Effect of microbial fuel cell operation time on the disinfection efficacy of electrochemically synthesised catholyte from urine.

Microbial fuel cells (MFCs) offer an excellent solution to tackle some of the major challenges currently faced by humankind: sustainable energy sources, waste management and water stress. Besides treating wastewater and producing useful electricity from urine, ceramic MFCs can also generate biocidal catholyte in-situ. It has been proved that the electricity generation from the MFCs has a high impact in the catholyte composition. Therefore, the catholyte composition constantly changes while electricity is generated. However, these changes in catholyte composition with time has not yet been studied and that could highly contribute to the disinfection efficacy. In this work, the evolution of the catholyte generation and composition with the MFC operation time has been chemically and microbiologically evaluated, during 42 days. The results show an increase in pH and conductivity with the operation time, reaching pH 11.5. Flow cytometry and luminometer analyses of bioluminescent pathogenic E. coli exposed to the synthesised catholyte revealed killing properties against bacterial cells. A bio-electrochemical system, capable of electricity generation and simultaneous production of bactericidal catholyte from human urine is presented. The possibility to electrochemically generate in-situ a bacterial killing agent from urine, offers a great opportunity for water reuse and resource recovery for practical implementations.

Effect of iron oxide content and microstructural porosity on the performance of ceramic membranes as microbial fuel cell separators.

Ceramic materials based on naturally occurring clays are a low cost and environmentally friendly alternative to commercial polymer-based membranes in bioelectrochemical systems. In this work, ceramic membranes containing different amounts of iron oxide (1.06, 2.76 and 5.75 vol.%) and sintered at different temperatures (1100, 1200 and 1300 °C) have been elaborated and tested as separators in urine-fed microbial fuel cells (MFCs). The results reveal that the presence of iron oxide in the ceramic membrane composition increases the structural porosity and reduces the pore size for the three temperatures investigated. On the other hand, it was also observed that the iron content mitigates the negative effect of the high sintering temperature on the power performance of the MFCs. In the case of the ceramic membranes sintered at 1300 °C, power output improved ca. 10-fold when the iron oxide content in the membrane increased from 1.06 up to 5.75 vol.% (30.9 and 286.6 µW, respectively). Amongst the different combinations of iron phase content and sintering temperatures, the maximum power output was obtained by MFCs working with separators containing 5.75 vol. % of iron oxide and sintered at 1100 °C (1.045 mW). Finally, the system was stable for 65 days, which supports the long-term functionality of the different materials assessed.

Evaluation of artificial neural network algorithms for predicting the effect of the urine flow rate on the power performance of microbial fuel cells.

Microbial fuel cell (MFC) power performance strongly depends on the biofilm growth, which in turn is affected by the feed flow rate. In this work, an artificial neural network (ANN) approach has been used to simulate the effect of the flow rate on the power output by ceramic MFCs fed with neat human urine. To this aim, three different second-order algorithms were used to train our network and then compared in terms of prediction accuracy and convergence time: Quasi-Newton, Levenberg-Marquardt, and Conjugate Gradient. The results showed that the three training algorithms were able to accurately simulate power production. Amongst all of them, the Levenberg-Marquardt was the one that presented the highest accuracy (R = 95%) and the fastest convergence (7.8 s). These results show that ANNs are useful and reliable tools for predicting energy harvesting from ceramic-MFCs under changeable flow rate conditions, which will facilitate the practical deployment of this technology.

Improving the power performance of urine-fed microbial fuel cells using PEDOT-PSS modified anodes.

