Shungui Zhou

Manganese dioxide as an alternative cathodic catalyst to platinum in microbial fuel cells.

In this paper, three manganese dioxide materials, alpha-MnO(2), beta-MnO(2), gamma-MnO(2) were tested as alternative cathodic catalysts to platinum (Pt) in air-cathode microbial fuel cells (MFCs). Prepared via hydrothermal method, the manganese dioxides were characterized by X-ray powder diffraction patterns (XRD), the Brunauer-Emmett-Teller (BET) method and their average oxidation states (AOS) were determined by the potential voltammetric titration method. The electro-catalytic activity of MnO(2) in neutral pH solution was determined by linear sweep voltammetry (LSV) and the results showed that all manganese dioxides can catalyze oxygen reduction reaction (ORR) in neutral medium with different catalytic activities. beta-MnO(2) appeared to hold the highest catalytic activity due to its highest BET surface area and AOS. Beta-MnO(2) was further used as cathode catalyst in both cube and tube air-cathode MFCs, in which using Klebsiella pneumoniae (K. pneumoniae) biofilm as biocatalyst and utilizing glucose as a substrate in the anode chamber. It was found that tube MFC produced higher output power, with the maximum volumetric power density of 3773+/-347 mW/m(3), than cube MFC. This study suggests that using beta-MnO(2) instead of Pt could potentially improve the feasibility of scaling up MFC designs for real applications by lowering production cost.

Scalable microbial fuel cell (MFC) stack for continuous real wastewater treatment.

A tubular air-cathode microbial fuel cell (MFC) stack with high scalability and low material cost was constructed and the ability of simultaneous real wastewater treatment and bioelectricity generation was investigated under continuous flow mode. At the two organic loading rates (ORLs) tested (1.2 and 4.9kg COD/m(3)d), five non-Pt MFCs connected in series and parallel circuit modes treating swine wastewater can enable an increase of the voltage and the current. The parallel stack retained high power output and the series connection underwent energy loss due to the substrate cross-conduction effect. With continuous electricity production, the parallel stack achieved 83.8% of COD removal and 90.8% of NH(4)(+)-N removal at 1.2kg COD/m(3)d, and 77.1% COD removal and 80.7% NH(4)(+)-N removal at 4.9kg COD/m(3)d. The MFC stack system in this study was demonstrated to be able to treat real wastewater with the added benefit of harvesting electricity energy.

Nanostructured macroporous bioanode based on polyaniline-modified natural loofah sponge for high-performance microbial fuel cells.

Microbial fuel cells (MFCs) are a promising technology to recover electrical energy from different types of waste. However, the power density of MFCs for practical applications is limited by the anode performance, mainly resulting from low bacterial loading capacity and low extracellular electron transfer (EET) efficiency. In this study, an open three-dimensional (3D) structured electrode was fabricated using a natural loofah sponge as the precursor material. The loofah sponge was directly converted into a continuous 3D macroporous carbon material via a simple carbonization procedure. The loofah sponge carbon (LSC) was decorated with nitrogen-enriched carbon nanoparticles by cocarbonizing polyaniline-hybridized loofah sponges to improve their microscopic structures. The macroscale porous structure of the LSCs greatly increased the bacterial loading capacity. The microscale coating of carbon nanoparticles favored EET due to the enhanced interaction between the bacteria and the anode. By using a single-chamber MFC equipped with the fabricated anode, a power density of 1090 ± 72 mW m(-2) was achieved, which is much greater than that obtained by similarly sized traditional 3D anodes. This study introduces a promising method for the fabrication of high-performance anodes from low-cost, sustainable natural materials.

Iron phthalocyanine supported on amino-functionalized multi-walled carbon nanotube as an alternative cathodic oxygen catalyst in microbial fuel cells.

Amino-functionalized multi-walled carbon nanotube (a-MWCNT)-supported iron phthalocyanine (FePc) (a-MWCNT/FePc) has been investigated as a catalyst for the oxygen reduction reaction (ORR) in an air-cathode single-chambered microbial fuel cell (MFC). Cyclic and linear sweep voltammogram are employed to investigate the electrocatalytic activity of the a-MWCNT/FePc for ORR. The maximum power density of 601 mWm(-2) is achieved from a MFC with the a-MWCNT/FePc cathode, which is the highest energy output compared to those MFCs with other materials supported FePc, such as carbon black, pristine MWCNT (p-MWCNT), carboxylic acid functionalized MWCNT (c-MWCNT), and even with a Pt/C cathode. Furthermore, cyclic voltammetry performed on the a-MWCNT/FePc electrode suggests that the a-MWCNT/FePc has an electrochemical activity for ORR via a four-electron pathway in a neutral pH solution. This work provides a potential alternative to Pt in MFCs for sustainable energy generation.

Enhanced performance of air-cathode two-chamber microbial fuel cells with high-pH anode and low-pH cathode

In the course of microbial fuel cell (MFC) operation, the acidification of the anode and the alkalization of the cathode inevitably occur, resulting in reduction of the overall performance. In an attempt to reverse the membrane pH gradient, a tubular air-cathode two-chamber MFC was developed that allowed pH adjustment in both compartments. With an anodic pH of 10.0 and a cathodic pH of 2.0, the tubular MFC provided an open circuit voltage of 1.04V and a maximum power density of 29.9W/m(3), which were respectively 1.5 and 3.8 times higher than those obtained in the same MFC working at neutral pH. Particularly, the suppression of methanogenesis at high alkaline anode (pH 10.0) contributed to a significant enhancement in coulombic efficiency. The MFC maintained 74% of its performance after 15 days of operation in continuous-flow mode. The appropriate pH adjustment strategy in both compartments ensures a promising improvement in MFC performance.

