Graphene and biochar-based cathode catalysts for microbial fuel cell: Performance evaluation, economic comparison, environmental and future perspectives.

Microbial fuel cells (MFCs) have been the prime focus of research in recent years because of their distinctive feature of concomitantly treating and producing electricity from wastewater. Nevertheless, the electrical performance of MFCs is hindered by a protracted oxygen reduction reaction (ORR), and often a catalyst is required to boost the cathodic reactions. Conventional transition metals-based catalysts are expensive and infeasible for field-scale usage. In this regard, carbon-based electrocatalysts like waste-derived biochar and graphene are used to enhance the commercialisation prospects of MFC technology. These carbon-catalysts possess unique properties like superior electrocatalytic activity, higher surface area, and high porosity conducive to ORR. Theoretically, graphene-based cathode catalysts yield superior results than a biochar-derived catalyst, though at a higher cost. In contrast, the synthesis of waste-extracted biochar is economical; however, its ability to catalyse ORR is debatable. Therefore, this review aims to make a side-by-side techno-economic assessment of biochar and graphene-based cathode catalyst used in MFC to predict the relative performance and typical cost of power recovery. Additionally, the life cycle analysis of the graphene and biochar-based materials has been briefly discussed to comprehend the associated environmental impacts and overall sustainability of these carbo-catalysts.

Waste coconut shell-derived carbon monolith as an efficient binder-free cathode for electrochemical advanced oxidation treatment of endocrine-disrupting compounds.

Discharge of endocrine-disrupting compounds such as methylparaben (MePa) into natural water bodies deteriorates the aquatic ecosystem. In this regard, electrochemical oxidation (EO) and electro-Fenton (EF) processes are acknowledged as effective methods to eliminate biorecalcitrant compounds from different wastewater matrices. In these systems, the H2O2-producing ability of carbon-based cathodes is put to advantage for producing homogenous hydroxyl radicals by simulating Fenton's reaction, which dramatically augments the contaminant removal efficiency. However, commercial carbon based cathodes are not economically affordable, especially for voluminous treatment. Hence in the present work, waste-derived carbonised coconut shell (CCS) monolith was employed as a cathode in EO and EF treatment of MePa. Almost the entire MePa with initial concentration of 10 mg/L was removed in 60 min by EO and 45 min by EF process at neutral pH, applied current density of 7.5 mA/cm2, NaCl concentration of 1.0 g/L and 10 mg/L of Fe2O3 dosing. The MePa removal efficiency of the CCS cathode-fitted system after 60 min was better than the commercial graphite plate and Ti-based mixed metal oxide employing system due to higher H2O2 electrosynthesis (H2O2 = 9.0 ± 0.6 mg/L after 60 min). Moreover, the same setup was used for treating 10 mg/L of MePa-spiked real sewage and demonstrated MePa and total organic carbon removal efficiency of 80.16 ± 2.31% and 37.42 ± 3.50%, respectively, in 45 min. Further, the CCS-mediated EF treatment achieved >90% removal of MePa for eight continuous batch cycles and recorded a current density drop of just 0.23% per cycle. The degradation pathway and toxicity assessment of the intermediates using the Ecological Structure Activity Relationships (ECOSAR) tool supported the eco-friendliness of the current treatment scheme.

Microbial fuel cell coupled Fenton oxidation for the cathodic degradation of emerging contaminants from wastewater: Applications and challenges.

Urbanization and industrialization have resulted in the escalation of the occurrence of emerging contaminants (EC) in the wastewater and ultimately to the receiving water bodies due to their bio-refractory nature. The presence of ECs in the water bodies adversely affects all three domains of life, viz. bacteria, archaea and eukaryotes, and eventually the ecosystem. Fenton oxidation is one of the most suitable method that is capable of degrading a variety of ECs by employing a strong oxidizing agent in the form of •OH. The coupling of Fenton oxidation with microbial fuel cell (MFC) offers benefits, such as low-cost, minimal requirement of external energy, and in-situ generation of oxidizing agents. The resulting system, termed as bio-electro-Fenton MFC (BEF-MFC), is capable of degrading the ECs in the cathodic chamber, while harvesting bioelectricity and simultaneously removing oxidizable organic matter from wastewater in the anodic chamber. This review discusses the applications of BEF-MFC for the treatment of dyes, pharmaceuticals, pesticides, and real complex wastewaters. Additionally, the effect of operating conditions on the performance of BEF-MFC are elaborated and emphasis is also given on possible future direction of research that can be adopted in BEF-MFC in the purview of up-scaling.