The need for improving the energy harvesting from Microbial Fuel Cells (MFCs) has boosted the design of new materials in order to increase the power performance of this technology and facilitate its practical application. According to this approach, in this work different poly(3,4-ethylenedioxythiophene)-polystyrenesulfonate (PEDOT-PSS) modified electrodes have been synthesised and evaluated as anodes in urine-fed MFCs. The electrochemical synthesis of PEDOT-PSS was performed by potentiostatic step experiments from aqueous solution at a fixed potential of 1.80 V (vs. a reversible hydrogen electrode) for different times: 30, 60, 120 and 240 s. Compared with other methods, this technique allowed us not only to reduce the processing time of the electrodes but also better control of the chemical composition of the deposited polymer and therefore, obtain more efficient polymer films. All modified anodes outperformed the maximum power output by MFCs working with the bare carbon veil electrode but the maximum value was observed when MFCs were working with the PEDOT-PSS based anode obtained after 30 s of electropolymerisation (535.1 µW). This value was 24.3% higher than using the bare carbon veil electrode. Moreover, the functionality of the PEDOT-PSS anodes was reported over 90 days working in continuous mode.

Optimisation of the internal structure of ceramic membranes for electricity production in urine-fed microbial fuel cells.

The need to find a feasible alternative to commercial membranes for microbial fuel cells (MFCs) poses an important challenge for the practical implementation of this technology. This work aims to analyse the influence of the internal structure of low-cost terracotta clay-based membranes on the behaviour of MFCs. To this purpose, 9 different combinations of temperature and time were used to prepare 27 MFC separators. The results show that the temperature has a significant effect on both porosity and pore size distribution, whereas the ramp time do not show a significant influence on these parameters. It was observed that kilning temperatures higher than 1030 °C dramatically reduce the porosity of the samples, reaching a minimum value of 16.85%, whereas the pore size increases as the temperature also increases. Among the membranes with similar porosities, those with a medium pore size distribution exhibited the lowest bulk resistance allowing MFCs to reach the highest power output (94.67 µW cm-2). These results demonstrate the importance of not only the porosity but also the pore size distribution of the separator in terms of MFC performance and longevity, which for these experiments was for 90 days.

Modelling the energy harvesting from ceramic-based microbial fuel cells by using a fuzzy logic approach.

Microbial fuel cells (MFCs) is a promising technology that is able to simultaneously produce bioenergy and treat wastewater. Their potential large-scale application is still limited by the need of optimising their power density. The aim of this study is to simulate the absolute power output by ceramic-based MFCs fed with human urine by using a fuzzy inference system in order to maximise the energy harvesting. For this purpose, membrane thickness, anode area and external resistance, were varied by running a 27-parameter combination in triplicate with a total number of 81 assays performed. Performance indices such as R2 and variance account for (VAF) were employed in order to compare the accuracy of the fuzzy inference system designed with that obtained by using nonlinear multivariable regression. R2 and VAF were calculated as 94.85% and 94.41% for the fuzzy inference system and 79.72% and 65.19% for the nonlinear multivariable regression model, respectively. As a result, these indices revealed that the prediction of the absolute power output by ceramic-based MFCs of the fuzzy-based systems is more reliable than the nonlinear multivariable regression approach. The analysis of the response surface obtained by the fuzzy inference system determines that the maximum absolute power output by the air-breathing set-up studied is 450  µ W when the anode area ranged from 160 to 200 cm2, the external loading is approximately 900 Ω and a membrane thickness of 1.6 mm, taking into account that the results also confirm that the latter parameter does not show a significant effect on the power output in the range of values studied.

Response of ceramic microbial fuel cells to direct anodic airflow and novel hydrogel cathodes.

The presence of air in the anode chamber of microbial fuel cells (MFCs) might be unavoidable in some applications. This study purposely exposed the anodic biofilm to air for sustained cycles using ceramic cylindrical MFCs. A method for improving oxygen uptake at the cathode by utilising hydrogel was also trialled. MFCs only dropped by 2 mV in response to the influx of air. At higher air-flow rates (up to 1.1 L/h) after 43-45 h, power did eventually decrease because chemical oxygen demand (COD) was being consumed (up to 96% reduction), but recovered immediately with fresh feedstock, highlighting no permanent damage to the biofilm. Two months after the application of hydrogel to the cathode chamber, MFC power increased 182%, due to better contact between cathode and ceramic surface. The results suggest a novel way of improving MFC performance using hydrogels, and demonstrates the robustness of the electro-active biofilm both during and following exposure to air.

