Roland D. Cusick

Anode microbial communities produced by changing from microbial fuel cell to microbial electrolysis cell operation using two different wastewaters

Conditions in microbial fuel cells (MFCs) differ from those in microbial electrolysis cells (MECs) due to the intrusion of oxygen through the cathode and the release of H(2) gas into solution. Based on 16S rRNA gene clone libraries, anode communities in reactors fed acetic acid decreased in species richness and diversity, and increased in numbers of Geobacter sulfurreducens, when reactors were shifted from MFCs to MECs. With a complex source of organic matter (potato wastewater), the proportion of Geobacteraceae remained constant when MFCs were converted into MECs, but the percentage of clones belonging to G. sulfurreducens decreased and the percentage of G. metallireducens clones increased. A dairy manure wastewater-fed MFC produced little power, and had more diverse microbial communities, but did not generate current in an MEC. These results show changes in Geobacter species in response to the MEC environment and that higher species diversity is not correlated with current.

Energy Capture from Thermolytic Solutions in Microbial Reverse-Electrodialysis Cells

Waste Not The organic matter in wastewater is a potentially vast and sustainable energy source; however, most wastewater treatment plants consume energy. Cusick et al. (p. 1474, published online 1 March) combined a microbial fuel cell with a reverse-electrodialysis system to boost the voltage output and the power density over a simple microbial fuel cell. The use of ammonium bicarbonate as a fuel for reverse electrodialysis while microorganisms simultaneously turn organic matter into electricity not only allows for the capturing of waste heat, but could eventually produce enough energy to offset the energy used in conventional wastewater treatment systems. Thermally induced salt gradients could augment the electricity generated by microbial fuel cells from wastewater. Reverse electrodialysis allows for the capture of energy from salinity gradients between salt and fresh waters, but potential applications are currently limited to coastal areas and the need for a large number of membrane pairs. Using salt solutions that could be continuously regenerated with waste heat (≥40°C) and conventional technologies would allow much wider applications of salinity-gradient power production. We used reverse electrodialysis ion-exchange membrane stacks in microbial reverse-electrodialysis cells to efficiently capture salinity-gradient energy from ammonium bicarbonate salt solutions. The maximum power density using acetate reached 5.6 watts per square meter of cathode surface area, which was five times that produced without the dialysis stack, and 3.0 ± 0.05 watts per square meter with domestic wastewater. Maximum energy recovery with acetate reached 30 ± 0.5%.

Phosphate recovery as struvite within a single chamber microbial electrolysis cell

An energy efficient method of concurrent hydrogen gas and struvite (MgNH(4)PO(4)·6H(2)O) production was investigated based on bioelectrochemically driven struvite crystallization at the cathode of a single chamber microbial electrolysis struvite-precipitation cell (MESC). The MESC cathodes were either stainless steel 304 mesh or flat plates. Phosphate removal ranged from 20% to 40%, with higher removals obtained using mesh cathodes than with flat plates. Cathode accumulated crystals were verified as struvite using a scanning electron microscope capable of energy dispersive spectroscopy (SEM-EDS). Crystal accumulation did not affect the rate of hydrogen production in struvite reactors. The rate of struvite crystallization (g/m(2)-h) and hydrogen production (m(3)/m(3)-d) were shown to be dependent on applied voltage and cathode material. Overall energy efficiencies (substrate and electricity) were high (73 ± 4%) and not dependent on applied voltage. These results show that MESCs may be useful both as a method for hydrogen gas and struvite production.

Hydrogen generation in microbial reverse-electrodialysis electrolysis cells using a heat-regenerated salt solution.

Hydrogen gas can be electrochemically produced in microbial reverse-electrodialysis electrolysis cells (MRECs) using current derived from organic matter and salinity-gradient energy such as river water and seawater solutions. Here, it is shown that ammonium bicarbonate salts, which can be regenerated using low-temperature waste heat, can also produce sufficient voltage for hydrogen gas generation in an MREC. The maximum hydrogen production rate was 1.6 m(3) H(2)/m(3)·d, with a hydrogen yield of 3.4 mol H(2)/mol acetate at a salinity ratio of infinite. Energy recovery was 10% based on total energy applied with an energy efficiency of 22% based on the consumed energy in the reactor. The cathode overpotential was dependent on the catholyte (sodium bicarbonate) concentration, but not the salinity ratio, indicating high catholyte conductivity was essential for maximizing hydrogen production rates. The direction of the HC and LC flows (co- or counter-current) did not affect performance in terms of hydrogen gas volume, production rates, or stack voltages. These results show that the MREC can be successfully operated using ammonium bicarbonate salts that can be regenerated using conventional distillation technologies and waste heat making the MREC a useful method for hydrogen gas production from wastes.

