Microbial Fermentation of Polyethylene Terephthalate (PET) Plastic Waste for the Production of Chemicals or Electricity.

Ideonella sakaiensis (I. sakaiensis) can grow on polyethylene terephthalate (PET) as the major carbon and energy source. Previous work has shown that PET conversion in the presence of oxygen released carbon dioxide and water while yielding adenosine triphosphate (ATP) through oxidative phosphorylation. This study demonstrates that I. sakaiensis is a facultative anaerobe that ferments PET to the feedstock chemicals acetate and ethanol in the absence of oxygen. In addition to PET, the pure monomer ethylene glycol (EG), the intermediate product ethanol, and the carbohydrate fermentation test substance maltose can also serve as fermenting substrates. Co-culturing of I. sakaiensis with the electrogenic and acetate-consuming Geobacter sulfurreducens produced electricity from PET or EG. This newly identified plastic fermentation process by I. sakaiensis provides thus a novel biosynthetic route to produce high-value chemicals or electricity from plastic waste streams.

Biocatalytic conversion of sunlight and carbon dioxide to solar fuels and chemicals.

This review discusses the progress in the assembly of photosynthetic biohybrid systems using enzymes and microbes as the biocatalysts which are capable of utilising light to reduce carbon dioxide to solar fuels. We begin by outlining natural photosynthesis, an inspired biomachinery to develop artificial photosystems, and the rationale and motivation to advance and introduce biological substrates to create more novel, and efficient, photosystems. The case studies of various approaches to the development of CO2-reducing microbial semi-artificial photosystems are also summarised, showcasing a variety of methods for hybrid microbial photosystems and their potential. Finally, approaches to investigate the relatively ambiguous electron transfer mechanisms in such photosystems are discussed through the presentation of spectroscopic techniques, eventually leading to what this will mean for the future of microbial hybrid photosystems.

Semi-biological approaches to solar-to-chemical conversion.

This review presents a comprehensive summary of the recent development in semi-artificial photosynthesis, a biological-material hybrid approach to solar-to-chemical conversion that provides new concepts to shape a sustainable future fuelled by solar energy. We begin with a brief introduction to natural and artificial photosynthesis, followed by a discussion of the motivation and rationale behind semi-artificial photosynthesis. Then, we summarise how various enzymes can be combined with synthetic materials for light-driven water oxidation, H2 evolution, CO2 reduction, and chemical synthesis more broadly. In the following section, we discuss the strategies to incorporate microorganisms in photocatalytic and (photo)electrochemical systems to produce fuels and chemicals with renewable sources. Finally, we outline emerging analytical techniques to study the bio-material hybrid systems and propose unexplored research opportunities in the field of semi-artificial photosynthesis.

A three-dimensional hybrid electrode with electroactive microbes for efficient electrogenesis and chemical synthesis.

Integration of electroactive bacteria into electrodes combines strengths of intracellular biochemistry with electrochemistry for energy conversion and chemical synthesis. However, such biohybrid systems are often plagued with suboptimal electrodes, which limits the incorporation and productivity of the bacterial colony. Here, we show that an inverse opal-indium tin oxide electrode hosts a large population of current-producing Geobacter and attains a current density of 3 mA cm-2 stemming from bacterial respiration. Differential gene expression analysis revealed Geobacter's transcriptional regulations to express more electron-relaying proteins when interfaced with electrodes. The electrode also allows coculturing with Shewanella for syntrophic electrogenesis, which grants the system additional flexibility in converting electron donors. The biohybrid electrode containing Geobacter can also catalyze the reduction of soluble fumarate and heterogenous graphene oxide, with electrons from an external power source or an irradiated photoanode. This biohybrid electrode represents a platform to employ live cells for sustainable power generation and biosynthesis.

Disparity of Cytochrome Utilization in Anodic and Cathodic Extracellular Electron Transfer Pathways of Geobacter sulfurreducens Biofilms.

