A novel carbon nanotube modified scaffold as an efficient biocathode material A novel carbon nanotube modified scaffold as an efficient biocathode material for improved microbial electrosynthesis for improved microbial electrosynthesis Abstract AbstractWe report on a novel biocompatible, highly conductive three-dimensional cathode manufactured by direct growth of flexible multiwalled carbon nanotubes on reticulated vitreous carbon (NanoWeb-RVC) for the improvement of microbial bioelectrosynthesis (MES). NanoWeb-RVC allows for an enhanced bacterial attachment and biofilm development within its hierarchical porous structure. 1.7 and 2.6 fold higher current density and acetate bioproduction rate normalized to total surface area were reached on NanoWeb-RVC versus a carbon plate control for the microbial reduction of carbon dioxide by mixed cultures. This is the first study showing better intrinsic efficiency as biocathode material of a threedimensional electrode versus a flat electrode: this comparison has been made considering the total surface area of the porous electrode, and not just the projected surface area. Therefore, the improved performance is attributed to the nanostructure of the electrode and not to an increase in surface area. Unmodified reticulated vitreous carbon electrodes lacking the nanostructure were found unsuitable for MES, with no biofilm development and no acetate production detected. The high surface area to volume ratio of the macroporous RVC maximizes the available biofilm area while ensuring effective mass transfer to and from the biofilm. The nanostructure enhances the bacteria-electrode interaction and microbial extracellular electron transfer. When normalized to projected surface area, current densities and acetate production rates of 3.7 mA cm-2 and 1.3 mM cm-2 d-1, respectively, were reached, making the NanoWeb-RVC an extremely efficient material from an engineering perspective as well. These values are the highest reported for any MES system to date.

The focus of this study was to investigate the effects of surface charge and surface hydrophobicity on anodic biofilm formation, biofilm community composition, and current generation in bioelectrochemical systems (BESs). Glassy carbon surfaces were modified with -OH, -CH3, -SO3(-), or -N(+)(CH3)3 functional groups by electrochemical reduction of aryl diazonium salts and then used as anodes with poised potential of -0.2 V (vs Ag/AgCl). The average startup times and final current densities for the -N(+)(CH3)3, -OH, -SO3(-), and -CH3, electrodes were (23 d, 0.204 mA/cm(2)), (25.4 d, 0.149 mA/cm(2)), (25.9 d, 0.114 mA/cm(2)), and (37.2 d, 0.048 mA/cm(2)), respectively. Biofilms on different surfaces were analyzed by nonturnover cyclic voltammetry (CV), fluorescence in situ hybridization (FISH), and 16S rRNA gene amplicon pyrosequencing. The results demonstrated that 1) differences in the maximum current output between surface modifications was correlated with biomass quantity, and 2) all biofilms were dominated by Geobacter populations, but the composition of -CH3-associated biofilms differed from those formed on surfaces with different chemical modification. This study shows that anode surface charge and hydrophobicity influences biofilm development and can lead to significant differences in BESs performance. Positively charged and hydrophilic surfaces were more selective to electroactive microbes (e.g. Geobacter) and more conducive for electroactive biofilm formation.

Adsorption of hydrated cations on hydrophilic surfaces has been related to a variety of phenomena associated with the short-range interaction forces and mechanisms of the adhesive contact between the surfaces. Here we have investigated the effect of the adsorption of cations on the lateral interaction. Using lateral force microscopy (LFM), we have measured the friction force between a silica particle and silica wafer in pure water and in electrolyte solutions of LiCl, NaCl, and CsCl salts. A significant lubrication effect was demonstrated for solutions of high electrolyte concentrations. It was found that the adsorbed layers of smaller and more hydrated cations have a higher lubrication capacity than the layers of larger and less hydrated cations. Additionally, we have demonstrated a characteristic dependence of the friction force on the sliding velocity of surfaces. A mechanism for the observed phenomena based on the microstructures of the adsorbed layers is proposed.