Effect of nitrogen addition on the performance of microbial fuel cell anodes

Carbon cloth anodes were modified with 4(N,N-dimethylamino)benzene diazonium tetrafluoroborate to increase nitrogen-containing functional groups at the anode surface in order to test whether the performance of microbial fuel cells (MFCs) could be improved by controllably modifying the anode surface chemistry. Anodes with the lowest extent of functionalization, based on a nitrogen/carbon ratio of 0.7 as measured by XPS, achieved the highest power density of 938 mW/m(2). This power density was 24% greater than an untreated anode, and similar to that obtained with an ammonia gas treatment previously shown to increase power. Increasing the nitrogen/carbon ratio to 3.8, however, decreased the power density to 707 mW/m(2). These results demonstrate that a small amount of nitrogen functionalization on the carbon cloth material is sufficient to enhance MFC performance, likely as a result of promoting bacterial adhesion to the surface without adversely affecting microbial viability or electron transfer to the surface.

Energy positive domestic wastewater treatment: the roles of anaerobic and phototrophic technologies

The negative energy balance of wastewater treatment could be reversed if anaerobic technologies were implemented for organic carbon oxidation and phototrophic technologies were utilized for nutrient recovery. To characterize the potential for energy positive wastewater treatment by anaerobic and phototrophic biotechnologies we performed a comprehensive literature review and analysis, focusing on energy production (as kJ per capita per day and as kJ m(-3) of wastewater treated), energy consumption, and treatment efficacy. Anaerobic technologies included in this review were the anaerobic baffled reactor (ABR), anaerobic membrane bioreactor (AnMBR), anaerobic fluidized bed reactor (AFB), upflow anaerobic sludge blanket (UASB), anaerobic sequencing batch reactor (ASBR), microbial electrolysis cell (MEC), and microbial fuel cell (MFC). Phototrophic technologies included were the high rate algal pond (HRAP), photobioreactor (PBR), stirred tank reactor, waste stabilization pond (WSP), and algal turf scrubber (ATS). Average energy recovery efficiencies for anaerobic technologies ranged from 1.6% (MFC) to 47.5% (ABR). When including typical percent chemical oxygen demand (COD) removals by each technology, this range would equate to roughly 40-1200 kJ per capita per day or 110-3300 kJ m(-3) of treated wastewater. The average bioenergy feedstock production by phototrophic technologies ranged from 1200-4700 kJ per capita per day or 3400-13 000 kJ m(-3) (exceeding anaerobic technologies and, at times, the energetic content of the influent organic carbon), with usable energy production dependent upon downstream conversion to fuels. Energy consumption analysis showed that energy positive anaerobic wastewater treatment by emerging technologies would require significant reductions of parasitic losses from mechanical mixing and gas sparging. Technology targets and critical barriers for energy-producing technologies are identified, and the role of integrated anaerobic and phototrophic bioprocesses in energy positive wastewater management is discussed.

Capacitive mixing power production from salinity gradient energy enhanced through exoelectrogen-generated ionic currents

Several approaches to generate electrical power directly from salinity gradient energy using capacitive electrodes have recently been developed, but power densities have remained low. By immersing the capacitive electrodes in ionic fields generated by exoelectrogenic microorganisms in bioelectrochemical reactors, we found that energy capture using synthetic river and seawater could be increased ∼65 times, and power generation ∼46 times. Favorable electrochemical reactions due to microbial oxidation of organic matter, coupled to oxygen reduction at the cathode, created an ionic flow field that enabled more effective passive charging of the capacitive electrodes and higher energy capture. This ionic-based approach is not limited to the use of river water-seawater solutions. It can also be applied in industrial settings, as demonstrated using thermolytic solutions that can be used to capture waste heat energy as salinity gradient energy. Forced charging of the capacitive electrodes, using energy generated by the bioelectrochemical system and a thermolytic solution, further increased the maximum power density to 7 W m−2 (capacitive electrode).

