Bidirectional Electron Transfer Research Articles

Marine Sediment Mixed With Activated Carbon Allows Electricity Production and Storage From Internal and External Energy Sources: A New Rechargeable Bio-Battery With Bi-Directional Electron Transfer Properties.

Marine sediment has a great potential to generate electricity with a bioelectrochemical system (BES) like the microbial fuel cell (MFC). In this study, we investigated the potential of marine sediment and activated carbon (AC) to generate and store electricity. Both internal and external energy supply was validated for storage behavior. Four types of anode electrode compositions were investigated. Two types were mixtures of different volumes of AC and Dutch Eastern Scheldt marine sediment (67% AC and 33% AC) and the others two were 100% AC or 100% marine sediment based. Each composition was duplicated. Operating these BES’s under MFC mode with solely marine sediment as the anode electron donor resulted in the creation of a bio-battery. The recharge time of such bio-battery does depend on the fuel content and its usage. The results show that by usage of marine sediment and AC electricity was generated and stored. The 100% AC and the 67% AC mixed with marine sediment electrode were over long term potentiostatic controlled at -100 mV vs. Ag/AgCl which resulted in a cathodic current and an applied voltage. After switching back to the MFC operation mode at 1000 Ω external load, the electrode turned into an anode and electricity was generated. This supports the hypothesis that external supply electrical energy was recovered via bi-directional electron transfer. With open cell voltage experiments these AC marine bioanodes showed internal supplied electric charge storage up to 100 mC at short self-charging times (10 and 60 s) and up to 2.4°C (3,666 C/m3 anode) at long charging time (1 h). Using a hypothetical cell voltage of 0.2 V, this value represents an internal electrical storage density of 0.3 mWh/kg AC marine anode. Furthermore it was remarkable that the BES with 100% marine sediment based electrode also acted like a capacitor similar to the charge storage behaviors of the AC based bioanodes with a maximum volumetric storage of 1,373 C/m3 anode. These insights give opportunities to apply such BES systems as e.g., ex situ bio-battery to store and use electricity for off-grid purpose in remote areas.

Excited‐State Charge Transfer in Covalently Functionalized MoS2 with a Zinc Phthalocyanine Donor–Acceptor Hybrid

AbstractThe functionalization of MoS2 is of paramount importance for tailoring its properties towards optoelectronic applications and unlocking its full potential. Zinc phthalocyanine (ZnPc) carrying an 1,2‐dithiolane oxide linker was used to functionalize MoS2 at defect sites located at the edges. The structure of ZnPc‐MoS2 was fully assessed by complementary spectroscopic, thermal, and microscopy imaging techniques. An energy‐level diagram visualizing different photochemical events in ZnPc‐MoS2 was established and revealed a bidirectional electron transfer leading to a charge separated state ZnPc.+‐MoS2.−. Markedly, evidence of the charge transfer in the hybrid material was demonstrated using fluorescence spectroelectrochemistry. Systematic studies performed by femtosecond transient absorption revealed the involvement of excitons generated in MoS2 in promoting the charge transfer, while the transfer was also possible when ZnPc was excited, signifying their potential in light‐energy‐harvesting devices.

Excited-State Charge Transfer in Covalently Functionalized MoS2 with a Zinc Phthalocyanine Donor-Acceptor Hybrid.

The functionalization of MoS2 is of paramount importance for tailoring its properties towards optoelectronic applications and unlocking its full potential. Zinc phthalocyanine (ZnPc) carrying an 1,2-dithiolane oxide linker was used to functionalize MoS2 at defect sites located at the edges. The structure of ZnPc-MoS2 was fully assessed by complementary spectroscopic, thermal, and microscopy imaging techniques. An energy-level diagram visualizing different photochemical events in ZnPc-MoS2 was established and revealed a bidirectional electron transfer leading to a charge separated state ZnPc.+ -MoS2 .- . Markedly, evidence of the charge transfer in the hybrid material was demonstrated using fluorescence spectroelectrochemistry. Systematic studies performed by femtosecond transient absorption revealed the involvement of excitons generated in MoS2 in promoting the charge transfer, while the transfer was also possible when ZnPc was excited, signifying their potential in light-energy-harvesting devices.

In Vivo Two-Way Redox Cycling System for Independent Duplexed Electrochemical Signal Amplification.