Towards the optimisation of ceramic-based microbial fuel cells: A three-factor three-level response surface analysis design.

Microbial fuel cells (MFCs) are an environment-friendly technology, which addresses two of the most important environmental issues worldwide: fossil fuel depletion and water scarcity. Modelling is a useful tool that allows us to understand the behaviour of MFCs and predict their performance, yet the number of MFC models that could accurately inform a scale-up process, is low. In this work, a three-factor three-level Box-Behnken design is used to evaluate the influence of different operating parameters on the performance of air-breathing ceramic-based MFCs fed with human urine. The statistical analysis of the 45 tests run shows that both anode area and external resistance have more influence on the power output than membrane thickness, in the range studied. The theoretical optimal conditions were found at a membrane thickness of 1.55 mm, an external resistance of 895.59â€¯Ω and an anode area of 165.72 cm2, corresponding to a maximum absolute power generation of 467.63 µW. The accuracy of the second order model obtained is 88.6%. Thus, the three-factor three-level Box-Behnken-based model designed is an effective tool which provides key information for the optimisation of the energy harvesting from MFC technology and saves time in terms of experimental work.

A New Method for Modulation, Control and Power Boosting in Microbial Fuel Cells.

Microbial fuel cells (MFCs) are energy transducers, which through the metabolic reactions of facultative anaerobic microorganisms, transform the energy in organic matter directly into electricity. Extrinsic parameters such as hydraulic retention time, fuel quality (type and concentration) and physicochemical environment of electrodes and biofilms (e.g., temperature, pH, salinity, and redox), can all influence system efficiency. This work proposes that MFCs can be "fine-tuned" by adjustment of any of the physicochemical conditions including redox potential; in this context, an entirely novel method was investigated as a practical means of tuning, modulating and monitoring the redox potential within the electrode chambers. The method uses additional electrodes - known as 3rd and 4th-pins for anode and cathode chambers, respectively - which can be used in individual units, modules, cascades or stacks, for optimising the production of a large variety of chemicals, as well as biomass, water and power. The results have shown that the power output modulation resulted in an up to 79% and 33% increase, when connected via 3rd and 4th pins, respectively. Apart from power improvement, this study also demonstrated a method of open circuit potential (OCP) sensing, by using the same additional electrodes to both monitor and control the MFC signal in real time.

Microalgae as substrate in low cost terracotta-based microbial fuel cells: Novel application of the catholyte produced.

In this work, the by-product generated during the operation of cylindrical MFCs, made out of terracotta material, is investigated as a feasible means of degrading live microalgae for the first time. In addition to the low cost materials of this design, the reuse of the solution produced in the cathode renders the technology truly green and capable of generating bioenergy. In this study, the effect of a light/dark cycle or dark conditions only on the digestion of live microalgae with the catholyte is investigated. The results show that a combination of light/dark improves degradation and allows algae to be used as substrate in the anode. The addition of 12.5mL of a 1:1 mix of catholyte and microalgae (pre-digested over 5days under light/dark) to the anode, increases the power generation from 7µW to 44µW once all the organic matter in the anode had been depleted.

Self sufficient wireless transmitter powered by foot-pumped urine operating wearable MFC.

The first self-sufficient system, powered by a wearable energy generator based on microbial fuel cell (MFC) technology is introduced. MFCs made from compliant material were developed in the frame of a pair of socks, which was fed by urine via a manual gaiting pump. The simple and single loop cardiovascular fish circulatory system was used as the inspiration for the design of the manual pump. A wireless programmable communication module, engineered to operate within the range of the generated electricity, was employed, which opens a new avenue for research in the utilisation of waste products for powering portable as well as wearable electronics.

Intermittent load implementation in microbial fuel cells improves power performance.