Minimal RED Cell Pairs Markedly Improve Electrode Kinetics and Power Production in Microbial Reverse Electrodialysis Cells

Power production from microbial reverse electrodialysis cell (MRC) electrodes is substantially improved compared to microbial fuel cells (MFCs) by using ammonium bicarbonate (AmB) solutions in multiple RED cell pair stacks and the cathode chamber. Reducing the number of RED membranes pairs while maintaining enhanced electrode performance could help to reduce capital costs. We show here that using only a single RED cell pair (CP), created by operating the cathode in concentrated AmB, dramatically increased power production normalized to cathode area from both acetate (Acetate: from 0.9 to 3.1 W/m(2)-cat) and wastewater (WW: 0.3 to 1.7 W/m(2)), by reducing solution and charge transfer resistances at the cathode. A second RED cell pair increased RED stack potential and reduced anode charge transfer resistance, further increasing power production (Acetate: 4.2 W/m(2); WW: 1.9 W/m(2)). By maintaining near optimal electrode power production with fewer membranes, power densities normalized to total membrane area for the 1-CP (Acetate: 3.1 W/m(2)-mem; WW: 1.7 W/m(2)) and 2-CP (Acetate: 1.3 W/m(2)-mem; WW: 0.6 W/m(2)) reactors were much higher than previous MRCs (0.3-0.5 W/m(2)-mem with acetate). While operating at peak power, the rate of wastewater COD removal, normalized to reactor volume, was 30-50 times higher in 1-CP and 2-CP MRCs than that in a single chamber MFC. These findings show that even a single cell pair AmB RED stack can significantly enhance electrical power production and wastewater treatment.

Exoelectrogenic biofilm as a template for sustainable formation of a catalytic mesoporous structure.

Mesoporous structures can increase catalytic activity by maximizing the ratio of surface area to volume, but current synthesis techniques utilize expensive polymers and toxic chemicals. A Geobacter sulfurreducens biofilm was used as a sustainable template to form mesoporous Pd structures while eliminating the need for synthetic chemicals. The bulk of the biofilm material was removed by thermal treatments after nanoparticle formation, producing a catalytic Pd mesoporous (pore size 9.7 ± 0.1 nm) structure attached to the graphite electrode with a 1.5-2 µm thick backbone composed of nanoparticles (∼200 nm). A control electrode electrochemically plated with Pd in the absence of a biofilm exhibited a variable planar Pd base (∼0.5-3 µm thick) with sporadic Pd extrusions (∼2 µm across, 1-5 µm tall) from the surface. The biotemplated mesoporous structure produced 15-20% higher stable current densities during H2 oxidation tests than the electrochemically plated control electrode, even though 30% less Pd was present in the biotemplated catalyst. These results indicate that electroactive biofilms can be used as a sustainable base material to produce nanoporous structures without the need for synthetic polymers. Biotechnol. Bioeng. 2014;111: 2349-2354.

Characterizing the Impacts of Deposition Techniques on the Performance of MnO2 Cathodes for Sodium Electrosorption in Hybrid Capacitive Deionization

Capacitive deionization (CDI) is currently limited by poor ion-selectivity and low salt adsorption capacity of porous carbon electrodes. To enhance selectivity and capacity via sodium insertion reactions, carbon aerogel electrodes were modified by depositing amorphous manganese dioxide layers via cyclic voltammetry (CV) and electroless deposition (ED). MnO2-coated electrodes were evaluated in a hybrid capacitive deionization system to understand the relationship between oxide coating morphology, electrode capacitance, and sodium removal efficacy. Both deposition techniques increased electrode capacitance, but only ED electrodes improved desalination performance over bare aerogels. SEM imaging revealed ED deposition distributed MnO2 throughout the aerogel, while CV deposition created a discrete crust, indicating that CV electrodes were limited by diffusion. Sodium adsorption capacity of ED electrodes increased with MnO2 mass deposition, reaching a maximum of 0.77 mmol-Na+ per gram of cathode (2.29 mmol-Na+ g-MnO2-1), and peak charge efficiency of 0.95. The presence of MnO2 also positively shifted the electrode potential window of sodium removal, reducing parasitic oxygen reduction and inverting the desalination cycle so that energy discharge coincides with salt removal (1.96 kg-NaCl kWh-1). These results highlight the importance of deposition technique in improving desalination with MnO2-coated electrodes.