Waste-derived iron catalyzed bio-electro-Fenton process for the cathodic degradation of surfactants.

The application of waste-derived iron for reuse in wastewater treatment is an effective way of utilizing waste and attaining sustainability in the overall process. In the present investigation, bio-electro-Fenton process was initiated for the cathodic degradation of surfactants using waste-iron catalyzed MFC (WFe-MFC). The waste-iron was derived from spent tonner ink using calcination at 600 °C. Three surfactants namely, sodium dodecyl sulphate (SDS), cetyltrimethylammonium bromide, and Triton x-100 were selected as target pollutants. The effect of experimental factors like application of catalyst, contact time, external resistance, and anodic substrate concentration on the SDS degradation was investigated. At a neutral pH, the cathodic surfactants removal efficiency in WFe-MFC was above 85% in a contact time of 180 min with the initial surfactant concentration of ∼20 mg L-1 and external resistance of 100 Ω. The long-term operation using secondary treated real wastewater with unchanged cathode proved that the catalyst was still active to produce effluent SDS concentration of less than 1 mg L-1 in 4 h of contact time after 16 cycles. In a way, the present investigation suggests a potential application for spent tonner ink in the form of Fenton catalyst for wastewater treatment via bio-electro-Fenton MFC.

Optimum dose of Chaetoceros for controlling methanogenesis to improve power production of microbial fuel cell.

The marine algae Chaetoceros contains hexadecatrienoic acid, which suppresses methanogen development and improves the coulombic efficiency (CE) of microbial fuel cells (MFC). To inhibit the methanogens, optimum concentration of marine algae should be added to the anaerobic sludge to enhance the performance of MFC. A varying concentration of Chaetoceros ranging from 1 to 20 mg/mL was carried out for pretreatment of an anaerobic-mix consortium to suppress methanogens. MFC inoculated with pretreated anaerobic sludge with 10 mg/mL Chaetoceros showed a maximum power density of 21.62 W/m3 and a maximum CE of 37.25%, which was considerably higher than the treatment with other concentrations. At 10 mg/mL concentration, Tafel analysis of the anode in the MFC showed a higher exchange current density of 66.35 mA/m2 and a lower charge transfer resistance of 0.97 Ω.m2, revealing higher bio-electrochemical activity. The performance of MFC improved when the concentration of Chaetoceros was increased up to 10 mg/mL, but then began to decline as the concentration increased further. Thus, the optimum dose of Chaetoceros to be added in the mix-anaerobic consortium to optimize the power performance of MFC was determined, which can be carried out in scaled-up MFCs.

Surfactant removal from wastewater using photo-cathode microbial fuel cell and laterite-based hybrid treatment system.

Sodium dodecyl sulfate (SDS) is a widely used anionic surfactant, which finds its way to the receiving water body due to the incapability of conventional wastewater treatment systems to completely remove it. A hybrid treatment system consisting of upflow microbial fuel cell (MFC) with titanium dioxide (TiO2) as a photocathode catalyst was developed for treating synthetic wastewater spiked with SDS (10.00 ± 0.46 mg L-1). Effluent from anodic chamber of MFC was passed through raw laterite soil filter followed by the photo-cathodic chamber with TiO2-coated cathode irradiated with the UV spectrum. This hybrid system was operated under varying hydraulic retention time (HRT) in anodic chamber of MFC. The SDS removal efficiency of more than 96% along with organic matter removal efficiency of more than 71% was obtained by this hybrid system at different HRTs. The MFC having cathode coated with TiO2 could generate a maximum power density of 0.73 W m-3 and 0.46 W m-3 at the HRT of 12 h and 8 h, respectively, showing the adverse effect of increased SDS loading rate on the electrical performance of MFC. This investigation highlighted the importance of HRT in anodic chamber of MFC and offered solution for effective removal of surfactant from wastewater.

Evaluating the suitability of tungsten, titanium and stainless steel wires as current collectors in microbial fuel cells.

