Nanoscaffold effects on the performance of air-cathodes for microbial fuel cells: Sustainable Fe/N-carbon electrocatalysts for the oxygen reduction reaction under neutral pH conditions.

Nanostructured electrocatalysts for microbial fuel cell air-cathodes were obtained via use of conductive carbon blacks for the synthesis of high performing 3D conductive networks. We used two commercially available nanocarbons, Black Pearls 2000 and multiwalled carbon nanotubes, as conductive scaffolds for the synthesis of nanocomposite electrodes by combining: a hydrothermally carbonized resin, a sacrificial polymeric template, a nitrogenated organic precursor and iron centers. The resulting materials are micro-mesoporous, possess high specific surface area and display N-sites (N/C of 3-5 at%) and Fe-centers (Fe/C < 1.5at.%) at the carbon surface as evidenced from characterization methods. Voltammetry studies of oxygen reduction reaction activity were carried out at neutral pH, which is relevant to microbial fuel cell applications, and activity trends are discussed in light of catalyst morphology and composition. Tests of the electrocatalyst using microbial fuel cell devices indicate that optimization of the nanocarbon scaffold for the Pt-free carbon-based electrocatalysts results in maximum power densities that are 25% better than those of Pt/C cathodes, at a fraction of the materials costs. Therefore, the proposed Fe/N-carbon catalysts are promising and sustainable high-performance cathodic materials for microbial fuel cells.

Controlling the Carbon-Bio Interface via Glycan Functional Adlayers for Applications in Microbial Fuel Cell Bioanodes.

Surface modification of electrodes with glycans was investigated as a strategy for modulating the development of electrocatalytic biofilms for microbial fuel cell applications. Covalent attachment of phenyl-mannoside and phenyl-lactoside adlayers on graphite rod electrodes was achieved via electrochemically assisted grafting of aryldiazonium cations from solution. To test the effects of the specific bio-functionalities, modified and unmodified graphite rods were used as anodes in two-chamber microbial fuel cell devices. Devices were set up with wastewater as inoculum and acetate as nutrient and their performance, in terms of output potential (open circuit and 1 kΩ load) and peak power output, was monitored over two months. The presence of glycans was found to lead to significant differences in startup times and peak power outputs. Lactosides were found to inhibit the development of biofilms when compared to bare graphite. Mannosides were found, instead, to promote exoelectrogenic biofilm adhesion and anode colonization, a finding that is supported by quartz crystal microbalance experiments in inoculum media. These differences were observed despite both adlayers possessing thickness in the nm range and similar hydrophilic character. This suggests that specific glycan-mediated bioaffinity interactions can be leveraged to direct the development of biotic electrocatalysts in bioelectrochemical systems and microbial fuel cell devices.

Tailored glycosylated anode surfaces: Addressing the exoelectrogen bacterial community via functional layers for microbial fuel cell applications.

Grafting of aryldiazonium cations bearing a p-mannoside functionality over microbial fuel cell (MFC) anode materials was performed to investigate the ability of aryl-glycoside layers to regulate colonisation by biocatalytic biofilms. Covalent attachment was achieved via spontaneous reactions and via electrochemically-assisted grafting using potential step experiments. The effect of different functionalisation protocols on MFC performance is discussed in terms of changes in wettability, roughness and electrochemical response of modified electrodes. Water contact angle measurements (WCA) show that aryl-mannoside grafting yields a significant increase in hydrophilic character. Surface roughness determinations via atomic force microscopy (AFM) suggest a more disordered glycan adlayer when electrografting is used to facilitate chemisorption. MFCs were used as living sensors to successfully test the coated electrodes: the response of the MFCs in terms of start-up time was accelerated when compared to that of MFC equipped with non-modified electrodes, this suggests a faster development of a mature biofilm community resulting from aryldiazonium modifications, as confirmed by cyclic voltammetry of MFC anodes. These results therefore indicate that modification with glycans offers a bioinspired route to accelerating biofilm colonisation without any adverse effects on final MFC outputs.

Untangling Cooperative Effects of Pyridinic and Graphitic Nitrogen Sites at Metal-Free N-Doped Carbon Electrocatalysts for the Oxygen Reduction Reaction.

Metal-free carbon electrodes with well-defined composition and smooth topography are prepared via sputter deposition followed by thermal treatment with inert and reactive gases. X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy show that three carbons of similar N/C content that differ in N-site composition are thus prepared: an electrode consisting of almost exclusively graphitic-N (NG ), an electrode with predominantly pyridinic-N (NP ), and one with ≈1:1 NG :NP composition. These materials are used as model systems to investigate the activity of N-doped carbons in the oxygen reduction reaction (ORR) using voltammetry. Results show that selectivity toward 4e-reduction of O2 is strongly influenced by the NG /NP site composition, with the material possessing nearly uniform NG /NP composition being the only one yielding a 4e-reduction. Computational studies on model graphene clusters are carried out to elucidate the effect of N-site homogeneity on the reaction pathway. Calculations show that for pure NG -doping or NP -doping of model graphene clusters, adsorption of hydroperoxide and hydroperoxyl radical intermediates, respectively, is weak, thus favoring desorption prior to complete 4e-reduction to hydroxide. Clusters with mixed NG /NP sites display synergistic effects, suggesting that co-presence of these sites improves activity and selectivity by achieving high theoretical reduction potentials while facilitating retention of intermediates.

Carbon-Supported Zirconium Oxide as a Cathode for Microbial Fuel Cell Applications.

Cost-effective electrode materials to be used as cathodes in lab-scale prototype microbial fuel cells (MFCs) were prepared from mixtures of carbon black (C) and zirconium oxide (ZrO2 ) of different composition. The catalytic activity of these cathodes in the oxygen reduction reaction (ORR) and their stability toward poisoning in typical MFC operative conditions were assessed by using electrochemical techniques. Scanning electron microscopy and Brunauer-Emmett-Teller measurements gave insights into sample morphology and surface area. The results indicated that the C/ZrO2 sample with a ZrO2 loading of 25 wt % (C/ZrO2 _25) represents the best compromise in terms of ORR activity and stability. C/ZrO2 _25 was assembled into cathodes of a prototype single-chamber MFC, which produced a maximum power density of 600 mW m-2 . A comparative cost analysis of energy production indicated that the cost of energy delivered by MFCs assembled with a C/ZrO2 cathode was more than 15 times lower than that of MFCs assembled with a reference Pt/C cathode.