Effects of exogenous riboflavin or cytochrome addition on the cathodic reduction of Cr(VI) in microbial fuel cell with Shewanella putrefaciens.

Bioreduction of Cr(VI) is recognized as a cost-effective and environmentally friendly method, attracting widespread interest. However, the slow rate of Cr(VI) bioreduction remains a practical challenge. Additionally, the direct removal efficiency of microbes for high concentrations of Cr(VI) is not ideal due to the toxicity. Therefore, this study investigated the effects of exogenous riboflavin or cytochrome on the cathodic reduction of Cr(VI) in microbial fuel cells. The results demonstrated that the exogenous riboflavin or cytochrome effectively improved the voltage output of the cells, with riboflavin increasing the voltage by 52.08%. Within the first 24 h, the Cr(VI) removal ratio in the normal, cytochrome, and riboflavin groups was 14.3%, 29.3%, and 53.8%, respectively. And the final removal ratio was 55.1%, 69.1%, and 98.0%, respectively. These results showed different enhancement effects of riboflavin and cytochrome on Cr(VI) removal. The analysis of riboflavin and cytochrome contents revealed that the additions did not have a significant impact on the autocrine riboflavin of S. putrefaciens, but affected the autocrine cytochrome. SEM, XPS, and FTIR results confirmed the presence of reduced Cr(III) on the cathode, which formed precipitate and adhered to the cathode surface. The EDS analysis showed that the amount of Cr on the cathode in normal, cytochrome, and riboflavin groups was 4.71%, 6.37%, 7.56%, respectively, which was consistent with the voltage and Cr(VI) removal data. These findings demonstrated the significant enhancement of exogenous riboflavin or cytochrome on Cr(VI) reduction, thereby providing data reference for the future bio-assisted remediation of Cr(VI) pollution.

Research on the Application and Mechanisms of Electroactive Microorganisms in Toxicants Monitoring: A Review.

A biological treatment is the core process for removing organic pollutants from industrial wastewater. However, industrial wastewater often contains large amounts of toxic and harmful pollutants, which can inhibit the activity of microorganisms in a treatment system, precipitate the deterioration of effluent quality, and threaten water ecological security from time to time. In most of the existing anaerobic biological treatment processes, toxic effects on microorganisms are determined according to the amounts of end-products of the biochemical reactions, and the evaluation results are relatively lacking. When microorganisms contact toxic substances, changes in biological metabolic activity precede the accumulation of reaction products. As sensitive units, electroactive microorganisms can generate electrical signals, a change in which can directly reflect the toxicity level. The applications of electroactive microorganisms for the toxicity monitoring of wastewater are very promising. Further attention needs to be paid to considering the appropriate evaluation index, the influence of the environment on test results, mechanisms, and other aspects. Therefore, we reviewed the literature regarding the above aspects in order to provide a research foundation for the practical application of electroactive microorganisms in toxicant monitoring.

Non-fragile guaranteed cost control of microbial fuel cells.

A microbial fuel cell (MFC), which is a new type of energy source, utilises electrogenic bacteria in sewage or soil to convert chemical energy into electrical energy. MFCs typically require an external controller to provide a stable output voltage to the external load. This study develops a non-fragile guaranteed cost (NFGC) controller to suppress the interference of the controller of an MFC and ensure that the quadratic cost function of the system satisfies certain performance indexes. First, for the convenience of controller design, a Takagi-Sugeno fuzzy model is established to approximate a single-chamber single-population MFC model. Subsequently, the linear matrix inequality method is used to design the NFGC controller. This control scheme can reduce the influence of controller disturbances on the system and ensure asymptotic stability of the closed-loop system under the specified upper bound of the provided cost function. The simulation results demonstrate that the developed control method has a shorter adjustment time and smaller steady-state error than traditional control methods such as sliding mode control (SMC), backstepping control, and fuzzy SMC.

Generation of green electricity from sludge using photo-stimulated bacterial consortium as a sustainable technology.