An appropriate current collector (CC) is crucial for harvesting substantial power in a microbial fuel cell (MFC). In the present study, stainless steel (SS) and titanium wires were used as the CCs for both the anode and cathode of MFC-1 and MFC-2, respectively. Tungsten wire (TW) was used as the anode CC in MFC-3, with SS wire as the cathode CC. In MFC-4, TW was used as the cathode CC with SS wire as the anode CC, and in MFC-5 both electrode CCs were TW. The power density, current density, oxidation current and bio-capacitance were compared to select the best and most cost effective CC material to enhance the power output of MFCs. Maximum power densities (mW/m2) of 32.28, 93.10, 225.38, 210.74, and 234.88 were obtained in MFC-1, MFC-2, MFC-3, MFC-4, and MFC-5, respectively. The highest current density (639.86 mA/m2) and coulombic efficiency (23.12 ± 1.5%) achieved in MFC-5 showed TW to be the best CC for both electrodes. The maximum oxidation current of 7.4 mA and 7 mA and bio-capacitance of 10.3 mF/cm2 and 9.7 mF/cm2 were achieved in MFC-3 and MFC-5, respectively, suggesting TW is the best as the anode CC and SS wire as the cathode CC to reduce MFC fabrication costs.

Increasing methane content in biogas and simultaneous value added product recovery using microbial electrosynthesis.

Electrosynthesis of multi-carbon compounds from the carbon dioxide present in biogas is a nascent approach towards purification of biogas. Microbial electrosynthesis (MES) cells, fabricated using different electrode materials, were operated using different electrolytes and mixed anaerobic culture as biocatalysts in the cathodic chamber under an applied cathode potential of -0.7 V vs standard hydrogen electrode (SHE). The rate of production of acetate, isobutyrate, propionate and 2-piperidinone from reduction of CO2 in the cathodic chamber of the MES was 0.81 mM/day, 0.63 mM/day, 0.44 mM/day and 0.53 mM/day, respectively. As methane was also present in the biogas, methyl derivatives of these acids were also found in traces in catholyte. It was observed that the use of nickel foam as an anode, 1 M NiSO4 solution as anolyte, graphite felt as a cathode, phosphate buffer solution as catholyte at a pH of 5.2 proved to be the best possible combination for MES for this study to get enhanced product yield at higher energy efficiency.

Pre-treatment of anodic inoculum with nitroethane to improve performance of a microbial fuel cell.

Methanogenic substrate loss is reported to be a major bottleneck in microbial fuel cell (MFC), which significantly reduces the power production capacity and coulombic efficiency (CE) of this system. Nitroethane is found to be a potent inhibitor of hydrogenotrophic methanogens in rumen fermentation process. Influence of nitroethane pre-treated sewage sludge inoculum on suppressing the methanogenic activity and enhancing the electrogenesis in MFC was evaluated. MFC inoculated with nitroethane pre-treated anodic inoculum demonstrated a maximum operating voltage of 541 mV, with CE and maximum volumetric power density of 39.85% and 20.5 W/m3, respectively. Linear sweep voltammetry indicated a higher electron discharge on the anode surface due to enhancement of electrogenic activity while suppressing methanogenic activity. A 63% reduction in specific methanogenic activity was observed in anaerobic sludge pre-treated with nitroethane, emphasizing the significance of this pre-treatment for suppressing methanogenesis and its utility for enhancing electricity generation in MFC.

Biotic conversion of sulphate to sulphide and abiotic conversion of sulphide to sulphur in a microbial fuel cell using cobalt oxide octahedrons as cathode catalyst.

Varying chemical oxygen demand (COD) and sulphate concentrations in substrate were used to determine reaction kinetics and mass balance of organic matter and sulphate transformation in a microbial fuel cell (MFC). MFC with anodic chamber volume of 1 L, fed with wastewater having COD of 500 mg/L and sulphate of 200 mg/L, could harvest power of 54.4 mW/m2, at a Coulombic efficiency of 14%, with respective COD and sulphate removals of 90 and 95%. Sulphide concentration, even up to 1500 mg/L, did not inhibit anodic biochemical reactions, due to instantaneous abiotic oxidation to sulphur, at high inlet sulphate. Experiments on abiotic oxidation of sulphide to sulphur revealed maximum oxidation taking place at an anodic potential of -200 mV. More than 99% sulphate removal could be achieved in a MFC with inlet COD/sulphate of 0.75, giving around 1.33 kg/m3 day COD removal. Bioelectrochemical conversion of sulphate facilitating sulphur recovery in a MFC makes it an interesting pollution abatement technique.

