Anodic Biofilm Research Articles

Microbial approach towards anode biofilm engineering enhances extracellular electron transfer for bioenergy production

Applying microbial electrolysis cells (MEC) is a biological approach to enhance the growth of high amounts of electroactive biofilm for extracellular electron transfer. The electroactive biofilm degrades the organics by oxidizing them at the anode and producing electrical energy. Addition of waste-activated sludge (WAS) with fat grease oil (FOG) produces an optimal reactor environment for microbial growth to enhance the exchange of electrons between cells via microbial electrolysis. The present work aimed to investigate the microbial approach to increase the extracellular electron transfer (EET) in microbial electrolysis cells. Results revealed that metabolites in electroactive microbes (EAM) grow viable cells that initiate high EET at anode sites. At optimum WAS with FOG addition, volatile fatty acid and current generation yield production was 2.94 ± 0.19 g/L and 17.91 ± 7.23 mA, accompanied by COD removal efficiency of 89.5 ± 14.4%, respectively. This study introduces a novel approach to anode biofilm engineering that significantly enhances extracellular electron transfer, offering a fresh perspective on bioenergy production. Our approach, which demonstrates that anodic biofilm enhances intercellular electron transfer, increases NADH-NAD ratio, and increases metabolite yield-fluxes, has the potential to revolutionize bio-electricity production. Results indicated that the electrolysis highlights MEC performance in power generation of 788 mV with 200 mL of anode volume of active viable cells by utilizing WAS with 11% FOG. The achievements of this study provide critical parameters for the anode biofilm engineering, demonstrating how growth cell volume, intercellular electron transfer, and increases in NADH-NAD ratio are evidence of an increase in the EET, compelling evidence for the resilience treatment and efficient current production. These findings are significant in advancing our understanding of bioenergy production.

A novel tubular single-chamber microbial electrolysis cell for efficient methane production from industrial potato starch wastewater

The integration of microbial electrolysis cells (MEC) with anaerobic digestion (AD) shows great promise for enhancing methane production from high-COD wastewater. However, an efficient MEC-AD reactor design remains elusive. Here, a novel tubular single-chamber MEC-AD reactor was constructed to treat potato starch wastewater (COD over 20000mg/L). The concentric and compact design of the stainless-steel cathode and anode reduced internal resistance, resulting in enhanced methane production. Applying -0.2V vs. Ag/AgCl to the anode increased methane production by 1.73 times compared to the open circuit and halved hydraulic retention time. Moreover, the reactor achieved an average methane content of 82.57%, which was 23.89% higher than the open circuit. The reactor showed a total COD removal of 92.2%, which was 24% higher than the open circuit. Additionally, base consumption to maintain pH was reduced to one-sixth of that in conventional AD, preventing volatile fatty acid accumulation. Microbial analysis showed Geobacter (63.4%) and Methanobacterium (96.8%) were highly enriched in the anode and cathode biofilms, respectively. The proportion of fermentative bacteria also increased in the MEC-AD system. These results demonstrate the effectiveness of the tubular single-chamber MEC-AD reactor in enhancing methane production from potato starch wastewater, with strong potential for scale-up applications.

Bacillus amyloliquefaciens strain NSB4 bacteria for treating wastewater for fuel cell application

Pollutants in water bodies come from a variety of sources, including but not limited to domestic, industrial, municipal etc. Water contamination and energy shortages are global problems that require significant attention. Therefore, it is essential to synthesize sustainable energy and transport waste-free water to the water reception points. Concerns about energy shortages and water contamination have prompted the development of microbial fuel cell technology. Microorganisms are used by the electrochemical cell nature of MFCs to digest the organic wastes and produce energy anaerobically. Focusing on single-chambered mediator-less MFCs operating in batch mode, this study assesses the efficacy of a novel bacterial strain Bacillus amyloliquefaciens NSB4, as an exoelectrogen regarding electricity yield and waste elimination. Results from the strain's electrochemical characterization showed a maximum current density of 0.4804A/m2 and a power density of 41.281mW/m2. Additionally, the columbic efficiency (72%) and COD reduction efficiency (90.46%) were also remarkably high. Growth of the anodic biofilm during the MFC process displayed the crucial performance of the exoelectrogen used. SEM images of the biofilm are also presented in the study.

