82 nC g-1/75 nC cm-3) compared with the traditional acrylic-based TENG (5.7 nC g-1/5.8 nC cm-3), which can effectively charge the SC (∼1 mF) to ∼1 V in minutes. This wallet-contained PC-SCPU is then demonstrated as a sustainable power source for driving wearable and portable electronic devices such as a wireless remote control, electric watch, or temperature sensor. This study presents a potential paper-based portable SCPU for practical and medical applications.

Design and Fabrication of a Dual-Photoelectrode Fuel Cell towards Cost-Effective Electricity Production from Biomass.

A photo fuel cell (PFC) offers an attractive way to simultaneously convert solar and biomass energy into electricity. Photocatalytic biomass oxidation on a semiconductor photoanode combined with dark electrochemical reduction of oxygen molecules on a metal cathode (usually Pt) in separated compartments is the common configuration for a PFC. Herein, we report a membrane-free PFC based on a dual electrode, including a W-doped BiVO4 photoanode and polyterthiophene photocathode for solar-stimulated biomass-to-electricity conversion. Air- and water-soluble biomass derivatives can be directly used as reagents. The optimal device yields an open-circuit voltage (VOC ) of 0.62 V, a short-circuit current density (JSC ) of 775 µA cm-2 , and a maximum power density (Pmax ) of 82 µW cm-2 with glucose as the feedstock under tandem illumination, which outperforms dual-photoelectrode PFCs previously reported. Neither costly separating membranes nor Pt-based catalysts are required in the proposed PFC architecture. Our work may inspire rational device designs for cost-effective electricity generation from renewable resources.