Electricity generation through a photo sediment microbial fuel cell using algae at the cathode.

Sediment microbial fuel cells (SMFCs) are bio-electrochemical devices generating electricity from redox gradients occurring across the sediment-water interface. Sediment microbial carbon-capture cell (SMCC), a modified SMFC, uses algae grown in the overlying water of sediment and is considered as a promising system for power generation along with algal cultivation. In this study, the performance of SMCC and SMFC was evaluated in terms of power generation, dissolved oxygen variations, sediment organic matter removal and algal growth. SMCC gave a maximum power density of 22.19 mW/m2, which was 3.65 times higher than the SMFC operated under similar conditions. Sediment organic matter removal efficiencies of 77.6 ± 2.1% and 61.0 ± 1.3% were obtained in SMCC and SMFC, respectively. With presence of algae at the cathode, a maximum chemical oxygen demand and total nitrogen removal efficiencies of 63.3 ± 2.3% (8th day) and 81.6 ± 1.2% (10th day), respectively, were observed. The system appears to be favorable from a resources utilization perspective as it does not depend on external aeration or membranes and utilizes algae and organic matter present in sediment for power generation. Thus, SMCC has proven its applicability for installation in an existing oxidation pond for sediment remediation, algae growth, carbon conversion and power generation, simultaneously.

Biomass granulation in an upflow anaerobic sludge blanket reactor treating 500 m3/day low-strength sewage and post treatment in high-rate algal pond.

A pilot-scale upflow anaerobic sludge blanket-moving bed biofilm (UASB-MBB) reactor followed by a high-rate algal pond (HRAP) was designed and operated to remove organic matter, nutrients and pathogens from sewage and to facilitate reuse. For an influent chemical oxygen demand (COD) concentration of 233 ± 20 mg/L, final effluent COD was 50 ± 6 mg/L. Successful biomass granulation was observed in the sludge bed of the upflow anaerobic sludge blanket (UASB) reactor after 5 months of operation. Ammonia removal in HRAP was 85.1 ± 2.4% with average influent and effluent ammonia nitrogen concentrations of 20 ± 3 mg/L and 3 ± 1 mg/L, respectively. Phosphate removal after treatment in the HRAP was 91 ± 1%. There was a 2-3 log scale pathogen removal after treatment in HRAP with most probable number (MPN) of the final effluent being 600-800 per 100 mL, which is within acceptable standards for surface irrigation. The blackwater after treatment in UASB-MBBR-HRAP is being reused for gardening and landscaping. This proper hydro-dynamically designed UASB reactor demonstrated successful granulation and moving bed media improved sludge retention in UASB reactor. This combination of UASB-MBB reactor followed by HRAP demonstrated successful sewage treatment for a year covering all seasons.

Biodegradation kinetics of thin-stillage treatment by Aspergillus awamori and characterization of recovered chitosan.

An attempt has been made to provide solution for distillery wastewater using fungal pretreatment followed by an anaerobic process to achieve higher organic matter removal, which is a challenge at present with currently adopted technologies. Submerged growth kinetics of distillery wastewater supernatant by Aspergillus awamori was also evaluated. The proposed kinetic models using a logistic equation for fungal growth and the Leudeking-Piret equation for product formation were validated experimentally, and substrate consumption equation was derived using estimated kinetic coefficients. Up to 59.6 % chemical oxygen demand (COD) and 70 % total organic carbon (TOC) removals were observed in 96 h of fungal incubation. Maximum specific growth rate of fungi, coefficient of biomass yield on substrate and growth-associated product formation coefficient were estimated to be 0.07 ± 0.01 h(-1), 0.614 kg biomass/kg utilized COD and 0.215 kg CO2/kg utilized TOC, respectively. The chitosan recovery of 0.072-0.078 kg/kg of dry mycelium was obtained using dilute sulphuric acid extraction, showing high purity and characteristic chitosan properties according to FTIR and XRD analyses. After anaerobic treatment of the fungal pretreated effluent with COD concentration of 7.920 ± 0.120 kg COD/m(3) (organic loading rate of 3.28 kg COD/m(3) day), overall COD reduction of 91.07 % was achieved from distillery wastewater.