Extracellular electron transfer (EET) in microorganisms is prevalent in nature and has been utilized in functional bioelectrochemical systems. EET of Geobacter sulfurreducens has been extensively studied and has been revealed to be facilitated through c-type cytochromes, which mediate charge between the electrode and G. sulfurreducens in anodic mode. However, the EET pathway of cathodic conversion of fumarate to succinate is still under debate. Here, we apply a variety of analytical methods, including electrochemistry, UV-vis absorption and resonance Raman spectroscopy, quartz crystal microbalance with dissipation, and electron microscopy, to understand the involvement of cytochromes and other possible electron-mediating species in the switching between anodic and cathodic reaction modes. By switching the applied bias for a G. sulfurreducens biofilm coupled to investigating the quantity and function of cytochromes, as well as the emergence of Fe-containing particles on the cell membrane, we provide evidence of a diminished role of cytochromes in cathodic EET. This work sheds light on the mechanisms of G. sulfurreducens biofilm growth and suggests the possible existence of a nonheme, iron-involving EET process in cathodic mode.

Dual-Function Electrocatalytic and Macroporous Hollow-Fiber Cathode for Converting Waste Streams to Valuable Resources Using Microbial Electrochemical Systems.

Dual-function electrocatalytic and macroporous hollow-fiber cathodes are recently proposed as promising advanced material for maximizing the conversion of waste streams such as wastewater and waste CO2 to valuable resources (e.g., clean freshwater, energy, value-added chemicals) in microbial electrochemical systems. The first part of this progress report reviews recent developments in this type of cathode architecture for the simultaneous recovery of clean freshwater and energy from wastewater. Critical insights are provided on suitable materials for fabricating these cathodes, as well as addressing some challenges in the fabrication process with proposed strategies to overcome them. The second and complementary part of the progress report highlights how the unique features of this cathode architecture can solve one of the intrinsic bottlenecks (gas-liquid mass transfer limitation) in the application of microbial electrochemical systems for CO2 reduction to value-added products. Strategies to further improve the availability of CO2 to microbial catalysts on the cathode are proposed. The importance of understanding microbe-cathode interactions, as well as electron transfer mechanisms at the cathode-cell and cell-cell interface to better design dual-function macroporous hollow-fiber cathodes, is critically discussed with insights on how the choice of material is important in facilitating direct electron transfer versus mediated electron transfer.

Proton Transport in the Outer-Membrane Flavocytochrome Complex Limits the Rate of Extracellular Electron Transport.

The microbial transfer of electrons to extracellularly located solid compounds, termed extracellular electron transport (EET), is critical for microbial electrode catalysis. Although the components of the EET pathway in the outer membrane (OM) have been identified, the role of electron/cation coupling in EET kinetics is poorly understood. We studied the dynamics of proton transport associated with EET in an OM flavocytochrome complex in Shewanella oneidensis MR-1. Using a whole-cell electrochemical assay, a significant kinetic isotope effect (KIE) was observed following the addition of deuterated water (D2 O). The removal of a flavin cofactor or key components of the OM flavocytochrome complex significantly increased the KIE in the presence of D2 O to values that were significantly larger than those reported for proton channels and ATP synthase, thus indicating that proton transport by OM flavocytochrome complexes limits the rate of EET.

Hollow Palladium Nanoparticles Facilitated Biodegradation of an Azo Dye by Electrically Active Biofilms.

Dye wastewater severely threatens the environment due to its hazardous and toxic effects. Although many methods are available to degrade dyes, most of them are far from satisfactory. The proposed research provides a green and sustainable approach to degrade an azo dye, methyl orange, by electrically active biofilms (EABs) in the presence of solid and hollow palladium (Pd) nanoparticles. The EABs acted as the electron generator while nanoparticles functioned as the electron carrier agents to enhance degradation rate of the dye by breaking the kinetic barrier. The hollow Pd nanoparticles showed better performance than the solid Pd nanoparticles on the dye degradation, possibly due to high specific surface area and cage effect. The hollow cavities provided by the nanoparticles acted as the reaction centers for the dye degradation.

Cell-secreted flavins bound to membrane cytochromes dictate electron transfer reactions to surfaces with diverse charge and pH.

