Annemiek ter Heijne

Copper Recovery Combined with Electricity Production in a Microbial Fuel Cell

A metallurgical microbial fuel cell (MFC) is an attractive alternative for recovery of copper from copper containing waste streams, as the metal is recovered in its metallic form at the cathode, while the energy for metal reduction can be obtained from oxidation of organic materials at the anode with possible additional production of electricity. We studied the recovery of copper in an MFC using a bipolar membrane as a pH separator. Under anaerobic conditions, the maximum power density was 0.43 W/m(2) at a current density of 1.7 A/m(2). In the presence of oxygen, MFC performance improved considerably to a maximum power density of 0.80 W/m(2) at a current density of 3.2 A/m(2). Pure copper crystals were formed on the cathode, and no CuO or Cu(2)O was detected. Removal efficiencies of >99.88% were obtained. The cathodic recovery of copper compared to the produced electricity was 84% (anaerobic) and 43% (aerobic). The metallurgy MFC with the Cu(2+) reducing cathode further enlarges the application range of MFCs.

New applications and performance of bioelectrochemical systems

Bioelectrochemical systems (BESs) are emerging technologies which use microorganisms to catalyze the reactions at the anode and/or cathode. BES research is advancing rapidly, and a whole range of applications using different electron donors and acceptors has already been developed. In this mini review, we focus on technological aspects of the expanding application of BESs. We will analyze the anode and cathode half-reactions in terms of their standard and actual potential and report the overpotentials of these half-reactions by comparing the reported potentials with their theoretical potentials. When combining anodes with cathodes in a BES, new bottlenecks and opportunities arise. For application of BESs, it is crucial to lower the internal energy losses and increase productivity at the same time. Membranes are a crucial element to obtain high efficiencies and pure products but increase the internal resistance of BESs. The comparison between production of fuels and chemicals in BESs and in present production processes should gain more attention in future BES research. By making this comparison, it will become clear if the scope of BESs can and should be further developed into the field of biorefineries.

Bioelectrochemical Systems: An Outlook for Practical Applications

Bioelectrochemical systems (BESs) hold great promise for sustainable production of energy and chemicals. This review addresses the factors that are essential for practical application of BESs. First, we compare benefits (value of products and cleaning of wastewater) with costs (capital and operational costs). Based on this, we analyze the maximum internal resistance (in mΩ m(2) ) and current density that is required to make microbial fuel cells (MFCs) and hydrogen-producing microbial electrolysis cells (MECs) cost effective. We compare these maximum resistances to reported internal resistances and current densities with special focus on cathodic resistances. Whereas the current densities of MFCs still need to be increased considerably (i.e., internal resistance needs to be decreased), MECs are closer to application as their current densities can be increased by increasing the applied voltage. For MFCs, the production of high-value products in combination with electricity production and wastewater treatment is a promising route.

Butler–Volmer–Monod model for describing bio-anode polarization curves

A kinetic model of the bio-anode was developed based on a simple representation of the underlying biochemical conversions as described by enzyme kinetics, and electron transfer reactions as described by the Butler-Volmer electron transfer kinetics. This Butler-Volmer-Monod model was well able to describe the measured bio-anode polarization curves. The Butler-Volmer-Monod model was compared to the Nernst-Monod model described the experimental data significantly better. The Butler-Volmer-Monod model has the Nernst-Monod model as its full electrochemically reversible limit. Contrary to the Nernst-Monod model, the Butler-Volmer-Monod model predicts zero current at equilibrium potential. Besides, the Butler-Volmer-Monod model predicts that the apparent Monod constant is dependent on anode potential, which was supported by experimental results.

Carbon dioxide reduction by mixed and pure cultures in microbial electrosynthesis using an assembly of graphite felt and stainless steel as a cathode

Carbon dioxide (CO2) reduction to multi-carbon compounds at the cathode using chemolithoautotrophs is an emerging application of microbial electrosynthesis (MES). In this study, CO2 reduction in MES was investigated at hydrogen evolving potentials, separately by a mixed culture and Clostridium ljungdahlii, using a graphite felt and stainless steel assembly as cathode. The mixed culture reactor produced acetate at the maximum rate of 1.3 mM d(-1), along with methane and hydrogen at -1.1 V/Ag/AgCl. Over 160 days of run-time in four fed-batches, 26% of bicarbonate was converted to acetate between day 28 and 41, whereas in the late batches, methane production prevailed. Out of 45 days of run-time in the C. ljungdahlii reactor, 2.4 mM d(-1) acetate production was achieved at -0.9 V/Ag/AgCl in Batch 1. Simultaneous product degradation occurred when the mixed culture was not selectively enriched. Hydrogen evolution is potentially the rapid way of transferring electrons to the biocatalysts for higher bioproduction rates.