Reduction of start-up time through bioaugmentation process in microbial fuel cells using an isolate from dark fermentative spent media fed anode.

An electrochemically active bacteria Pseudomonas aeruginosa IIT BT SS1 was isolated from a dark fermentative spent media fed anode, and a bioaugmentation technique using the isolated strain was used to improve the start-up time of a microbial fuel cell (MFC). Higher volumetric current density and lower start-up time were observed with the augmented system MFC-PM (13.7 A/m(3)) when compared with mixed culture MFC-M (8.72 A/m(3)) during the initial phase. This enhanced performance in MFC-PM was possibly due to the improvement in electron transfer ability by the augmented strain. However, pure culture MFC-P showed maximum volumetric current density (17 A/m(3)) due to the inherent electrogenic properties of Pseudomonas sp. An electrochemical impedance spectroscopic (EIS) study, along with matrix-assisted laser desorption/ionization-time-of-flight (MALDI-TOF) analysis, supported the influence of isolated species in improving the MFC performance. The present study indicates that the bioaugmentation strategy using the isolated Pseudomonas sp. can be effectively utilized to decrease the start-up time of MFC.

Preparation of a fouling-resistant sustainable cathode for a single-chambered microbial fuel cell.

Two different binder materials of varying water affinity, viz. poly vinyl alcohol (PVA) and poly-tetrafluoroethylene (PTFE), and biocide vanillin were tested for cathode fouling in a single chamber air-cathode microbial fuel cell (MFC) constructed with a low-cost baked clayware cylinder and operated under fed-batch mode. PVA and PTFE loadings of 0.5 mg/cm(2) were used for MFC-1 and MFC-2, respectively as a binder; and a 1:1 mixture of PVA + PTFE was used as binder in MFC-3 with same binder loading. Vanillin was mixed with PVA and also applied at a loading of 0.5 mg/cm(2) for MFC-4. Results showed organic matter removal efficiencies around 90% for all MFCs both before and after fouling. Coulombic efficiency was, however, found to decrease 50% after fouling in the MFC-3 coated with both PVA and PTFE. After 5 weeks of operation, due to fouling 56, 40 and 69% reduction in power densities were observed in MFC-1, MFC-2 and MFC-3, respectively. In the MFC-4 having PVA and vanillin, the least fouling was observed. A consistent volumetric power of 233 mW/m(3) was observed for MFC-4, thus potentially offering a suitable solution to alleviate the problem of fouling in the making of single-chamber air-cathode MFCs.

Multi-chamber microbial desalination cell for improved organic matter and dissolved solids removal from wastewater.

A five-chamber microbial desalination cell (MDC) with anode, cathode, one central desalination chamber and two concentrate chambers separated by ion exchange membranes was operated in batch mode for more than 60 days. The performance of the MDC was evaluated for chemical oxygen demand (COD) removal, total dissolved solids (TDS) removal and energy production. An average COD removal of 81 ± 2.1% was obtained using acetate-fed wastewater as substrate in the anodic chamber inoculated with mixed anaerobic sludge. TDS removals of 58, 70 and 78% were observed with salt concentration of 8, 20 and 30 g/L, respectively, in the middle desalination chamber. The MDC produced a maximum power output of 16.87 mW/m(2) during polarization. The highest Coulombic efficiency of 12 ± 2.4% was observed in this system using mixed anaerobic sludge as inoculum. The system effectively demonstrated capability for simultaneous organic matter removal and desalination along with power generation.

Controlling methanogenesis and improving power production of microbial fuel cell by lauric acid dosing.

Methanogens compete with anodophiles for substrate and thus reduce the power generation and coulombic efficiency (CE) of the microbial fuel cell (MFC). Performance of a baked clayware membrane MFC inoculated with mixed anaerobic sludge pretreated with lauric acid was investigated in order to enhance power recovery by controlling methanogenesis. In the presence of lauric acid pretreated inoculum, MFC produced maximum volumetric power density of 4.8 W/m(3) and the CE increased from 3.6% (for untreated inoculum) to 11.6%. Cyclic voltammetry (CV) and electro-kinetic evaluation indicated a higher bio-catalytic activity at the anode of the MFC inoculated with lauric acid pretreated sludge. With the lauric acid pretreated inoculum a higher catalytic current of 114 mA, exchange current density of 40.78 mA/m(2) and lower charge transfer resistance of 0.00016 Ωm(2) were observed during oxidation at the anode. Addition of lauric acid significantly achieved suppression of methanogenesis and enhanced the sustainable power generation of MFC by 3.9 times as compared with control MFC inoculated with sludge without any pretreatment.