Magnetic, conductive nanoparticles as building blocks for steerable micropillar-structured anodic biofilms

In bioelectrochemical systems (BES), biofilm formation and architecture are of crucial importance, especially for flow-through applications. The interface between electroactive microorganisms and the electrode surface plays an important and often limiting role, as the available surface area influences current generation, especially for poor biofilm forming organisms. To overcome the limitation of the available electrode surface, nanoparticles (NPs) with a magnetic iron core and a conductive, hydrophobic carbon shell were used as building blocks to form conductive, magnetic micropillars on the anode surface. The formation of this dynamic three-dimensional electrode architecture was monitored and quantified in situ using optical coherence tomography (OCT) in conjunction with microfluidic BES systems. By cyclic voltammetry the assembled three-dimensional anode extensions were found to be electrically conductive and increased the available electroactive surface area. The NPs were used as controllable carriers for the electroactive model organisms Shewanella oneidensis and Geobacter sulfurreducens, resulting in a 5-fold increase in steady-state current density for S. oneidensis, which could be increased 22-fold when combined with Poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT:PSS) aggregates. In the case of G. sulfurreducens, the steady-state current density was not increased, but was achieved four times faster. The study presents a controllable, scalable and easy-to-use method to increase the electrode surface area in existing BES by applying a magnetic field and adding conductive magnetic NPs. These findings can most likely also be transferred to other electroactive microorganisms.

Redox potential shapes spatial heterogeneity of mixed-cultured electroactive biofilm treating wastewater

The core of bioelectrochemical systems (BESs) is electrochemically active microorganisms (EAMs), which exert spatial heterogeneity on electrode surface and influences BESs performance. Setting an optimal potential is an effective strategy for improving and optimizing BESs performance, however, how the electrode potential affects spatial structure of microbial community within anode biofilm is not known. Using a complex substrate-fed BES with a wastewater inoculum, this study investigated the community structure and composition of the stratified biofilm developed under the potential of −0.3 V, 0 V, +0.3 V and +0.6 V (vs. saturated calomel electrode) by freezing microtome method and high-throughput sequencing analysis. The spatial heterogeneity of biofilm community was found to be dependent on the electrode potential and a less-stratified community structure was observed for +0.6 V than other potentials. Within the biofilms, the inner layers selected more Geobacter and the outer layers enriched more Acinetobacter and Serratia, potentially suggested a stratification of electron transfer pathway and metabolite-based interspecies communications. The results demonstrated the response of spatial heterogeneity of anode biofilm community to the change of electrode potential, which help to understand the selective and enrichment of kinetically efficient anodic microbiome by electron potential.

Pilot microbial electrolysis cell closes the hydrogen loop for hydrothermal wet waste conversion to jet fuel

The global shift toward net-zero emissions necessitates resource recovery from wet waste. In this study, we demonstrate the first feasibility of combining pilot-scale microbial electrolytic cells (MECs) with hydrothermal liquefaction (HTL) for simultaneous post-hydrothermal liquefaction wastewater (PHW) treatment and efficient hydrogen (H₂) production to meet biocrude upgrading requirements. Long-term single reactor operation revealed that fixed anode potential enabled rapid startup, and low catholyte pH and high salinity were effective in suppression of cathodic methanogenesis and acetogenesis – resulting in high current density of 16.6 A m−2 and 9.3 A m−2 when feeding synthetic wastewater and PHW respectively. Additionally, the anode biofilm exhibited spatial variations in response to local environmental conditions. Onsite parallel or serial operations of multiple MECs showed good performance using actual PHW with a record-high H2 production rate of 0.5 L LR day−1 for MEC over 10 liters scale, and the optimal chemical oxygen demand (COD)-to-H2 yield reached 0.127 kg-H2 per kg-COD, supporting a self-sufficient, closed-loop upgrade to jet fuel.