Certain conjugated oligoelectrolytes (COEs) modify biological function by improving charge transfer across biological membranes as demonstrated by their ability to boost performance in bioelectrochemical systems. Molecular level understanding of the nature of the COE/membrane interactions is lacking. Thus, we investigated cell membrane perturbation by three COEs differing in the number of aromatic rings and presence of a fluorine substitution. Molecular dynamic simulations showed that membrane deformation by all COEs resulted from membrane thinning as the lipid phosphate heads were drawn toward the center of the bilayer layer by positively charged COE side chains. The four-ringed COE, which most closely resembled the lipid bilayer in length, deformed the membrane the least and was least disruptive, as supported by toxicity testing (minimum inhibitory concentration (MIC) = 64 μmol L(-1)) and atomic force microscopy (AFM). Extensive membrane thinning was observed from three-ringed COEs, reducing membrane thickness to <3.0 nm in regions where the COEs were located. Severe localized membrane pitting was observed when the central aromatic ring was unfluorinated, as evident from AFM and simulations. Fluorinating the central aromatic ring delocalized thinning but induced greater membrane disorder, indicated by changes in deuterium order parameter of the acyl chains. The fluorinated three-ringed compound was less toxic (MIC 4 μmol L(-1)) than the nonfluorinated three-aromatic-ringed COE (MIC 2 μmol L(-1)); thus, hydrophobic polar interactions resulting from fluorine substitution of OPV COEs dissipate membrane perturbations. Correlating specific structural features with cell membrane perturbation is an important step toward designing non-antimicrobial membrane insertion molecules.

Bioelectrochemical systems encompass a range of electrochemical systems wherein microorganisms are used as biocatalysts. These range from classical microbial fuel cells to novel microbial electrosynthesis processes. The future of practical applications relies on increased performance. In all cases the development of new electrode materials is essential to overcome the low current densities of bioelectrochemical systems. Here we describe a new biocompatible, highly conductive three-dimensional scaffold electrode, NanoWeb-RVC, with a hierarchical porous structure, synthesized by direct growth of carbon nanotubes on a macroporous substrate. The nanostructure of these electrodes enhances the rate of bacterial extracellular electron transfer while the macrostructure ensures efficient mass transfer to and from the electrode surface. NanoWeb-RVC electrodes showed a current density of (6.8 ± 0.3) mA cm-2, almost three times higher than a control electrode with the same macroporous structure but lacking the nanostructure. This current density is among the highest reported to date for a microbial bioanode. to overcome the low current densities of bioelectrochemical systems. Here we describe a new biocompatible, highly conductive three-dimensional scaffold electrode, NanoWeb-RVC, with a hierarchical porous structure, synthetised by direct growth of carbon nanotubes on a macroporous substrate. The nanostructure of these electrodes enhances the rate of bacterial extracellular electron transfer while the macrostructure ensures efficient mass transfer to and from the electrode surface. NanoWeb-RVC electrodes showed a current density of (6.8 ± 0.3) mA cm -2 , almost three times higher than a control electrode with the same macroporous structure but lacking the nanostructure. This current density is among the highest reported to date for a microbial bioanode.

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Stainless steel (SS) can be an attractive material to create large electrodes for microbial bioelectrochemical systems (BESs), due to its low cost and high conductivity. However, poor biocompatibility limits its successful application today. Here we report a simple and effective method to make SS electrodes biocompatible by means of flame oxidation. Physicochemical characterization of electrode surface indicated that iron oxide nanoparticles (IONPs) were generated in situ on an SS felt surface by flame oxidation. IONPs-coating dramatically enhanced the biocompatibility of SS felt and consequently resulted in a robust electroactive biofilm formation at its surface in BESs. The maximum current densities reached at IONPs-coated SS felt electrodes were 16.5 times and 4.8 times higher than the untreated SS felts and carbon felts, respectively. Furthermore, the maximum current density achieved with the IONPs-coated SS felt (1.92 mA/cm(2), 27.42 mA/cm(3)) is one of the highest current densities reported thus far. These results demonstrate for the first time that flame oxidized SS felts could be a good alternative to carbon-based electrodes for achieving high current densities in BESs. Most importantly, high conductivity, excellent mechanical strength, strong chemical stability, large specific surface area, and comparatively low cost of flame oxidized SS felts offer exciting opportunities for scaling-up of the anodes for BESs.