The use of electrochemical impedance spectroscopy (EIS) in the evaluation of the electrochemical properties of a microbial fuel cell.

Electrochemical impedance spectroscopy (EIS) has been used to determine several electrochemical properties of the anode and cathode of a mediator-less microbial fuel cell (MFC) under different operational conditions. These operational conditions included a system with and without the bacterial catalyst and EIS measurements at the open-circuit potential of the anode and the cathode or at an applied cell voltage. In all cases the impedance spectra followed a simple one-time-constant model (OTCM) in which the solution resistance is in series with a parallel combination of the polarization resistance and the electrode capacitance. Analysis of the impedance spectra showed that addition of Shewanella oneidensis MR-1 to a solution of buffer and lactate greatly increased the rate of the lactate oxidation at the anode under open-circuit conditions. The large decrease of open-circuit potential of the anode increased the cell voltage of the MFC and its power output. Measurements of impedance spectra for the MFC at different cell voltages resulted in determining the internal resistance (R(int)) of the MFC and it was found that R(int) is a function of cell voltage. Additionally, R(int) was equal to R(ext) at the cell voltage corresponding to maximum power, where R(ext) is the external resistance that must be applied across the circuit to obtain the maximum power output.

Electrodeposition of platinum-iridium alloy nanowires for hermetic packaging of microelectronics.

An electrodeposition technique was applied for fabrication of dense platinum-iridium alloy nanowires as interconnect structures in hermetic microelectronic packaging to be used in implantable devices. Vertically aligned arrays of platinum-iridium alloy nanowires with controllable length and a diameter of about 200 nm were fabricated using a cyclic potential technique from a novel electrodeposition bath in nanoporous aluminum oxide templates. Ti/Au thin films were sputter deposited on one side of the alumina membranes to form a base material for electrodeposition. Scanning Electron Microscopy (SEM) and Energy Dispersive Spectroscopy (EDS) were used to characterize the morphology and the chemical composition of the nanowires, respectively. SEM micrographs revealed that the electrodeposited nanowires have dense and compact structures. EDS analysis showed a 60:40% platinum-iridium nanowire composition. Deposition rates were estimated by determining nanowire length as a function of deposition time. High Resolution Transmission Electron Microscopy (HRTEM) images revealed that the nanowires have a nanocrystalline structure with grain sizes ranging from 3 nm to 5 nm. Helium leak tests performed using a helium leak detector showed leak rates as low as 1 × 10(-11) mbar L s(-1) indicating that dense nanowires were electrodeposited inside the nanoporous membranes. Comparison of electrical measurements on platinum and platinum-iridium nanowires revealed that platinum-iridium nanowires have improved electrical conductivity.

Electricity generation from a floating microbial fuel cell.

A floating microbial fuel cell (FMFC) has been designed and its performance has been evaluated for 153 days. The power output gradually increased to a maximum value of 390 mW/m(3) at 125 days. The polarization resistance of the anode (R(p)(a)) changed with operating time reaching a minimum value at 125 days, while the polarization resistance of the cathode (R(p)(c)) was relatively constant and much smaller than R(p)(a). It has been demonstrated that the observed changes of the internal resistance (R(int)) and the maximum power (P(max)) with exposure time were mainly due to the changes of R(p)(a). Compared with sediment MFCs for which the anode is embedded in marine or river sediments, the application of the FMFC, which could be installed in a buoy, is not limited by the depth of the ocean. The FMFC has the potential to supply electricity to low-power consuming electronic devices at remote locations.

Surface modification of neural stimulating/recording electrodes with high surface area platinum-iridium alloy coatings.

High-surface area platinum-iridium alloys were electrodeposited by on Pt and Au microelectrodes using a potential sweep technique. Detailed investigations of the structure and morphology and the electrochemical properties of the electrodeposited Pt-Ir alloy coatings were performed. Scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS) were used for the determination of the surface morphology and the chemical composition of the Pt-Ir coatings, respectively. The elemental analysis by EDS showed a nearly 60-40% Pt-Ir composition of the coatings. The electrochemical properties of the Pt-Ir coatings were evaluated using cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). CV and EIS measurements revealed that the Pt-Ir coated electrodes exhibit significantly increased charge storage capacity and real surface area compared to uncoated Pt electrodes. Charge injection experiments of the Pt-Ir coated microelectrodes revealed low potential excursions, indicating high charge injection capabilities within safe potential limits.

Performance of microbial fuel cells with and without Nafion solution as cathode binding agent.