Bifunctional electrode materials: Enhancing microbial fuel cell efficiency with 3D hierarchical porous Fe3O4/Fe-N-C structures

The rational development of high-performance anode and cathode electrodes for microbial fuel cells (MFCs) is crucial for enhancing MFC performance. However, complex synthesis methods and single-performance electrode materials hinder their large-scale implementation. Here, three-dimensional hierarchical porous (3DHP) Fe3O4/Fe-N-C composites were prepared via the hard template method. Notably, Fe3O4/Fe-N-C-0.04-600 demonstrated uniformly dispersed Fe3O4 nanoparticles and abundant Fe-Nx and pyridinic nitrogen, showing excellent catalytic performance for oxygen reduction reaction (ORR) with a half-wave potential (E1/2) of 0.74 V (vs. RHE), surpassing Pt/C (0.66 V vs. RHE). Moreover, Fe3O4/Fe-N-C-0.04-600 demonstrated favorable biocompatibility as an anode material, enhancing anode biomass and extracellular electron transfer efficiency. Sequencing results confirmed its promotion of electrophilic microorganisms in the anode biofilm. MFCs employing Fe3O4/Fe-N-C-0.04-600 as both anode and cathode materials achieved a maximum power density of 831.8 ± 27.7 mW m−2, enduring operation for 38 days. This study presents a novel approach for rational MFC design, emphasizing bifunctional materials capable of serving as anode materials for microorganism growth and as cathode catalysts for ORR catalysis.

Vanadium (V) reduction and the performance of electroactive biofilms in microbial fuel cells with Shewanella putrefaciens

The electron transfer ability of biofilms significantly influences the electrochemical activity of microbial fuel cells (MFCs). However, there is limited understanding of pentavalent vanadium (V(V)) bioreduction and microbial response characteristics in MFCs. In this study, the effect of gradient concentrations of V(V) on the performance of EABs with Shewanella putrefaciens in MFCs was investigated. The results showed that as V(V) concentration increased (0–100 mg/L), the voltage output, power densities, polarization, and electrode potential decreased. V(V) was found to act as an electron acceptor and was reduced during MFCs operation, with a yield of 83.16% being observed at 25 mg/L V(V). Cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) indicated declining electrochemical performance of the MFCs with escalating V(V) concentration. The content of protein and polysaccharide from extracellular polymeric substances (EPS) in anodic biofilms increased to 66.75 and 49.15 mg/L at 75 mg/L V(V), respectively. Three-dimensional fluorescence spectroscopy confirmed increased humic substances in EPS extraction with V(V) exposure. The functional genes narG, nirK, and gor involved in V(V) reduction were upregulated with rising V(V) concentration through quantitative polymerase chain reaction (qPCR) analysis. Additionally, riboflavin, cytochrome c, nicotinamide adenine dinucleotide (NADH), and electron transport system activity (ETSA), key indicators for assessing electron transfer behavior, exhibited a negative correlation with various V(V) concentrations, decreasing by 31.81%, 57.14%, 67.39%, and 51.41%, respectively, at a concentration of 100 mg/L V(V) compared to the blank control. These findings contribute valuable insights into the response of EABs to V(V) exposure, presenting potential strategies for enhancing their effectiveness in the treatment of vanadium-contaminated wastewater.

Impact of extended starvation conditions on bioelectrocatalytic activity of a methane-producing microbial electrolysis cell

The performance of a methane-producing microbial electrolysis cell (MEC) markedly relies on the activity and resilience of its electroactive anodic biofilm. Here, the capability of an MEC anodic biofilm to recover following extended starvation periods (90 days) and to function under different applied anode potentials (i.e., +0.20 and −0.10 V, vs. Standard Hydrogen Electrode-SHE) was investigated. Cyclic voltammetry proved to be an insightful means to characterize the biofilm electrocatalytic activity and to track the dynamics of biofilm reactivation. Under all tested conditions the anodic biofilm rapidly and completely recovered from starvation in less than 144 h. However, starvation reduced the electron transfer redundancy of the biofilm causing the disappearance of redox sites operating at the more positive potentials (around 0.0 V vs. SHE) and retaining those having a formal potential lower than −0.18 V vs. SHE. This study presents compelling evidence for the resilience and efficiency of methane-producing MEC.