An in vivo two-way redox cycling system based on whole-cell bidirectional electron transfer was developed and applied for independent duplexed electrochemical signal amplification. This duplexed signal amplification system was established by activating the bacterial "inwards" electron transfer at low electrode potential for oxidative cycling, while accomplishing the bacterial "outwards" electron transfer at high electrode potential for reductive cycling. Therefore, with this two-way bioredox cycling system, simultaneous and independent amplification of the electrochemical signals for oxidation and reduction was achieved. More impressively, by using this duplexed signal amplification system, ultrasensitive and simultaneous detection of two different warfare toxins of Pseudomonas aeruginosa was achieved (sensitivity was improved 302 and 579 times, respectively), which makes it possible for double-checking early diagnosis of the P. aeruginosa infections.

Combined spectroelectrochemical and proteomic characterizations of bidirectional Alcaligenes faecalis-electrode electron transfer

Bioelectrochemical systems use microbes as catalysts for current production or consumption. Up to now only a few microbes have been demonstrated to be capable of both outward and inward extracellular electron transfer (EET) (i.e. bidirectional electron transfer). However, the mechanisms of electron exchange between microbes and extracellular solids remain uncertain. Here, we showed that Alcaligenes faecalis catalyzed an outward EET and generated electricity at a poised potential of +0.3V vs. SHE, whereas it conducted an inward EET for autotrophic denitrification at −0.5V vs. SHE. Both cyclic voltammetry and in situ electrochemical FTIR spectroscopy revealed that different redox components were utilized during the outward and inward EET. Electron transport inhibitor experiments indicated for the first time that complex I, II, III, and the quinone pool on the plasma membrane were involved in the bidirectional EET. Comparative proteomics showed that the protein expression profile of outward-EET biofilms differed greatly from those of inward-EET biofilms, implying that the pili and outer membrane proteins might be responsible for the interfacial outward and inward EET, respectively. These results suggest different electron transport conduits of A. faecalis biofilms could be used for bidirectional EET.

Bidirectional Electron-Transfer in Polypeptides with Various Secondary Structures

The protein-mediated bidirectional electron transfer (ET) is the foundation of protein molecular wire, and plays an important role in the rapid detection of oxo-guanine-adenine DNA mismatches by MutY glycosylase. However, the influences of structural transitions on bidirectional ET are still not clear. In this work, the modified through-bond coupling (MTBC) model was further refined to correlate the structural transition and ET rate more quantitatively. With this model, various polyglycine structures (310-helix, α-helix, β-sheets, linear, polyproline helical I and II) were studied to explore the influences of structural transitions on bidirectional ET. It was found that the HOMO-LUMO gaps (ΔE) in CN (from the carboxyl to amino terminus) direction are much lower than that in opposite direction, except for polypro I. However, with the equal tunneling energy, the differences between bidirectional ET rates are slight for all structures. In structural transitions, we found that the ET rates are not only affected by the Ramachandran angles, but also correlated to the alignment of C = O vectors, the alignment of peptide planes and the rearrangement of other structure factors. The detailed information can be used to rationalize the inhomogeneous ET across different protein structures and design more efficient protein molecular wires.

Electron-transfer-induced and phononic heat transport in molecular environments.

A unified theory of heat transport in environments that sustain intersite phononic coupling and electron hopping is developed. The heat currents generated by both phononic transport and electron transfer between sites characterized by different local temperatures are calculated and compared. Using typical molecular parameters we find that the electron-transfer-induced heat current can be comparable to that of the standard phononic transport for donor-acceptor pairs with efficient bidirectional electron transfer rates (relatively small intersite distance and favorable free-energy difference). In most other situations, phononic transport is the dominant heat transfer mechanism.

Electrochemical and spectroscopic insights into the mechanisms of bidirectional microbe-electrode electron transfer in Geobacter soli biofilms

Few electroactive bacteria have shown the capacity of exchanging electrons with electrode in both directions, and the mechanisms of such bidirectional electron transfer remain uncertain hitherto. In this study, we demonstrate that Geobacter soli biofilms could directly donate electrons to and accept electrons from graphite electrode. Under anodic conditions, G. soli oxidizes acetate to generate current, and under cathodic conditions, nitrate is reduced by a truncated denitrification pathway with nitrous oxide as end product. Cyclic voltammetry, differential pulse voltammetry and electrochemical in situ FTIR spectra demonstrate that distinct external membrane redox systems exist in the anode and cathode biofilms, which supports the conclusion that G. soli uses different electron transfer conduits for bidirectional electron transfer. These results expand the horizon of bidirectional electron transfer mechanisms, meanwhile this study represents a first report that Geobacter species might utilize electrode as electron donor for incomplete denitrification.