Microbial fuel cell (MFC) is a bio-electrical energy generator that uses respiring microbes to transform organic matter present in sludge into electrical energy. The primary goal of this work was to introduce a new approach to the green electricity generation technology. In this context a total of 6 bacterial isolates were recovered from sludge samples collected from El-Sheikh Zayed water purification plant, Egypt, and screened for their electrogenic potential. The most promising isolates were identified according to 16S rRNA sequencing as Escherichia coli and Enterobacter cloacae, promising results were achieved on using them in consortium at optimized values of pH (7.5), temperature (30°C) and substrate (glucose/pyruvate 1%). Low level red laser (λ = 632.8nm, 8mW) was utilized to promote the electrogenic efficiency of the bacterial consortium, maximum growth was attained at 210 sec exposure interval. In an application of adding standard inoculum (107 cfu/mL) of the photo-stimulated bacterial consortium to sludge based MFC a significant increase in the output potential difference values were recorded, the electricity generation was maintained by regular supply of external substrate. These results demonstrate the future development of the dual role of MFCs in renewable energy production and sludge recycling.

Research progress of MOFs/carbon nanocomposites on promoting ORR in microbial fuel cell cathodes.

With the rapid development of the economy, energy demand is more urgent. Microbial fuel cells (MFCs) have the advantages of non-toxic, safety, and environmental protection, and are considered the ideal choice for the next generation of energy storage equipment. However, the slow kinetics of oxygen reduction reaction (ORR) on MFC air cathodes and the high cost of traditional platinum (Pt) catalysts hinder their practical application, so there is a need to develop efficient, low-cost, and stable electrocatalysts as alternatives. Recently, metal-organic framework (MOFs) has attracted wide attention in electrocatalysis. Electrocatalysts prepared by the nanocomposite of MOFs and carbon nanomaterials have multiple advantages, such as adjustable chemical properties, high specific surface area, and good electrical conductivity, which have been proven to be a promising electrocatalytic material. In this paper, the latest research progress of metal-organic frames (MOFs) and carbon nanocomposites is reviewed, and the preparation methods and modification of MOFs and carbon nanofibers, carbon nanotubes, and graphene composites are introduced, respectively, as well as their applications in MFC cathode. Finally, the main prospects of MOFs/carbon nanocomposite catalysts are put forward.

Sustained-release nitrate combined with microbial fuel cell: A novel strategy for PAHs and odor removal from sediment.

Nitrate addition is a biostimulation technique that can improve both the oxidation of acid volatile sulfide (AVS) through autotrophic denitrification and the biodegradation of polycyclic aromatic hydrocarbons (PAHs) via heterotrophic denitrification. However, during the remediation, parts of the dissolved nitrate in the sediment migrates from the sediment to the overlying water, leading to the loss of effective electron acceptor. To overcome this limitation, a combined approached was proposed, which involved nitrocellulose addition and a microbial fuel cell (MFC). Results indicated the nitrate could be slowly released and maintained at a higher concentration over long term. In the combined system, the removal efficiencies of PAHs and AVS were 71.56% and 89.76%, respectively. Furthermore, the voltage attained for the MFC-nitrocellulose treatment was maintained at 146.1 mV on Day 70, which was 5.37 times higher than that of the MFC-calcium nitrate treatment. Sediments with nitrocellulose resulted in lower levels of nitrate and ammonium in the overlying water. Metagenomic results revealed that the combined technology improved the expression of nitrogen-cycling genes. The introduction of MFC inhibited sulfide regeneration during incubation by suppressing the enzyme activity like EC4.4.1.2. The enhanced biostimulation provided potential for in-situ bioremediation utilizing MFC coupled with slow-released nitrate (i.e., nitrocellulose) treatment.

Application of Magnetite-Nanoparticles and Microbial Fuel Cell on Anaerobic Digestion: Influence of External Resistance.

In this paper, the application of magnetite-nanoparticles and a microbial fuel cell (MFC) was studied on the anaerobic digestion (AD) of sewage sludge. The experimental set-up included six 1 L biochemical methane potential (BMP) tests with different external resistors: (a) 100 Ω, (b) 300 Ω, (c) 500 Ω, (d) 800 Ω, (e) 1000 Ω, and (f) a control with no external resistor. The BMP tests were carried out using digesters with a working volume of 0.8 L fed with 0.5 L substrate, 0.3 L inoculum, and 0.53 g magnetite-nanoparticles. The results suggested that the ultimate biogas generation reached 692.7 mL/g VSfed in the 500 Ω digester, which was substantially greater than the 102.6 mL/g VSfed of the control. The electrochemical efficiency analysis also demonstrated higher coulombic efficiency (81.2%) and maximum power density (30.17 mW/ m2) for the 500 Ω digester. The digester also revealed a higher maximum voltage generation of 0.431 V, which was approximately 12.7 times the 0.034 V of the lowest-performing MFC (100 Ω digester). In terms of contaminants removed, the best-performing digester was the digester with 500 Ω, which reduced contaminants by more than 89% on COD, TS, VS, TSS and color. In terms of cost-benefit analysis, this digester produced the highest annual energy profit (48.22 ZAR/kWh or 3.45 USD/kWh). This infers the application of magnetite-nanoparticles and MFC on the AD of sewage sludge is very promising for biogas production. The digester with an external resistor of 500 Ω showed a high potential for use in bioelectrochemical biogas generation and contaminant removal for sewage sludge.