The variety of solid surfaces to and from which microbes can deliver electrons by extracellular electron transport (EET) processes via outer-membrane c-type cytochromes (OM c-Cyts) expands the importance of microbial respiration in natural environments and industrial applications. Here, we demonstrate that the bifurcated EET pathway of OM c-Cyts sustains the diversity of the EET surface in Shewanella oneidensis MR-1 via specific binding with cell-secreted flavin mononucleotide (FMN) and riboflavin (RF). Microbial current production and whole-cell differential pulse voltammetry revealed that RF and FMN enhance EET as bound cofactors in a similar manner. Conversely, FMN and RF were clearly differentiated in the EET enhancement by gene-deletion of OM c-Cyts and the dependency of the electrode potential and pH. These results indicate that RF and FMN have specific binding sites in OM c-Cyts and highlight the potential roles of these flavin-cytochrome complexes in controlling the rate of electron transfer to surfaces with diverse potential and pH.

Enhanced performance of a microbial fuel cell using CNT/MnO2 nanocomposite as a bioanode material.

The anode electrode material is a crucial factor for the overall performance of a microbial fuel cell (MFC). In this study, a plain carbon paper modified with the CNT/MnO2 nanocomposite was used as the anode for the MFC and a mixed culture inoculum was used as the biocatalyst. The modified anode showed better electrochemical performance than that of plain carbon paper, and Brunauer Emmett Teller (BET) analysis showed the high surface area (94.6 m2/g) of the composite. The Mn4+ in the nanocomposite may enhance the electron transfer between the microorganisms and the anode material which facilitates electron conduction. Additionally, MnO2 can be used to store electrons due to its supercapacitance, which is comparable to that of the cytochromes present in the outer cell membranes of electrochemically active microorganisms. The MFC with a modified anode produced a maximum power density of 120 +/- 1.7 mW/m2, while the corresponding current density was 0.262 +/- 0.015 A/m2 at an external resistor of 800 omega with an open circuit voltage (OCV) of 1.07 +/- 0.02 V. The unusually high OCV may be attributed to the high charge density developed on the bioanode by the charge accumulation in the MnO2 of the bioanode. This study showed that the CNT/MnO2 nanocomposite can be an excellent anode material for MFC.

Synthesis of positively charged gold nanoparticles using a stainless-steel mesh.

A novel, rapid, one-pot, and facile approach was developed to synthesize positively charged gold nanoparticles [(+) AuNPs] by employing an aqueous solution of HAuCl4 x 3H2O as a precursor at 30 degrees C and a stainless-steel mesh as a reducing agent. The penetration of Cl- ions into the stainless-steel surface results in corrosion on the stainless-steel surface and excretion of electrons which are used for reduction of Au3+ --> Au0. As a result, (+) AuNPs 5-20 nm in size, mostly monodispersed, were synthesized within 3 h. The as-synthesized AuNPs were charaterized by UV-vis, DLS, XRD, TEM, HR-TEM, EDX and SAED. The utilization of non-toxic chemicals and easily available materials, and the non-requirement of energy input, make this methodology easy, inexpensive, and efficient. The new findings about the role of the stainless-steel mesh, which provides electrons in the presence of Cl- ions, for the reduction of Au3+ --> Au0, makes it a novel material for (+) AuNPs synthesis.

Oxygen vacancy induced band gap narrowing of ZnO nanostructures by an electrochemically active biofilm.

Band gap narrowing is important and advantageous for potential visible light photocatalytic applications involving metal oxide nanostructures. This paper reports a simple biogenic approach for the promotion of oxygen vacancies in pure zinc oxide (p-ZnO) nanostructures using an electrochemically active biofilm (EAB), which is different from traditional techniques for narrowing the band gap of nanomaterials. The novel protocol improved the visible photocatalytic activity of modified ZnO (m-ZnO) nanostructures through the promotion of oxygen vacancies, which resulted in band gap narrowing of the ZnO nanostructure (Eg = 3.05 eV) without dopants. X-ray diffraction, UV-visible diffuse reflectance spectroscopy, X-ray photoelectron spectroscopy, electron paramagnetic resonance spectroscopy, Raman spectroscopy, photoluminescence spectroscopy and high resolution transmission electron microscopy confirmed the oxygen vacancy and band gap narrowing of m-ZnO. m-ZnO enhanced the visible light catalytic activity for the degradation of different classes of dyes and 4-nitrophenol compared to p-ZnO, which confirmed the band gap narrowing because of oxygen defects. This study shed light on the modification of metal oxide nanostructures by EAB with a controlled band structure.

Band gap narrowing of titanium dioxide (TiO2) nanocrystals by electrochemically active biofilms and their visible light activity.