Electron transfer pathways in a multiheme cytochrome MtrF

In MtrF, an outer-membrane multiheme cytochrome, the 10 heme groups are arranged in heme binding domains II and IV along the pseudo-C2 axis, forming the electron transfer (ET) pathways. Previous reports based on molecular dynamics simulations showed that the redox potential (Em) values for the heme pairs located in symmetrical positions in domains II and IV were similar, forming bidirectional ET pathways [Breuer M, Zarzycki P, Blumberger J, Rosso KM (2012) J Am Chem Soc 134(24):9868-9871]. Here, we present the Em values of the 10 hemes in MtrF, solving the linear Poisson-Boltzmann equation and considering the protonation states of all titratable residues and heme propionic groups. In contrast to previous studies, the Em values indicated that the ET is more likely to be downhill from domain IV to II because of localization of acidic residues in domain IV. Reduction of hemes in MtrF lowered the Em values, resulting in switching to alternative downhill ET pathways that extended to the flavin binding sites. These findings present an explanation of how MtrF serves as an electron donor to extracellular substrates.

Polarity inversion of bioanode for biocathodic reduction of aromatic pollutants

The enrichment of specific pollutant-reducing consortium is usually required prior to the startup of biocathode bioelectrochemical system (BES) and the whole process is time consuming. To rapidly establish a non-specific functional biocathode, direct polar inversion from bioanode to biocathode is proposed in this study. Based on the diverse reductases and electron transfer related proteins of anode-respiring bacteria (ARB), the acclimated electrochemically active biofilm (EAB) may catalyze reduction of different aromatic pollutants. Within approximately 12 d, the acclimated bioanodes were directly employed as biocathodes for nitroaromatic nitrobenzene (NB) and azo dye acid orange 7 (AO7) reduction. Our results indicated that the established biocathode significantly accelerated the reduction of NB to aniline (AN) and AO7 to discolored products compared with the abiotic cathode and open circuit controls. Several microbes possessing capabilities of nitroaromatic/azo dye reduction and bidirectional electron transfer were maintained or enriched in the biocathode communities. Cyclic voltammetry highlighted the decreased over-potentials and enhanced electron transfer of biocathode as well as demonstrated the ARB Geobacter containing cytochrome c involved in the backward electron transfer from electrode to NB. This study offers new insights into the rapid establishment and modularization of functional biocathodes for the potential treatment of complicated electron acceptors-coexisting wastewaters.

Visualizing the bidirectional electron transfer in a Schottky junction consisting of single CdS nanoparticles and a planar gold film.

Bidirectional electron transfer crossing the metal/semiconductor interface regulates the light absorption and carrier separation efficiency of plasmonic-semiconductor hybrid nanomaterials. Existing studies have been largely focused on a localized surface plasmon resonance (LSPR) effect contributed by an ensemble of metal nanomaterials. Herein, we constructed a Schottky junction that consisted of single CdS nanoparticles and a planar gold film, and investigated hot electrons excited by the surface plasmon polaritons (SPPs) propagating in the gold film. When illuminating the interface with blue light, photoinduced electrons were found to inject from the CdS nanoparticle to the gold film. In a reverse process, SPPs were generated on shining a red beam into the gold film via a Kretschmann configuration, resulting in the injection of hot electrons into CdS nanoparticles. A recently developed plasmonic microscopy method was employed to monitor the entire process, providing the ability to image a single nanoparticle to visualize the bidirectional electron transfer dynamics in a Schottky junction involving propagating SPPs. The present study advances the understanding of the mechanism of hot electron transfer, which is anticipated to aid in the rational design and optimization of plasmonic-semiconductor hybrid nanomaterials with broad applications in photocatalysis, photovoltaic devices, and photoelectrochemical sensing.