Improved bioelectrochemical performance of MnO2 nanorods modified cathode in microbial fuel cell.

The property of cathode in the microbial fuel cell (MFC) was one of the key factors limiting its output performance. MnO2 nanorods were prepared by a simple hydrothermal method as cathode catalysts for MFCs. There were a number of typical characteristic crystal planes of MnO2 nanorods like (110), (310), (121), and (501). Additionally, there were great many hydroxyl groups on the surface of nanorod-like MnO2, which provided a rich set of active adsorption sites. The maximum power density (Pmax) of MnO2-MFC was 180 mW/m2, which was 1.51 times that of hydrothermally synthesized MnO2 (119.07 mW/m2), 4.28 times that of naturally synthesized MnO2 (42.05 mW/m2), and 5.61 times that of the bare cathode (32.11 mW/m2). The maximum voltage was 234 mV and the maximum stabilization time was 4 days. The characteristics of MnO2, including rod-like structure, high specific surface area, and high conductivity, were conducive to providing more active sites for oxygen reduction reaction (ORR). Therefore, the air cathode modified by MnO2 nanorods was a kind of fuel cell electrode with great application potential.

A pathway for promoting bioelectrochemical performance of microbial fuel cell by synthesizing graphite carbon nitride doped on single atom catalyst copper as cathode catalyst.

In this study, a simple distributed feeding method was used to dope graphite phase carbon nitride (g-C3N4) on single atom catalyst (SAC) copper (Cu) to form composite material (Cu-SA/CN). Cu-SA/CN was formed by mutual doping of polyhedral block Cu and irregular g-C3N4. There were obvious crystal face peaks at 28.4, 43.3, 47.3 and 56.2°. Large solid Cu and small irregular g-C3N4 were successfully combined and C, Cu, N and O elements were uniformly distributed on the surface of Cu-SA/CN. The valence bond of N-CN, C-NC, CC and OH was found. When the Cu content was 0.03 mol, Cu-SA/CN3 showed excellent redox activity. The maximum power density of Cu-SA/CN3-MFC was 456.976 mW/m2, the maximum voltage was 599 mV, which could be stable for 7 d. Cu-SA/CN3 was proved to provide more electrically active sites, strong catalytic oxygen reduction ability and conductivity.

Microbial electrochemical system: an emerging technology for remediation of polycyclic aromatic hydrocarbons from soil and sediments.

Worldwide industrialization and other human activities have led to a frightening stage of release of hazardous, highly persistent, toxic, insoluble, strongly adsorbed to the soil and high molecular weight ubiquitous polycyclic aromatic hydrocarbons (PAHs) in soils and sediments. The various conventional remediation methods are being used to remediate PAHs with certain drawbacks. Time taking process, high expenditure, excessive quantities of sludge generation, and various chemical requirements do not only make these methods outdated but produce yet much resistant and toxic intermediate metabolites. These disadvantages may be overcome by using a microbial electrochemical system (MES), a booming technology in the field of bioremediation. MES is a green remediation approach that is regulated by electrochemically active microorganisms at the electrode in the system. The key advantage of the system over the conventional methods is it does not involve any additional chemicals, takes less time, and generates minimal sludge or waste during the remediation of PAHs in soils. However, a comprehensive review of the MES towards bioremediation of PAHs adsorbed in soil and sediment is still lacking. Therefore, the present review intended to summarize the recent information on PAHs bioremediation, application, risks, benefits, and challenges based on sediment microbial fuel cell and microbial fuel cell to remediate mount-up industrial sludge, soil, and sediment rich in PAHs. Additionally, bio-electrochemically active microbes, mechanisms, and future perspectives of MES have been discussed.

Biofilm formation in xenobiotic-degrading microorganisms.