We report a simple biogenic-route to narrow the band gap of TiO2 nanocrystals for visible light application by offering a greener method. When an electrochemically active biofilm (EAB) was challenged with a solution of Degussa-TiO2 using sodium acetate as the electron donor, greyish blue-colored TiO2 nanocrystals were obtained. A band gap study showed that the band gap of the modified TiO2 nanocrystals was significantly reduced (E(g) = 2.85 eV) compared to the unmodified white Degussa TiO2 (E(g) = 3.10 eV).

Production of bioelectricity, bio-hydrogen, high value chemicals and bioinspired nanomaterials by electrochemically active biofilms.

Microorganisms naturally form biofilms on solid surfaces for their mutual benefits including protection from environmental stresses caused by contaminants, nutritional depletion or imbalances. The biofilms are normally dangerous to human health due to their inherited robustness. On the other hand, a recent study suggested that electrochemically active biofilms (EABs) generated by electrically active microorganisms have properties that can be used to catalyze or control the electrochemical reactions in a range of fields, such as bioenergy production, bioremediation, chemical/biological synthesis, bio-corrosion mitigation and biosensor development. EABs have attracted considerable attraction in bioelectrochemical systems (BESs), such as microbial fuel cells and microbial electrolysis cells, where they act as living bioanode or biocathode catalysts. Recently, it was reported that EABs can be used to synthesize metal nanoparticles and metal nanocomposites. The EAB-mediated synthesis of metal and metal-semiconductor nanocomposites is expected to provide a new avenue for the greener synthesis of nanomaterials with high efficiency and speed than other synthetic methods. This review covers the general introduction of EABs, as well as the applications of EABs in BESs, and the production of bio-hydrogen, high value chemicals and bio-inspired nanomaterials.

Gold nanoparticles produced in situ mediate bioelectricity and hydrogen production in a microbial fuel cell by quantized capacitance charging.

Oppan quantized style: By adding a gold precursor at its cathode, a microbial fuel cell (MFC) is demonstrated to form gold nanoparticles that can be used to simultaneously produce bioelectricity and hydrogen. By exploiting the quantized capacitance charging effect, the gold nanoparticles mediate the production of hydrogen without requiring an external power supply, while the MFC produces a stable power density.

Efficient decolorization of real dye wastewater and bioelectricity generation using a novel single chamber biocathode-microbial fuel cell.

Large scale applications of microbial fuel cells (MFCs) have been severely hindered by several problems such as high internal resistance, low power output, expensive materials, and complicated configuration. To address these issues, a granular activated carbon based single chamber microbial fuel cell (GACB-SCMFC) has been designed using GAC-biocathodes without using any expensive materials for the simultaneous decolorization of real dye wastewater and electricity generation. The GACB-SCMFC produced a power density of 8 W/m(3) which indicates the GAC-biocathode can be a good alternative to platinum and other chemical catalysts. The dye wastewater was primarily treated at the anode and further polishing steps were occurred at the aerobic cathode. Toxicity measurement shows that the effluent after GACB-SCMFC operation was much less toxic compared to the original dye wastewater. Additional advantage of the GACB-SCMFC is that pH was automatically adjusted from 12.2 to 8 during 48 h of hydraulic retention time (HRT).

Granular activated carbon based microbial fuel cell for simultaneous decolorization of real dye wastewater and electricity generation.

Decolorization of dye wastewater before discharge is pivotal because of its immense color and toxicities. In this study, a granular activated carbon based microbial fuel cell (GACB-MFC) was used without using any expensive materials like Nafion membrane and platinum catalyst for simultaneous decolorization of real dye wastewater and bioelectricity generation. After 48 hours of GACB-MFC operation, 73% color was removed at anode and 77% color was removed at cathode. COD removal was 71% at the anode and 76% at the cathode after 48 hours. Toxicity measurements showed that cathode effluent was almost nontoxic after 24 hours. The anode effluent was threefold less toxic compared to original dye wastewater after 48 hours. The GACB-MFC produced a power density of 1.7 W/m(3) with an open circuit voltage 0.45 V. One of the advantages of the GACB-MFC system is that pH was automatically adjusted from 12.4 to 7.2 and 8.0 at the anode and cathode during 48 hours operation.