Enrichment of Geobacter on Anode Biofilms from Domestic Wastewater without Posing Anode Potential in Microbial Electrochemical Cells

Enrichment of Geobacter on Anode Biofilms from Domestic Wastewater without Posing Anode Potential in Microbial Electrochemical Cells

Carbon chain elongation characterizations of electrode-biofilm microbes in electro-fermentation

The higher efficiency of electro-fermentation in synthesizing medium-chain fatty acids (MCFAs) compared to traditional fermentation has been acknowledged. However, the functional mechanisms of electrode-biofilm enhancing MCFAs synthesis remain research gaps. To address this, this study proposed a continuous flow electrode-biofilm reactor for chain elongation (CE). After 225 days of operation, stable electrode-biofilms formed and notably improved caproate yield by more than 38 %. The electrode-biofilm was enriched with more CE microorganisms and electroactive bacteria compared to the suspended sludge microorganisms, including Caproicibacterium, Oscillibacter and Pseudoramibacter. Besides, the upregulated CE pathways were evaluated by metagenomic analysis, and the results indicated that the pathways such as acetyl-CoA and malonyl-[acp] formation, reverse beta-oxidation, and fatty acid biosynthesis pathway were all markedly enhanced in cathodic biofilm, more than anodic biofilm and suspended microorganisms. Moreover, microbial community regulated processes like bacterial chemotaxis, flagellar assembly and quorum sensing, crucial for electrode-biofilm formation. Electron transfer, energy metabolism, and microbial interactions were found to be prominently upregulated in the cathodic biofilm, surpassing levels observed in anodic biofilm and suspended sludge microorganisms, which further enhanced CE efficiency. In addition, the statistical analyses further highlighted key microbial functions and interactions within the cathodic biofilm. Oscillospiraceae_bacterium was identified to be the most active microbe, alongside pivotal roles played by Caproiciproducens_sp._NJN-50, Clostridiales_bacterium, Prevotella_sp. and Pseudoclavibacter_caeni. Eventually, the proposed microbial collaboration mechanisms of cathodic biofilm were ascertained. Overall, this study uncovered the biological effects of the electrode-biofilm on MCFAs electrosynthesis, thereby advancing biochemicals production and filling the knowledge gaps in CE electroactive biofilm reactors.

The effect of inoculum source of different pollution levels on the performances of microbial fuel cell biosensors

Selection of inoculum sources is a key factor in constructing microbial fuel cells (MFCs), and the property of inoculum sources is greatly affected by the degree of environmental pollution. However, limited attention has been paid to how these differences affect the response of MFC biosensors. Here the effects of inoculum sources with varying pollution levels on the performances of constructed MFCs were evaluated, and the microbial communities were analyzed before and after inoculation. The results showed significant differences in the detection of biochemical oxygen demand (BOD) and toxicity (Cu2+) among the five groups of MFC biosensors. Combined with the data of the microbial community, the results indicated that the increase rate of the initial start-up voltage is related to the abundance of original electroactive bacteria (EAB) in the inoculum source. The higher the abundance of EAB, the faster increase rate in the initial start-up voltage and the shorter start-up time. The difference in the detection range of the BOD should be related to the ability of the microbial communities to withstand the organic shock loads. The microbial community's tolerance to Cu2+ was affected by the original water quality of the inoculum source. The high metal ion content leads to low sensitivity of MFC biosensor to Cu2+ ion. Enterobacteriaceae were abundant in all the five groups of MFCs, indicating that the dominant bacteria can be enriched in MFC anode biofilms with the inoculum sources of different pollution levels. The microbial community compositions of the anode biofilms were affected by the inoculum sources of different pollution levels, which in turn resulted in the differences in MFCs performances.