The increased presence of xenobiotics affects living organisms and the environment at large on a global scale. Microbial degradation is effective for the removal of xenobiotics from the ecosystem. In natural habitats, biofilms are formed by single or multiple populations attached to biotic/abiotic surfaces and interfaces. The attachment of microbial cells to these surfaces is possible via the matrix of extracellular polymeric substances (EPSs). However, the molecular machinery underlying the development of biofilms differs depending on the microbial species. Biofilms act as biocatalysts and degrade xenobiotic compounds, thereby removing them from the environment. Quorum sensing (QS) helps with biofilm formation and is linked to the development of biofilms in natural contaminated sites. To date, scant information is available about the biofilm-mediated degradation of toxic chemicals from the environment. Therefore, we review novel insights into the impact of microbial biofilms in xenobiotic contamination remediation, the regulation of biofilms in contaminated sites, and the implications for large-scale xenobiotic compound treatment.

Determining the Dose-Response Curve of Exoelectrogens: A Microscale Microbial Fuel Cell Biosensor for Water Toxicity Monitoring.

Nowadays, the development of real-time water quality monitoring sensors is critical. However, traditional water monitoring technologies, such as enzyme-linked immunosorbent assay (ELISA), liquid chromatography, mass spectroscopy, luminescence screening, surface plasma resonance (SPR), and analysis of living bioindicators, are either time consuming or require expensive equipment and special laboratories. Because of the low cost, self-sustainability, direct current output and real-time response, microbial fuel cells (MFCs) have been implemented as biosensors for water toxicity monitoring. In this paper, we report a microscale MFC biosensor to study the dose-response curve of exoelectrogen to toxic compounds in water. The microscale MFC biosensor has an anode chamber volume of 200 µL, which requires less sample consumption for water toxicity monitoring compared with macroscale or mesoscale MFC biosensors. For the first time, the MFC biosensor is exposed to a large formaldehyde concentration range of more than 3 orders of magnitudes, from a low concentration of 1 × 10-6 g/L to a high concentration of 3 × 10-3 g/L in water, while prior studies investigated limited formaldehyde concentration ranges, such as a small concentration range of 1 × 10-4 g/L to 2 × 10-3 g/L or only one high concentration of 0.1 g/L. As a result, for the first time, a sigmoid dose-response relationship of normalized dose-response versus formaldehyde concentration in water is observed, in agreement with traditional toxicology dose-response curve obtained by other measurement techniques. The biosensor has potential applications in determining dose-response curves for toxic compounds and detecting toxic compounds in water.

Impact of reactor configuration on pilot-scale microbial fuel cell performance.

Different microbial fuel cell (MFC) configurations have been successfully operated at pilot-scale levels (>100 L) to demonstrate electricity generation while accomplishing domestic or industrial wastewater treatment. Two cathode configurations have been primarily used based on either oxygen transfer by aeration of a liquid catholyte or direct oxygen transfer using air-cathodes. Analysis of several pilot-scale MFCs showed that air-cathode MFCs outperformed liquid catholyte reactors based on power density, producing 233% larger area-normalized power densities and 181% higher volumetric power densities. Reactors with higher electrode packing densities improved performance by enabling larger power production while minimizing the reactor footprint. Despite producing more power than the liquid catholyte MFCs, and reducing energy consumption for catholyte aeration, pilot MFCs based on air-cathode configuration failed to produce effluents with chemical oxygen demand (COD) levels low enough to meet typical threshold for discharge. Therefore, additional treatment would be required to further reduce the organic matter in the effluent to levels suitable for discharge. Scaling up MFCs must incorporate designs that can minimize electrode and solution resistances to maximize power and enable efficient wastewater treatment.

[Construction and performance analysis of a microbial electrochemical sensor for monitoring heavy metals in water environment].

A microbial fuel cell (MFC)-based microbial electrochemical sensor was developed for real-time on-line monitoring of heavy metals in water environment. The microbial electrochemical sensor was constructed with staggered flow distribution method to optimize the parameters such as external resistance value and external circulation rate. The inhibition of concentration of simulated heavy metal wastewater on voltage under optimal parameters was analyzed. The results showed that the best performance of MFC electrochemical sensor was achieved when the external resistance value was 130 Ω and the external circulation rate was 1.0 mL/min. In this case, the microbial electrochemical sensors were responsive to 1-10 mg/L Cu2+, 0.25-1.25 mg/L Cd2+, 0.25-1.25 mg/L Cr6+ and 0.25-1.00 mg/L Hg2+ within 60 minutes. The maximum rejection rates of the output voltage were 92.95%, 73.11%, 82.76% and 75.80%, respectively, and the linear correlation coefficients were all greater than 0.95. In addition, the microbial electrochemical sensor showed a good biological reproducibility. The good performance for detecting heavy metals by the newly developed microbial electrochemical sensor may facilitate the real-time on-line monitoring of heavy metals in water environment.