This study reports on the response of small-scale MFCs to intermittent loading, in terms of power output over time. The aim was to understand the evolution with time of power output under different duty cycles, in conditions close to practical implementation. Inexpensive ceramic membranes were compared to cation exchange membranes, under continuous flow and with a pre-digester connected. Results show that at the minute-scale, all the duty cycles investigated, produced 78% higher power bursts from the MFCs (500µW) than when under continuous loading (280µW). These results were recorded from MFCs employing ceramic membranes, whereas the difference in performance for MFCs employing commercially available cation-exchange-membranes was insignificant. When normalising to daily energy production, only specific duty cycles produced more power than continuous loading. Furthermore, the introduction of a pre-digester increased the MFC power outputs 10-fold, thus confirming that separating fermentation from electro-active respiration, significantly enhances the system performance.

Bi-directional electrical characterisation of microbial fuel cell.

The electrical performance of microbial fuel cells in steady-state is usually investigated by standard characterisation methods that reveal many important parameters e.g. maximum power. This paper introduces a novel "bi-directional" method to study how the acquisition parameters (i.e. sweep rate and sweep regime) can influence measurements and consequently performance estimations. The investigation exhibited considerable differences (hysteresis) between the forward and backward characterisation regimes, indicating a difficulty to reach steady-state under certain conditions. Moreover, it is found that fast sweep rates (time-step of 2 min) can lead to an overestimation of the short-circuit currents, while prolonged operation with high external loads leads to maximum power overestimation and extended conditioning at high currents can result in its underestimation.

Effects of sulphate addition and sulphide inhibition on microbial fuel cells.

The effects of adding sulphate in: (i) standard activated sludge microbial fuel cells (MFCs) and (ii) larger-scale leachate-treating columns - both as individual units and as a system connected in cascade - are reported. S-replete power output was ∼2-fold higher than that of the S-deplete MFC. Furthermore, the effects of evolved sulphide (S(2-)) inhibition were investigated. The overall decrease in power output from the sulphide inhibitor (Na(2)MoO(4)) additions was 83% for the S-replete and 90% for the S-deplete. The second phase with the leachate treating units shows an improvement of 32-86% (depended on leachate strength) in current output as a result of adding sulphate. When leachate column MFCs were connected fluidically in series, the amount of Na(2)SO(4) made available downstream was decreasing (increase in power was 99%, 40% and 12% for columns in cascade). Results demonstrated the beneficial effects of added sulphur sources to both activated sludge and leachate-treating MFCs.

Improved energy output levels from small-scale Microbial Fuel Cells.

This study reports on the findings from the investigation into small-scale (6.25 mL) MFCs, connected together as a network of multiple units. The MFCs contained unmodified (no catalyst) carbon fibre electrodes and for initial and later experiments, a standard ion-exchange membrane for the proton transfer from the anode to the cathode. The anode microbial culture was of the type commonly found in domestic wastewater fed with 5 mM acetate as the carbon-energy (C/E) source. The cultures were mature and acclimatised in the MFC environment for approximately 2 months before being re-inoculated in the experimental MFC units. The cathode was of the O(2) diffusion open-to-air type, but for the purposes of the polarization experiments, the cathodic electrodes were moistened with ferricyanide. The main aim of this study was to investigate the effects of connecting multiples of MFC units together as a method of scale up by using stacks and comparison of the effects of different PEM and MFC structural materials on the performance. Impedance matching (maximum-power-transfer) was achieved through calculation of total internal impedance. Three different PEM materials were compared in otherwise identical MFCs in sets of three. For individual isolated MFCs, Hyflon E87-03 was shown to produce twice, whilst E87-10 produced approximately 1.5 times the power output of the control (standard) PEM. However, when MFCs containing the E87-03 and E87-10 membranes were connected in a stack, the system suffered from severe instability and cell reversal. To study the effects of the various polymeric MFC structural materials, four small-scale units were manufactured from three different types of RP material; acrylo-butadiene-styrene coated (ABS), ABS coated (ABS-MEK) and polycarbonate (polyC). The stack of four (4) units prototyped out of polyC produced the highest power density values in polarisation experiments (80 mW/m(2)).