Microbial Community Analysis of a Methane-Producing Biocathode in a Bioelectrochemical System

A methane-producing biocathode that converts CO2 into methane was studied electrochemically and microbiologically. The biocathode produced methane at a maximum rate of 5.1 L CH4/m2 projected cathode per day (1.6 A/m2) at −0.7 V versus NHE cathode potential and 3.0 L CH4/m2 projected cathode per day (0.9 A/m2) at −0.6 V versus NHE cathode potential. The microbial community at the biocathode was dominated by three phylotypes of Archaea and six phylotypes of bacteria. The Archaeal phylotypes were most closely related to Methanobacterium palustre and Methanobacterium aarhusense. Besides methanogenic Archaea, bacteria seemed to be associated with methane production, producing hydrogen as an intermediate. Biomass density varied greatly with part of the carbon electrode covered with a dense biofilm, while only clusters of cells were found on other parts. Based on our results, we discuss how inoculum enrichment and changing operational conditions may help to increase biomass density and to select for microorganisms that produce methane.

Bioelectrochemical Power-to-Gas: State of the Art and Future Perspectives

Bioelectrochemical power-to-gas (BEP2G) is considered a potentially convenient way of storing renewable surplus electricity in the form of methane. In methane-producing bioelectrochemical systems (BESs), carbon dioxide and electrical energy are converted into methane, using electrodes that supply either electrons or hydrogen to methanogenic archaea. This review summarizes the performance of methane-producing BESs in relation to cathode potential, electrode materials, operational strategies, and inoculum. Analysis and estimation of energy input and production rates show that BEP2G may become an attractive alternative for thermochemical methanation, and biochemical methanogenesis. To determine if BEP2G can become a future power-to-gas technology, challenges relating to cathodic energy losses, choice of a suitable electron donor, efficient reactor design/operation, and experience with large reactors need to be overcome.

Microbial Communities and Electrochemical Performance of Titanium-Based Anodic Electrodes in a Microbial Fuel Cell

ABSTRACT Four types of titanium (Ti)-based electrodes were tested in the same microbial fuel cell (MFC) anodic compartment. Their electrochemical performances and the dominant microbial communities of the electrode biofilms were compared. The electrodes were identical in shape, macroscopic surface area, and core material but differed in either surface coating (Pt- or Ta-coated metal composites) or surface texture (smooth or rough). The MFC was inoculated with electrochemically active, neutrophilic microorganisms that had been enriched in the anodic compartments of acetate-fed MFCs over a period of 4 years. The original inoculum consisted of bioreactor sludge samples amended with Geobacter sulfurreducens strain PCA. Overall, the Pt- and Ta-coated Ti bioanodes (electrode-biofilm association) showed higher current production than the uncoated Ti bioanodes. Analyses of extracted DNA of the anodic liquid and the Pt- and Ta-coated Ti electrode biofilms indicated differences in the dominant bacterial communities. Biofilm formation on the uncoated electrodes was poor and insufficient for further analyses. Bioanode samples from the Pt- and Ta-coated Ti electrodes incubated with Fe(III) and acetate showed several Fe(III)-reducing bacteria, of which selected species were dominant, on the surface of the electrodes. In contrast, nitrate-enriched samples showed less diversity, and the enriched strains were not dominant on the electrode surface. Isolated Fe(III)-reducing strains were phylogenetically related, but not all identical, to Geobacter sulfurreducens strain PCA. Other bacterial species were also detected in the system, such as a Propionicimonas-related species that was dominant in the anodic liquid and Pseudomonas-, Clostridium-, Desulfovibrio-, Azospira-, and Aeromonas-related species.

High rate copper and energy recovery in microbial fuel cells.

Bioelectrochemical systems (BESs) are a novel, promising technology for the recovery of metals. The prerequisite for upscaling from laboratory to industrial size is that high current and high power densities can be produced. In this study we report the recovery of copper from a copper sulfate stream (2 g L-1 Cu2+) using a laboratory scale BES at high rate. To achieve this, we used a novel cell configuration to reduce the internal voltage losses of the system. At the anode, electroactive microorganisms produce electrons at the surface of an electrode, which generates a stable cell voltage of 485 mV when combined with a cathode where copper is reduced. In this system, a maximum current density of 23 A m-2 in combination with a power density of 5.5 W m-2 was produced. XRD analysis confirmed 99% purity in copper of copper deposited onto cathode surface. Analysis of voltage losses showed that at the highest current, most voltage losses occurred at the cathode, and membrane, while anode losses had the lowest contribution to the total voltage loss. These results encourage further development of BESs for bioelectrochemical metal recovery.

Feasibility Study on Electrochemical Impedance Spectroscopy for Microbial Fuel Cells: Measurement Modes & Data Validation

Electrochemical impedance spectroscopy (EIS) is in potential a powerful tool for the in depth analysis of microbial fuels cells (MFCs). To prevent the risk of drawing false conclusions from invalid EIS measurements we investigated the feasibility of this method on an MFC by checking: linearity, causality, stability and finiteness. EIS application under steady state conditions was partly feasible. For further application EIS on MFCs we recommend to: (1) use the constant anode or cathode potential measurement mode with a fast couple at the counter electrode; (2) record the polarization curve and measure at different amplitudes to check the linearity condition; (3) perform preliminary measurements to reveal measurement presets; (4) apply prolonged pretreatment to facilitate the stability criterion; (5) perform duplicate measurements to examine the stability; (6) use a broad frequency range to validate the finiteness criterion; (7) use a statistical based validation check based on the Kramers-Kronig transformation.