Pilot scale microbial fuel cells using air cathodes for producing electricity while treating wastewater.

Microbial fuel cells (MFCs) can generate electrical energy from the oxidation of the organic matter, but they must be demonstrated at large scales, treat real wastewaters, and show the required performance needed at a site to provide a path forward for this technology. Previous pilot-scale studies of MFC technology have relied on systems with aerated catholytes, which limited energy recovery due to the energy consumed by pumping air into the catholyte. In the present study, we developed, deployed, and tested an 850 L (1400 L total liquid volume) air-cathode MFC treating domestic-type wastewater at a centralized wastewater treatment facility. The wastewater was processed over a hydraulic retention time (HRT) of 12 h through a sequence of 17 brush anode modules (11 m2 total projected anode area) and 16 cathode modules, each constructed using two air-cathodes (0.6 m2 each, total cathode area of 20 m2) with the air side facing each other to allow passive air flow. The MFC effluent was further treated in a biofilter (BF) to decrease the organic matter content. The field test was conducted for over six months to fully characterize the electrochemical and wastewater treatment performance. Wastewater quality as well as electrical energy production were routinely monitored. The power produced over six months by the MFC averaged 0.46 ± 0.35 W (0.043 W m-2 normalized to the cross-sectional area of an anode) at a current of 1.54 ± 0.90 A with a coulombic efficiency of 9%. Approximately 49 ± 15 % of the chemical oxygen demand (COD) was removed in the MFC alone as well as a large amount of the biochemical oxygen demand (BOD5) (70%) and total suspended solid (TSS) (48%). In the combined MFC/BF process, up to 91 ± 6 % of the COD and 91 % of the BOD5 were removed as well as certain bacteria (E. coli, 98.9%; fecal coliforms, 99.1%). The average effluent concentration of nitrate was 1.6 ± 2.4 mg L-1, nitrite was 0.17 ± 0.24 mg L-1 and ammonia was 0.4 ± 1.0 mg L-1. The pilot scale reactor presented here is the largest air-cathode MFC ever tested, generating electrical power while treating wastewater.

Enhanced bioelectrochemical performance of microbial fuel cell with titanium dioxide-attached dual metal organic frameworks grown on zinc aluminum - layered double hydroxide as cathode catalyst.

In this study, a three-step distributed feeding method was used to prepare TiO2-attached dual CoZn-metal organic frameworks growing on ZnAl-layered double hydroxide (TiO2@ZIF-67/ZIF-8@ZnAl-LDH) as cathode catalyst of microbial fuel cell (MFC). The composite material was a composite core-shell structure constructed by multi-layer coating with sheet-like ZnAl-LDH as the base, dual MOFs as the magnetic core and TiO2 as the rough surface. The composite material had crystal planes (009), (110), (101) interface. The rough surface, core-shell core and polyhedral structure of TiO2@ZIF-67/ZIF-8@ZnAl-LDH were observed. The complete distribution of Ti, Zn, Al, and Co in the material was observed and offered active sites. The contents of Ti (15.97 %), Al (5.53 %), Na (5.04 %), N (3.52%), Zn (1.47 %) were found out. TiO2@ZIF-67/ZIF-8@ZnAl-LDH was excellent in electrochemical activity and the maximum power density was 409.6 mW/m2, the stable continuous output voltage was 538.4 mV for 8 d.

Improving oxygen reduction reaction of microbial fuel cell by titanium dioxide attaching to dual metal organic frameworks as cathode.

In this study, a two-step simple distributed feeding method was used to prepare the core-shell nanocomposite dual metal organic frameworks (D-MOFs, TiO2@ZIF-67/ZIF-8). There were three obvious peaks (011), (112), (222) interface in D-MOFs core, which fully showed that ZIF-67/ZIF-8 crystal core was successfully synthesized. The morphology of composite material was core-shell structure with a rough surface, and Ti, Co, Zn, Al were uniformly distributed on the surface. TiO2@ZIF-67/ZIF-8 also had excellent electrochemical activity and the maximum power density of TiO2@ZIF-67/ZIF-8 microbial fuel cell (MFC) was 341.506 mW/m2, which was 1.30 times of ZIF-67/ZIF-8-MFC (262.144 mW/m2) and 2.07 times of ZIF-67-MFC (164.836 mW/m2). And the continuous output voltage of TiO2@ZIF-67/ZIF-8-MFC was 413.43 mV, which could maintain stable voltage output for 8.3 days. D-MOFs as the core of composites ensured the integrity, stability and high activity of materials; Rough TiO2 as the surface of the material provided surface area and reaction center.