A directional electrode separator improves anodic biofilm current density in a well-mixed single-chamber bioelectrochemical system

In this study, a directional electrode separator (DES) was designed and incorporated into a single-chamber bioelectrochemical system (BES) to reduce migration and reoxidation of hydrogen. This issue arises when H2, generated at the cathode, travels to the anode where anodic biofilms use H2. To test the feasibility of our design, a 3D-printed BES reactor equipped with a DES was inoculated with anaerobic digestor granules and operated under fed-batch conditions using fermented corn stover effluent. The DES equipped reactor achieved significantly higher current densities (∼53 A/m²) compared to a conventional single-chamber BES without a separator (∼16 A/m²), showing a 3.3 times improvement. Control abiotic electrochemical experiments revealed that the DES exhibited significantly higher proton conductivity (456±127 µS/mm) compared to a proton exchange membrane (67±21 µS/mm) with a statistical significance of P=0.03. The DES also effectively reduced H2 migration to the anode by 21-fold relative to the control. Overall, incorporating a DES in a single-chamber BES enhanced anodic current density by reducing H2 migration to the anode.

External circuit loading mode regulates anode biofilm electrochemistry and pollutants removal in microbial fuel cells

This study investigated the effects of different external circuit loading mode on pollutants removal and power generation in microbial fuel cells (MFC). The results indicated that MFC exhibited distinct characteristics of higher maximum power density (Pmax) (named MFC-HP) and lower Pmax (named MFC-LP). And the capacitive properties of bioanodes may affect anodic electrochemistry. Reducing external load to align with the internal resistance increased Pmax of MFC-LP by 54.47 %, without no obvious effect on MFC-HP. However, intermittent external resistance loading (IER) mitigated the biotoxic effects of sulfamethoxazole (SMX) (a persistent organic pollutant) on chemical oxygen demand (COD) and NH4+-N removal and maintained high Pmax (424.33 mW/m2) in MFC-HP. Meanwhile, IER mode enriched electrochemically active bacteria (EAB) and environmental adaptive bacteria Advenella, which may reduce antibiotic resistance genes (ARGs) accumulation. This study suggested that the external circuit control can be effective means to regulate electrochemical characteristics and pollutants removal performance of MFC.

Isolation of Electrochemically Active Bacteria from an Anaerobic Digester Treating Food Waste and Their Characterization.

Studies have used anaerobic-digester sludge and/or effluent as inocula for bioelectrochemical systems (BESs), such as microbial fuel cells (MFCs), for power generation, while limited studies have isolated and characterized electrochemically active bacteria (EAB) that inhabit anaerobic digesters. In the present work, single-chamber MFCs were operated using the anaerobic-digester effluent as the sole source of organics and microbes, and attempts were made to isolate EAB from anode biofilms in MFCs by repeated anaerobic cultivations on agar plates. Red colonies were selected from those grown on the agar plates, resulting in the isolation of three phylogenetically diverse strains affiliated with the phyla Bacillota, Campylobacterota and Deferribacterota. All these strains are capable of current generation in pure-culture BESs, while they exhibit different electrochemical properties as assessed by cyclic voltammetry. The analyses of their cell-free extracts show that cytochromes are abundantly present in their cells, suggesting their involvement in current generation. The results suggest that anaerobic digesters harbor diverse EAB, and it would be of interest to examine their ecological niches in anaerobic digestion.

An effective, novel and low-cost proton exchange membrane for microbial fuel cell-based bioelectricity production