The performance of tubular microbial fuel cells (MFC) with and without Nafion solution as binding agent for the cathode catalyst preparation was investigated using different electrochemical techniques. The current output of both types of MFCs was monitored as a function of time using an external resistor. The current did not change much with time and was higher for the water cell (WC) than for the Nafion cell (NC). Cell voltage (U(c))-current (I) curves were recorded using a potentiodynamic technique. From the U(c)-I curves power concentration (P)-I and P-U(c) curves were constructed. The water cell (without Nafion) also achieved a higher maximum power output. The internal resistance that was determined from the cell voltage at which the power concentration reached its maximum value was higher for the NC than that for the WC, possibly due to the higher cathodic polarization resistance of the NC cell. The impedance for the cathodes decreased with exposure time for both cells due to increased porosity of the surface layers covering the cathode materials. No changes of the impedance were observed for the WC anode. For the NC anode the impedance spectra changed from a one-time constant system to a two-time constant system at the longer exposure time.

Self-sustained phototrophic microbial fuel cells based on the synergistic cooperation between photosynthetic microorganisms and heterotrophic bacteria.

A sediment-type self-sustained phototrophic microbial fuel cell (MFC) was developed to generate electricity through the synergistic interaction between photosynthetic microorganisms and heterotrophic bacteria. Under illumination, the MFC continuously produced electricity without the external input of exogenous organics or nutrients. The current increased in the dark and decreased with the light on, possibly because of the negative effect of the oxygen produced via photosynthesis. Continuous illumination inhibited the current production while the continuous dark period stimulated the current production. Extended darkness resulted in a decrease of current, probably because of the consumption of the organics accumulated during the light phase. Using color filters or increasing the thickness of the sediment resulted in a reduction of the oxygen-induced inhibition. Molecular taxonomic analysis revealed that photosynthetic microorganisms including cyanobacteria and microalgae predominated in the water phase, adjacent to the cathode and on the surface of the sediment. In contrast, the sediments were dominated by heterotrophic bacteria, becoming less diverse with increasing depth. In addition, results from the air-cathode phototrophic MFC confirmed the light-induced current production while the test with the two-chamber MFC (in the dark) indicated the presence of electricigenic bacteria in the sediment.

Electricity production coupled to ammonium in a microbial fuel cell.

The production of electricity from ammonium was examined using a rotating-cathode microbial fuel cell (MFC). The addition of ammonium chloride, ammonium sulfate, or ammonium phosphate (monobasic) resulted in electricity generation, while adding sodium chloride, nitrate, or nitrite did not cause any increase in current production. The peak current increased with increasing amount of ammonium addition up to 62.3 mM of ammonium chloride, suggesting that ammonium was involved in electricity generation either directly as the anodic fuel or indirectly as substrates for nitrifiers to produce organic compounds for heterotrophs. Adding nitrate or nitrite with ammonium increased current production compared to solely ammonium addition. Using 16S rRNA-linked molecular analyses, we found ammonium-oxidizing bacteria and denitrifying bacteria on both the anode and cathode electrodes, whereas no anammox bacteria were detected. The dominant ammonium-oxidizing bacteria were closely related to Nitrosomonas europaea. The present MFC achieved an ammonium removal efficiency of 49.2 +/- 5.9 or 69.7 +/- 3.6%, depending on hydraulic retention time, but exhibited a very low Coulombic efficiency.

Effect of electrolyte pH on the rate of the anodic and cathodic reactions in an air-cathode microbial fuel cell.

The measurement of electricity generation from an air-cathode microbial fuel cell (MFC) with a mixed bacteria culture at different pH showed that this MFC could tolerate an initial (feed solution) pH as high as 10. The optimal initial pH was between 8 and 10 with higher current generation compared to lower or higher pH. The bacterial metabolism exhibited a buffer effect and changed the electrolyte pH. The impedance spectra of the anode and cathode of the MFC at the open-circuit potential (OCP) revealed that the anodic microbial process preferred a neutral pH and microbial activities decreased at higher or lower pH; while the cathodic reaction was improved with increasing pH.

Current production and metal oxide reduction by Shewanella oneidensis MR-1 wild type and mutants.

Shewanella oneidensis MR-1 is a gram-negative facultative anaerobe capable of utilizing a broad range of electron acceptors, including several solid substrates. S. oneidensis MR-1 can reduce Mn(IV) and Fe(III) oxides and can produce current in microbial fuel cells. The mechanisms that are employed by S. oneidensis MR-1 to execute these processes have not yet been fully elucidated. Several different S. oneidensis MR-1 deletion mutants were generated and tested for current production and metal oxide reduction. The results showed that a few key cytochromes play a role in all of the processes but that their degrees of participation in each process are very different. Overall, these data suggest a very complex picture of electron transfer to solid and soluble substrates by S. oneidensis MR-1.