Gram-positive bacteria covered bioanode in a membrane-electrode assembly for use in bioelectrochemical systems.

A novel strain of Gram-positive bacteria Paenibacillus profundus YoMME was recognized by sequencing of 16S rRNA gene and after that tested for exoelectrogenicity for the first time. It was found that at an applied potential of -0.195 V (vs. SHE) the bacteria are capable of generating electricity and forming electroactive biofilms for 3-4 days. A tendency for the decrease in double-layer capacitance and the increase in the charge transfer resistance during the maturation of the biofilm was established. The formed bioanodes were used as a part of a membrane-electrode assembly (MEA) together with a selected cathode (E-Tek) and a separator (Zirfon). The applicability of MEA with the bioanode was tested by operating a newly designed bioelectrochemical system in a microbial fuel cell (MFC) or microbial electrolysis cell (MEC) mode. A current density of 200 mA m-2 was generated by the MFC after the improvement of the cathodic reaction through facilitated air access. The Coulombic efficiency in different MFC runs ranged from 5.2 to 7.4%. It was also determined that 0.65 V applied cell voltage is appropriate for the operation of the cell in the electrolysis mode, during which a current density of 2-3 Am-2 was reached. This, along with the evolved gas on the cathode, shows that as an anodic biocatalyst P. profundus YoMME assists the electrolysis processes at a significantly lower voltage than the theoretical one (1.23 V) for water decomposition. The hydrogen production rate varied between 0.5 and 0.7 m3/m3d and the cathodic hydrogen recovery ranged from 49.5 to 61.5 %. The estimated energy efficiency based on the electricity input exceeds 100 %, which indicates that additional energy is being gained from the biotic oxidation of the available organics.

Enhanced performance of microbial fuel cell with electron mediators from tetracycline hydrochloride degradation.

Tetracycline hydrochloride (TCH) is a typical antibiotic pollutant with high toxicity and persistence. The degradation of TCH and the generation of the associated electron mediator in a dual chamber microbial fuel cells (MFCs) were studied. The results of liquid chromatography revealed that TCH could be effectively removed (>93%) in MFCs mode. The maximum COD removal was 88.14 ± 1.47% in MFCs while it was 69.57 ± 1.36% in open circuit MFCs. According to cyclic voltammetry, the presence of the relevant redox peaks clearly suggested that the intermediates from TCH degradation could act as endogenous electron mediator. The highest power density of 120.02 ± 2.76 mW/m2 and the lowest internal resistance of 18.68 Ω were achieved in MFC with 2 mg/L of TCH. Microbial community analysis illustrated that Bacteroides, Comamonas, Clostridium_sensu_stricto, Desulfovibrio and Geobacter were enriched and played a dominant role in TCH degradation and power generation. Electrochemical active bacteria had certain tolerance to TCH and the inhibiting threshold value of TCH was below 5 mg/L. This study provided a new thinking that low concentration of TCH could produce electron mediators to improve the performance of MFC system.

The potential of Co3O4 nanoparticles attached to the surface of MnO2 nanorods as cathode catalyst for single-chamber microbial fuel cell.

A simple two-step hydrothermal method was used to prepare the cathode catalyst of microbial fuel cell (MFC). MnO2@Co3O4 composite was successfully prepared by in-situ growth of nano-particle-like Co3O4 on nano-rod-like MnO2. The hybrid products had (121), (310), (311), (400) and (511) crystal planes, rod-like and point-like structures were observed. MnO2@Co3O4 nanohybrids were rich in a variety of metallic elements and provided rich electrochemically active sites. The maximum voltage of MnO2@Co3O4-MFC was 425 mV, the maximum stabilization time was 4 d. The maximum output power was 475 mW/m2, which was 2.24 times that of Co3O4-MFC (212 mW/m2) and 2.63 times of MnO2-MFC (180 mW/m2). The rod-like structure of MnO2 could effectively improve the ion flow efficiency and reduce the transfer resistance, and the point-like structure of Co3O4 can increase the specific surface area of the complex and provide more active sites.