Oxygen-reducing biocathodes operating with passive oxygen transfer in microbial fuel cells.

Oxygen-reducing biocathodes previously developed for microbial fuel cells (MFCs) have required energy-intensive aeration of the catholyte. To avoid the need for aeration, the ability of biocathodes to function with passive oxygen transfer was examined here using air cathode MFCs. Two-chamber, air cathode MFCs with biocathodes produced a maximum power density of 554 ± 0 mW/m(2), which was comparable to that obtained with a Pt cathode (576 ± 16 mW/m(2)), and 38 times higher than that produced without a catalyst (14 ± 3 mW/m(2)). The maximum current density with biocathodes in this air-cathode MFC was 1.0 A/m(2), compared to 0.49 A/m(2) originally produced in a two-chamber MFC with an aqueous cathode (with cathode chamber aeration). Single-chamber, air-cathode MFCs with the same biocathodes initially produced higher voltages than those with Pt cathodes, but after several cycles the catalytic activity of the biocathodes was lost. This change in cathode performance resulted from direct exposure of the cathodes to solutions containing high concentrations of organic matter in the single-chamber configuration. Biocathode performance was not impaired in two-chamber designs where the cathode was kept separated from the anode solution. These results demonstrate that direct-air biocathodes can work very well, but only under conditions that minimize heterotrophic growth of microorganisms on the cathodes.

Layer-by-Layer Thinning of PdSe2 Flakes via Plasma Induced Oxidation and Sublimation.

Controlled O2/Ar plasma exposure and subsequent low temperature inert atmosphere annealing of chemical vapor deposition (CVD) grown PdSe2 flakes etch PdSe2 layer-by-layer in an atomic layer etching-like (ALE) process. X-ray photoelectron spectroscopy (XPS) shows that exposure to a remote inductively coupled plasma (ICP) oxygen plasma oxidizes the top layer of the PdSe2 to form PdO2 and SeO2. After an in situ annealing, XPS shows no trace of PdO2 or SeO2, suggesting the byproducts are volatile at low temperature. Atomic force microscopy of PdSe2 exposed to various O2 + Ar plasmas (O2 = 25-100%) demonstrates a clear trend between the oxygen concentration and the number of layers etched per cycle. PdSe2 field effect transistors (FETs) were characterized at various stages of two ALE-like cycles, and the electrical properties are correlated to the oxidation and byproduct desorption and layer reduction.

Controlling the occurrence of power overshoot by adapting microbial fuel cells to high anode potentials.

Power density curves for microbial fuel cells (MFCs) often show power overshoot, resulting in inaccurate estimation of MFC performance at high current densities. The reasons for power overshoot are not well understood, but biofilm acclimation and development are known factors. In order to better explore the reasons for power overshoot, exoelectrogenic biofilms were developed at four different anode potentials (-0.46 V, -0.24 V, 0 V, and 0.50 V vs. Ag/AgCl), and then the properties of the biofilms were examined using polarization tests and cyclic voltammetry (CV). The maximum power density of the MFCs was 1200±100 mW/m(2). Power overshoot was observed in MFCs incubated at -0.46 V, but not those acclimated at more positive potentials, indicating that bacterial activity was significantly influenced by the anode acclimation potential. CV results further indicated that power overshoot of MFCs incubated at the lowest anode potential was associated with a decreasing electroactivity of the anodic biofilm in the high potential region, which resulted from a lack of sufficient electron transfer components to shuttle electrons at rates needed for these more positive potentials.

Enhanced start-up of anaerobic facultatively autotrophic biocathodes in bioelectrochemical systems.

Biocathodes in bioelectrochemical systems (BESs) can be used to convert CO2 into diverse organic compounds through a process called microbial electrosynthesis. Unfortunately, start-up of anaerobic biocathodes in BESs is a difficult and time consuming process. Here, a pre-enrichment method was developed to improve start-up of anaerobic facultatively autotrophic biocathodes capable of using cathodes as the electron donor (electrotrophs) and CO2 as the electron acceptor. Anaerobic enrichment of bacteria from freshwater bog sediment samples was first performed in batch cultures fed with glucose and then used to inoculate BES cathode chambers set at -0.4V (versus a standard hydrogen electrode; SHE). After two weeks of heterotrophic operation of BESs, CO2 was provided as the sole electron acceptor and carbon source. Consumption of electrons from cathodes increased gradually and was sustained for about two months in concert with a significant decrease in cathode chamber headspace CO2. The maximum current density consumed was -34 ± 4 mA/m(2). Biosynthesis resulted in organic compounds that included butanol, ethanol, acetate, propionate, butyrate, and hydrogen gas. Bacterial community analyses based on 16S rRNA gene clone libraries revealed Trichococcus palustris DSM 9172 (99% sequence identity) as the prevailing species in biocathode communities, followed by Oscillibacter sp. and Clostridium sp. Isolates from autotrophic cultivation were most closely related to Clostridium propionicum (99% sequence identity; ZZ16), Clostridium celerecrescens (98-99%; ZZ22, ZZ23), Desulfotomaculum sp. (97%; ZZ21), and Tissierella sp. (98%; ZZ25). This pre-enrichment procedure enables simplified start-up of anaerobic biocathodes for applications such as electrofuel production by facultatively autotrophic electrotrophs.