Microbial Fuel Cells (MFCs) are a substitute for fossil-fuel-based electricity generation. They are innovative bioelectrochemical systems that use microbial catalysts to convert organic waste directly into electrical energy. However, MFCs face several commercialization challenges, including expensive Proton Exchange Membranes (PEMs), making them unaffordable. The present research aims to develop cost-effective, environmentally friendly, high-performance PEM to make MFC technology more viable. The study analyzed using MFCs with different PEMs with native microflora and Serratia marcescens (AATB1) as biocatalysts to produce bioelectricity and treat septic tank wastewater (STWW). The experiment included a control group with sterile STWW. The study involves fabricating and characterizing the optimized Novel Cement Supported Conductive Salts PEM (NCSCS PEM) using SEM, TGA, and EIS techniques. The commercial Nafion 117 and salt bridge were used to compare NCSCS PEM in MFCs. The anode biofilm was investigated using CV, CLSM, and SEM. The MFCs with Nafion 117, NCSCS PEM, and Salt bridge produced power densities of 126.6 ± 1.06 mW/m2, 204.04 ± 0.87 mW/m2, and 188.26 ± 1.13 mW/m2, respectively. Moreover, Our study shows a greater PEM cost reduction with commercial Nafion 117 PEM in terms of consumed cost of $7.04, $0.21, and $2.41 for making MFCs with Nafion 117 (9 cm2), NCSCS PEM (15 cm3) (with 97.02 % reduced cost) and salt bridge (15 cm3) (with 65.77 % reduced cost) respectively. Our MFC setup cost was reduced by 70.29 % by replacing Nafion 117 with durable NCSCS PEM. Using our cost-effective, better-performing, durable NCSCS in MFC makes the MFC technology or any other technology that needs PEM feasible on a larger scale.

Magnetic biochar enhanced microbial electrolysis cell with anaerobic digestion for complex organic matter degradation in landfill leachate

Combining microbial electrolytic cells with anaerobic digestion (MEC-AD) was considered as an important method for enhancing complex organic matter degradation. However, the magnetic biochar (MBC) addition would be an effective approach for enhancing biodegradation in MEC-AD. By designing orthogonal experiments, the optimal parameters of MBC-enhanced MEC-AD system for landfill leachate treatment were determined. The results indicated that the optimal conditions were identified as HRT of 72 h, electrode spacing of 2.5 cm, and applied voltage of 0.8 V. Under these conditions, the COD removal efficiency reached a maximum of 54.7 %. Additionally, the UV–vis, 3D-EEM, and GC–MS indicated the macromolecules 13-Docosenamide (Z), Bis(2-ethylhexyl) benzene-1,4-dicarboxylate and bis(2-ethylhexyl) phthalate were degraded. 13-Docosenamide (Z) was almost completely removed under the conditions of 0.8 V applied voltage, 2.5 cm electrode spacing and 24 h HRT, with a removal efficiency of 99.91 %. Significant differences were observed in the microbial core genera among the MEC-AD systems. The core genera in the anodic and cathodic biofilms were primarily fermentative and electroactive bacteria, including Soehngenia (2.2 % - 32.1 %, 3.2 % - 26.4 %) and Desulfomicrobium (1.1 % - 10.2 %, 2.0 % - 29.3 %). Fermentative bacteria, norank_f__Bacteroidetes_vadinHA17, established cooperative relationships with electroactive bacteria Acinetobacter. The enrichment of electrochemically active bacteria optimized microbial interactions, thereby synergistically enhancing the biotransformation of complex organic matter in landfill leachate.

Impact of Air-Cathodes on Operational Stability of Single-Chamber Microbial Fuel Cell Biosensors for Wastewater Monitoring

The increasing global water pollution leads to the need for urgent development of rapid and accurate water quality monitoring methods. Microbial fuel cells (MFCs) have emerged as real-time biosensors for biochemical oxygen demand (BOD), but they grapple with several challenges, including issues related to reproducibility, operational stability, and cost-effectiveness. These challenges are substantially shaped by the selection of an appropriate air-breathing cathode. Previous studies indicated a critical influence of the cathode on both the enduring electrochemical performance of MFCs and the taxonomic diversity at the electroactive anode. However, the effect of different gas diffusion electrodes (GDE) on 3D-printed single-chamber MFCs for BOD biosensing application and its effect on the bioelectroactive anode was not investigated before. Our study focuses on comparing GDE cathode materials to enhance MFC performance for precise and rapid BOD analysis in wastewater. We examined for over 120 days two Pt-coated air-breathing cathodes with distinct carbonaceous gas diffusion layers (GDLs) and catalyst layers (CLs): cost-effective carbon paper (CP) with hand-coated CL and more expensive woven carbon cloth (CC) with CL pre-applied by the supplier. The results show significant differences in electrochemical characteristics and anodic biofilm composition between MFCs with CP and CC GDE cathodes. CP-MFCs exhibited lower sensitivity (16.6 C L mg−1 m−2) and a narrower dynamic range (25 to 600 mg L−1), attributed to biofouling-related degradation of the GDE. In contrast, CC-MFCs demonstrated superior performance with higher sensitivity (37.6 C L mg−1 m−2) and a broader dynamic range (25 to 800 mg L−1). In conclusion, our study underscores the pivotal role of cathode selection in 3D-printed MFC biosensors, influencing anodic biofilm enrichment time and overall BOD assessment performance. We recommend the use of cost-effective CP GDL with hand-coated CL for short-term MFC biosensor applications, while advocating for CC GDL supplied with CL as the preferred choice for long-term sensing implementations with enduring reliability.

