Sustainable technologies for energy production and storage are currently in great demand. Bioelectrochemical systems (BESs) offer promising solutions for both. Several attempts have been made to improve carbon felt electrode characteristics with various pretreatments in order to enhance performance. This study was motivated by gaps in current knowledge of the impact of pretreatments on the enrichment and microbial composition of bioelectrochemical systems. Therefore, electrodes were treated with poly(neutral red), chitosan, or isopropanol in a first step and then fixed in microbial electrolysis cells (MECs). Four MECs consisting of organic substance-degrading bioanodes and methane-producing biocathodes were set up and operated in batch mode by controlling the bioanode at 400 mV vs. Ag/AgCl (3M NaCl). After 1 month of operation, Enterococcus species were dominant microorganisms attached to all bioanodes and independent of electrode pretreatment. However, electrode pretreatments led to a decrease in microbial diversity and the enrichment of specific electroactive genera, according to the type of modification used. The MEC containing isopropanol-treated electrodes achieved the highest performance due to presence of both Enterococcus and Geobacter. The obtained results might help to select suitable electrode pretreatments and support growth conditions for desired electroactive microorganisms, whereby performance of BESs and related applications, such as BES-based biosensors, could be enhanced.
Bioelectric Energy Sources , Biofilms , Carbon Fiber , Electrodes , Carbon , Electrolysis , Geobacter
In this report, we present results on the electrocatalytic activity of conducting polymers [polyaniline (PANI) and polypyrrole (PPy)] toward the electrochemical oxygen reduction reaction (ORR) to hydrogen peroxide (H2O2). The electropolymerization of the polymers and electrolysis conditions were optimized for H2O2 production. On flat glassy carbon (GC) electrodes, the faradaic efficiency (FE) for H2O2 production was significantly improved by the polymers. Rotating disc electrode (RDE) studies revealed that this is mainly a result of blocking further H2O2 to the water reduction pathway by the polymers. PPy on carbon paper (CP) significantly increased the molar production of H2O2 by over 250% at an average FE of above 95% compared to bare CP with a FE of 25%. Thus, the polymers are acting as catalysts on the electrode for the ORR, although their catalytic mechanisms differ from other electrocatalysts.
Mechanically interlocking redox-active anthraquinone onto single-walled carbon nanotubes (AQ-MINT) gives a new and advanced example of a noncovalent architecture for an electrochemical platform. Electrochemical studies of AQ-MINT as an electrode reveal enhanced electrochemical stability in both aqueous and organic solvents compared to physisorbed AQ-based electrodes. While maintaining the electrochemical properties of the parent anthraquinone molecules, we observe a stable oxygen reduction reaction to hydrogen peroxide (H2O2). Using such AQ-MINT electrodes, 7 and 2 µmol of H2O2 are produced over 8 h under basic and neutral conditions, while the control system of SWCNTs produces 2.2 and 0.5 µmol, respectively. These results reveal the potential of this rotaxane-type immobilization approach for heterogenized electrocatalysis.
Using enzymes as bioelectrocatalysts is an important step toward the next level of biotechnology for energy production. In such biocatalysts, a sacrificial cofactor as an electron and proton source is needed. This is a great obstacle for upscaling, due to cofactor instability and product separation issues, which increase the costs. Here, we report a cofactor-free electroreduction of CO2 to a high energy density chemical (methanol) catalyzed by enzyme-graphene hybrids. The biocatalyst consists of dehydrogenases covalently bound on a well-defined carboxyl graphene derivative, serving the role of a conductive nanoplatform. This nanobiocatalyst achieves reduction of CO2 to methanol at high current densities, which remain unchanged for at least 20 h of operation, without production of other soluble byproducts. It is thus shown that critical improvements on the stability and rate of methanol production at a high Faradaic efficiency of 12% are possible, due to the effective electrochemical process from the electrode to the enzymes via the graphene platform.
Biocatalysis , Carbon Dioxide/chemistry , Enzymes, Immobilized/chemistry , Graphite/chemistry , Methanol/chemical synthesis , Oxidation-Reduction
Microbial electrosynthetic cells containing Methylobacterium extorquens were studied for the reduction of CO2 to formate by direct electron injection and redox mediator-assisted approaches, with CO2 as the sole carbon source. The formation of a biofilm on a carbon felt (CF) electrode was achieved while applying a constant potential of -0.75â V versus Ag/AgCl under CO2 -saturated conditions. During the biofilm growth period, continuous H2 evolution was observed. The long-term performance for CO2 reduction of the biofilm with and without neutral red as a redox mediator was studied by an applied potential of -0.75â V versus Ag/AgCl. The neutral red was introduced into the systems in two different ways: homogeneous (dissolved in solution) and heterogeneous (electropolymerized onto the working electrode). The heterogeneous approach was investigated in the microbial system, for the first time, where the CF working electrode was coated with poly(neutral red) by the oxidative electropolymerization thereof. The formation of poly(neutral red) was characterized by spectroscopic techniques. During long-term electrolysis up to 17 weeks, the formation of formate was observed continuously with an average Faradaic efficiency of 4 %. With the contribution of neutral red, higher formate accumulation was observed. Moreover, the microbial electrosynthetic cell was characterized by means of electrochemical impedance spectroscopy to obtain more information on the CO2 reduction mechanism.
Carbon Dioxide/metabolism , Neutral Red/metabolism , Biocatalysis , Biofilms , Electrochemical Techniques/methods , Formates/metabolism , Methylobacterium extorquens/physiology , Neutral Red/chemistry , Oxidation-Reduction , Polymerization
We report on a self-assembled system comprising a molecular copper-porphyrin photoelectrocatalyst, 5-(4-carboxy-phenyl)-10,15,20-triphenylporphyrinatocopper(II) (CuTPP-COOH), covalently bound to self-organized, anodic titania nanotube arrays (TiO2 NTs) for photoelectrochemical reduction of oxygen. Visible light irradiation of the porphyrin-covered TiO2 NTs under cathodic polarization up to -0.3â V vs. Normal hydrogen electrode (NHE) photocatalytically produces H2O2 in pH neutral electrolyte, at room temperature and without need of sacrificial electron donors. The formation of H2O2 upon irradiation is proven and quantified by direct colorimetric detection using 4-nitrophenyl boronic acid (p-NPBA) as a reactant. This simple approach for the attachment of a small molecular catalyst to TiO2 NTs may ultimately allow for the preparation of a low-cost H2O2 evolving cathode for efficient photoelectrochemical energy storage under ambient conditions.