マルチへムシトクロム蛋白質MtrFの電子移動経路

In MtrF, an outer-membrane multiheme cytochrome, the 10 heme groups are arranged in heme binding domains II and IV along the pseudo-C2 axis, forming the electron transfer (ET) pathways. Previous reports based on molecular dynamics simulations showed that the redox potential (Em) values for the heme pairs located in symmetrical positions in domains II and IV were similar, forming bidirectional ET pathways [Breuer M, Zarzycki P, Blumberger J, Rosso KM (2012) J Am Chem Soc 134(24):9868–9871]. Here, we present the Em values of the 10 hemes in MtrF, solving the linear Poisson–Boltzmann equation and considering the protonation states of all titratable residues and heme propionic groups. In contrast to previous studies, the Em values indicated that the ET is more likely to be downhill from domain IV to II because of localization of acidic residues in domain IV. Reduction of hemes in MtrF lowered the Em values, resulting in switching to alternative downhill ET pathways that extended to the flavin binding sites. These findings present an explanation of how MtrF serves as an electron donor to extracellular substrates.

Analysis of electrode microbial communities in an up-flow bioelectrochemical system treating azo dye wastewater

Bioelectrochemical system (BES) is a rapidly developing technology covering contamination remediation, resource recovery and power generation. Electrode biofilms play a key role in BES operation. In this work, a single chamber up-flow bioelectrochemical system (UBES) was assembled with two preinoculated anodes and two raw cathodes for azo dye wastewater treatment. Microbial community structures of these electrodes after long-term operation (more than 200 days) were carried out by high-throughput Illumina 16S rRNA gene MiSeq sequencing platform. Microorganisms belonging to Enterobacter, Desulfovibrio and Enterococcus, which are capable of bidirectional extracellular electron transfer, were found to be the dominant members in all biofilms. Neither the polarity nor the position of the electrodes obviously altered the microbial community structures. This study provides a feasible strategy to build electrode active biofilms in a BES for azo dye wastewater treatment and gives great inspirations to bring this technology closer to application.

Response of anodic bacterial community to the polarity inversion for chloramphenicol reduction

Chloramphenicol (CAP) is a frequently detected environmental pollutant. In this study, an electroactive biofilm for CAP reduction was established by initially in the anode and then inverting to the cathode. The established biocathode could enhance the reduction of CAP to the nitro-group reduced CAP (AMCl2) and further dechlorinated form (AMCl), both had lost the antibacterial activity. The phylogenetic diversity of the acclimated biofilm was decreased after the polar inversion. Proportions of functional bacterial genera, including Geobacter, Desulfovibrio and Pseudomonas responsible for the bidirectional electron transfer and nitroaromatics reduction, had increased 28%, 104% and 43% in the cathode. The relatively high abundances (over 50%) of Geobacter in anode and cathode were rarely detected for the nitroaromatics reduction. This study provides new insights into the electroactive biofilm structure improvement by the polarity inversion strategy for refractory antibiotics degradation.

Adsorption of formate species on Cu(h,k,l) low index surfaces

We report a density functional theory study on the relative stability of formate species on Cu(h,k,l) low index surfaces using a range of exchange-correlation functionals. We find that these functionals predict similar geometries for the formate molecule adsorbed on the Cu surface. A comparison of the calculated vibrational transition energies of a perpendicular configuration of formate on Cu surface shows an excellent agreement with the experimental spectrum obtained from inelastic neutron spectroscopy. From the calculations on adsorption energy we find that formate is most stable on the Cu(110) surface as compared to Cu(111) and Cu(100) surfaces. Bader analysis shows that this feature could be related to the higher charge transfer from the Cu(110) surface and optimum charge density at the interfacial region due to bidirectional electron transfer between the formate and the Cu surface. Analysis of the partial density of states finds that in the –5.5eV to –4.0eV region, hybridization between O p and the non-axial Cu dyz and dxz orbitals takes place on the Cu(110) surface, which is energetically more favourable than on the other surfaces.

Nanotechnology to rescue bacterial bidirectional extracellular electron transfer in bioelectrochemical systems

Advanced nanostructured electrode materials largely improve the bacterial bidirectional extracellular electron transfer in bioelectrochemical systems.

Excitation dependent bidirectional electron transfer in phthalocyanine-functionalised MoS2 nanosheets.