Insight into a single-chamber air-cathode microbial fuel cell for nitrate removal and ecological roles.

Bioelectrochemical systems are sustainable and potential technology systems in wastewater treatment for nitrogen removal. The present study fabricated an air-cathode denitrifying microbial fuel cell (DNMFC) with a revisable modular design and investigated metabolic processes using nutrients together with the spatiotemporal distribution characteristics of dominated microorganisms. Based on the detection of organics and solvable nitrogen concentrations as well as electron generations in DNMFCs under different conditions, the distribution pattern of nutrients could be quantified. By calculation, it was found that heterotrophic denitrification performed in DNMFCs using 56.6% COD decreased the Coulombic efficiency from 38.0% to 16.5% at a COD/NO3 --N ratio of 7. Furthermore, biological denitrification removed 92.3% of the nitrate, while the residual was reduced via electrochemical denitrification in the cathode. Correspondingly, nitrate as the electron acceptor consumed 16.7% of all the generated electrons, and the residual electrons were accepted by oxygen. Microbial community analysis revealed that bifunctional bacteria of electroactive denitrifying bacteria distributed all over the reactor determined the DNMFC performance; meanwhile, electroactive bacteria were mainly distributed in the anode biofilm, anaerobic denitrifying bacteria adhered to the wall, and facultative anaerobic denitrifying bacteria were distributed in the wall and cathode. Characterizing the contribution of specific microorganisms in DNMFCs comprehensively revealed the significant role of electroactive denitrifying bacteria and their cooperative relationship with other functional bacteria.

Improving Scalability of copper recovery in saline microbial fuel cells with microtubular polypyrrole-based cathodic electrocatalysts

Microbial fuel cells (MFC) are emerging energy-efficient systems for copper (Cu) electrowinning from waste streams by coupling it with anodic oxidation of organics in wastewater. However, there is a lack of research examining scalable electrocatalysts for Cu electrowinning at low cathodic overpotentials in highly saline catholytes often found in e-waste leachates. The challenge of developing resilient anodic biofilms that withstand the antagonistic effects of ions migrating from catholytes in saline MFC also needs to be addressed. In this study, polypyrrole (PPy) cathodic electrocatalysts were developed and coupled with a robust halophilic anodic biofilm in MFC to improve the kinetics of Cu electrowinning from acidic chloride-based catholytes. Electrochemical characterisation of these cathodes revealed shuttling of electrons by redox-active PPy via the formation of intermediate Cu+-complexes as an energy-efficient pathway for producing metallic Cu. High power densities ranging from 0.63 ± 0.17 to 0.73 ± 0.05 W m−2 were achieved with undoped-PPy and phytic acid doped-PPy cathodes with simultaneous recovery of ∼97% Cu. These electrocatalysts also exhibited low charge transfer resistance (3–8 mΩ m2) that met the requisites for scalable cathodes in MFC. However, a decrease in the efficiency of PPy cathodes was observed over 5 d due to competing reactions at their interfaces, including re-oxidation of deposited Cu and cathodic corrosion, with further studies suggested to enhance their corrosion resistance. Nonetheless, integrating PPy electrocatalysts for Cu electrowinning in saline MFC has advanced its outlooks as an energy-efficient downstream process for urban mining of Cu from e-waste.