Nickel adsorbed algae biochar based oxygen reduction reaction catalyst.

Lately, the bio electrochemical systems are emerging as an efficient wastewater treatment and energy conversion technology. However, their scaling-up is considerably restrained by slow-rate of cathodic oxygen reduction reaction (ORR) or otherwise by the high cost associated with the available efficient ORR catalysts. In this investigation, a cost-effective and eco-friendly approach for synthesizing Ni based ORR catalyst utilizing biosorption property of microalgae is accomplished. The synthesised Ni adsorbed algal biochar (NAB) served as an efficient cathode catalyst for enhancing ORR in a microbial carbon-capture cell (MCC). On increasing the initial concentration of Ni2+ in the aqueous medium from 100 mgL-1 to 500 mgL-1, the biosorption capacity was found to increase from 3 mgg-1 to 32 mgg-1 of algae cell. The MCC operated with NAB based cathode catalyst loading of 2 mgcm-2 exhibited 3.5 times higher power density (4.69 Wm-3) as compared to the one with commercial activated carbon. A significant organic matter removal (82 %) in the anodic chamber with simultaneous algal biomass productivity in the cathodic chamber was attained by MCC with cathode loaded with 2 mgcm-2 of NAB. Hence, this easily synthesised low-cost catalyst, out of waste stream, proved its ability to improve the performance of MCC.

Ibuprofen degradation by mixed bacterial consortia: Metabolic pathway and microbial community analysis.

Degradation of ibuprofen, one of the most consumed drugs globally, by a mixed bacterial consortium was investigated. A contaminated hospital soil was used to enrich a bacterial consortium possessing the ability to degrade 4 mg/L ibuprofen in 6 days, fed on 6 mM acetate as a supplementary carbon source. Maximum ibuprofen degradation achieved was 99.51%, and for optimum ibuprofen degradation modelled statistically, the initial ibuprofen concentration, and temperature were determined to be 0.515 mg/L and 35 °C, respectively. The bacterial community analyses demonstrated an enrichment of Pseudomonas, Achromobacter, Bacillus, and Enterococcus in the presence of ibuprofen, suggesting their probable association with the biodegradation process. The biodegradation pathway developed using open-source metabolite predictors, GLORYx and BioTransformer suggested multiple degradation routes. Hydroxylation and oxidation were found to be the major mechanisms in ibuprofen degradation. Mono-hydroxylated metabolites were identified as well as predicted by the bioinformatics-based packages. Oxidation, dehydrogenation, super-hydroxylation, and hydrolysis were some other identified mechanisms.

Effect of pH and distance between electrodes on the performance of a sediment microbial fuel cell.

The performance of three sediment microbial fuel cells (SMFCs) was evaluated at different feed water pH and electrode spacing for chemical oxygen demand (COD) removal, total nitrogen (TN) removal, and power density; while offering in situ remediation of aquaculture pond water. SMFC-A was operated at the feed water pH of 6.5 and spacing between the electrodes of 100 cm. SMFC-B and SMFC-C were operated at feed water pHs of 8.5 and 6.5, respectively, and distance between electrodes of 50 cm. The anode and cathode were connected with concealed copper wire through an external load of 100 Ω. The average amount of total COD removal rate and TN removal rate, per unit area of cathode, were 1.72 ± 0.06 and 0.021 ± 0.007 g/m(2) d in SMFC-A, 1.03 ± 0.08 and 0.024 ± 0.005 g/m(2) d in SMFC-B, and 1.14 ± 0.01 and 0.017 ± 0.001 g/m(2) d in SMFC-C, respectively. SMFC-A, operated with higher distance between electrodes, demonstrated better removal of organic matter and highest open circuit voltage of 0.903 V. SMFCs with less feed pH (6.5) gave higher COD removal and feed pH of 8.5 gave higher TN removal. SMFCs operated with lesser distance between electrodes gave higher power density.