Two-dimensional (2D) transition metal chalcogenides such as 2D MoS2 are considered prime candidate materials for the design of next generation optoelectronics. Functionalisation of these materials is considered to be a key step in tailoring their properties towards specific applications and unlocking their full potential. Here we present a van der Waals functionalisation strategy for creating MoS2 nanosheets decorated with free base phthalocyanine chromophores. The semiconducting sheets are found to intimately interact with these optoelectronically active chromophores, resulting in an electronic heterostructure that exhibits enhanced optoelectronic properties and exploitable charge transfer. We show that by utilising laterally confined MoS2 nanosheets, the conduction band of the semiconductor could be positioned between the chromophore's S1 and S2 states. Consequently, bidirectional photoinduced electron transfer processes are observed, with excitation of the functionalised nanosheet's semiconductor transition resulting in electron transfer to the phthalocyanine's LUMO, and excitation of the chromophore's S2 state leading to electron injection into the MoS2 conduction band. However, charge transfer from the dye's S1 transition to the MoS2 nanosheet is found to be thermodynamically unfavourable, resulting in intense radiative recombination. These findings may enable controlling and tuning the charge carrier density of semiconducting nanosheets via optical means through the exploitation of photoinduced electron transfer. Furthermore this work provides access to 2D semiconductor-hybrids with tailored absorption profiles and photoluminescence.

Bidirectional microbial electron transfer: Switching an acetate oxidizing biofilm to nitrate reducing conditions

Up to date a few electroactive bacteria embedded in biofilms are described to catalyze both anodic and cathodic reactions in bioelectrochemical systems (i.e. bidirectional electron transfer). How these bacteria transfer electrons to or from the electrode is still uncertain. In this study the extracellular electron transfer mechanism of bacteria within an electroactive biofilm was investigated by using cyclic voltammetry (CV) and differential pulse voltammetry (DPV). First, a mature anodic electroactive biofilm was developed from an activated sludge sample (inoculum), acetate as electron donor and a poised electrode (+397mV vs. SHE). Later, this biofilm was "switched" to biocathodic conditions by feeding it with a medium containing nitrates and poising the electrode at -303mV vs. SHE. The electrochemical characterization indicated that both, acetate oxidation and nitrate reduction took place at a similar formal potential of -175±05 and -175±34mV vs. SHE, respectively. The biofilm was predominantly composed by Geobacter sp. at both experimental conditions. Taken together, the results indicated that both processes could be catalyzed by using the same electron conduit, and most likely by the same bacterial consortium. Hence, this study suggests that electroactive bacteria within biofilms could use the same electron transfer conduit for catalyzing anodic and cathodic reactions.

Adjustable bidirectional extracellular electron transfer between Comamonas testosteroni biofilms and electrode via distinct electron mediators

Abstract Bidirectional extracellular electron transfer of strain Comamonas testosteroni I2 was for the first time investigated with electrochemical active biofilms developed under different conditions. The electrochemical active biofilm developed under microbial fuel cell conditions was capable of anodic electron transfer via attached redox species with standard potential of 0.04 V (vs. SCE). Meanwhile the above redox species lost its catalytic capability when the biofilm was developed under a constant potential (− 0.4 V vs. SCE). Instead, the microbe adjusted its electron transfer strategy to a soluble shuttle (standard potential − 0.20 V vs. SCE) and enabled a cathodic current. Air exposure experiment verified that the soluble shuttle at negative potential had a positive response to the oxygen; meanwhile the anodic electron transfer via the attached species was rarely influenced.

Enhancing Bidirectional Electron Transfer of Shewanella oneidensis by a Synthetic Flavin Pathway.

Flavins regulate the rate and direction of extracellular electron transfer (EET) in Shewanella oneidensis. However, low concentration of endogenously secreted flavins by the wild-type S. oneidensis MR-1 limits its EET efficiency in bioelectrochemical systems (BES). Herein, a synthetic flavin biosynthesis pathway from Bacillus subtilis was heterologously expressed in S. oneidensis MR-1, resulting in ∼25.7 times' increase in secreted flavin concentration. This synthetic flavin module enabled enhanced bidirectional EET rate of MR-1, in which its maximum power output in microbial fuel cells increased ∼13.2 times (from 16.4 to 233.0 mW/m(2)), and the inward current increased ∼15.5 times (from 15.5 to 255.3 μA/cm(2)).