Long-term evaluation of a 10-liter serpentine-type microbial fuel cell stack treating brewery wastewater

A 10-liter serpentine-type microbial fuel cell (MFC) stack was constructed by extending 40 tubular air-cathode MFC units in a 3-D alignment pattern. When operated in series and fed with brewery wastewater, the stack produced an open circuit voltage of 23.0V and a maximum power density of 4.1W/m(3) (at 0.7A/m(3)). During long-term performance (180days), electrochemical tests were conducted to explore the reasons for deterioration in performance of the stack system. Cyclic voltammetric measurements suggested that the cathodes, not the anodes, were responsible for the decrease in performance over time. After the cathode surface was rinsed with water, the power density produced by the stack system fully recovered instantaneously, due to the decrease in cathode alkalization and increase in humidity of the cathode side. This study provided an optimal configuration of a MFC stack for MFC scale-up towards large-scale applications.

Membrane-less cloth cathode assembly (CCA) for scalable microbial fuel cells

One of the main challenges for scaling up microbial fuel cell (MFC) technologies is developing low-cost cathode architectures that can generate high power output. This study developed a simple method to convert non-conductive material (canvas cloth) into an electrically conductive and catalytically active cloth cathode assembly (CCA) in one step. The membrane-less CCA was simply constructed by coating the cloth with conductive paint (nickel-based or graphite-based) and non-precious metal catalyst (MnO(2)). Under the fed-batch mode, the tubular air-chamber MFCs equipped with Ni-CCA and graphite-CCA generated the maximum power densities of 86.03 and 24.67 mW m(-2) (normalized to the projected cathode surface area), or 9.87 and 2.83 W m(-3) (normalized to the reactor liquid volume), respectively. The higher power output of Ni-CCA-MFC was associated with the lower volume resistivity of Ni-CCA (1.35 x 10(-2)Omega cm) than that of graphite-CCA (225 x 10(-2)Omega cm). At an external resistance of 100 Omega, Ni-CCA-MFC and graphite-CCA-MFC removed approximately 95% COD in brewery wastewater within 13 and 18d, and achieved coulombic efficiencies of 30.2% and 19.5%, respectively. The accumulated net water loss through the cloth by electro-osmotic drag exhibited a linear correlation (R(2)=0.999) with produced coulombs. With a comparable power production, such CCAs only cost less than 5% of the previously reported membrane cathode assembly. The new cathode configuration here is a mechanically durable, economical system for MFC scalability.

Microbially-reduced graphene scaffolds to facilitate extracellular electron transfer in microbial fuel cells.

A one-pot method is exploited by adding graphene oxide (GO) and acetate into an microbial fuel cell (MFC) in which GO is microbially reduced, leading to in situ construction of a bacteria/graphene network in the anode. The obtained microbially reduced graphene (MRG) exhibits comparable conductivity and physical characteristics to the chemically reduced graphene. Electrochemical measurements reveal that the number of exoelectrogens involved in extracellular electron transfer (EET) to the solid electrode, increases due to the presence of graphene scaffolds, and the EET is facilitated in terms of electron transfer kinetics. As a result, the maximum power density of the MFC is enhanced by 32% (from 1440 to 1905 mW m(-2)) and the coulombic efficiency is improved by 80% (from 30 to 54%). The results demonstrate that the construction of the bacteria/graphene network is an effective alternative to improve the MFC performance.

Electrocatalytic activity of anodic biofilm responses to pH changes in microbial fuel cells.

This study investigates the effects of anodic pH on electricity generation in microbial fuel cells (MFCs) and the intrinsic reasons behind them. In a two-chamber MFC, the maximum power density is 1170 ± 58 mW m(-2) at pH 9.0, which is 29% and 89% higher than those working at pH 7.0 and 5.0, respectively. Electrochemical measurements reveal that pH affects the electron transfer kinetics of anodic biofilms. The apparent electron transfer rate constant (k(app)) and exchange current density (i(0)) are greater whereas the charge transfer resistance (R(ct)) is smaller at pH 9.0 than at other conditions. Scanning electron microscopy verifies that alkaline conditions benefit biofilm formation in MFCs. These results demonstrate that electrochemical interactions between bacteria and electrodes in MFCs are greatly enhanced under alkaline conditions, which can be one of the important reasons for the improved MFC output.

In Situ Investigation of Cathode and Local Biofilm Microenvironments Reveals Important Roles of OH– and Oxygen Transport in Microbial Fuel Cells

Mass transport within a cathode, including OH(-) transport and oxygen diffusion, is important for the performance of air-cathode microbial fuel cells (MFCs). However, little is known regarding how mass transport profiles are associated with MFC performance and how they are affected by biofilm that inevitably forms on the cathode surface. In this study, the OH(-) and oxygen profiles of a cathode biofilm were probed in situ in an MFC using microelectrodes. The pH of the catalyst layer interface increased from 7.0 ± 0.1 to 9.4 ± 0.3 in a buffered MFC with a bare cathode, which demonstrates significant accumulation of OH(-) in the cathode region. Furthermore, the pH of the interface increased to 10.0 ± 0.3 in the presence of the local biofilm, which indicates that OH(-) transport was severely blocked. As a result of the significant OH(-) accumulation, the maximum power density of the MFC decreased from 1.8 ± 0.1 W/m(2) to 1.5 ± 0.08 W/m(2). In contrast, oxygen crossover, which was significant under low current flow conditions, was limited by the cathode biofilm. As a result of the blocked oxygen crossover, higher MFC coulombic efficiency (CE) was achieved in the presence of the cathode biofilm. These results indicate that enhanced OH(-) transport and decreased oxygen crossover would be beneficial for high-performance MFC development.