Cathode in photocatalytic fuel cell (PFC) plays a crucial role in degradation of organic contaminants. In this study, synthesized copper oxide (CuO) was loaded on carbon plate and used as photocathode in PFC for degradation of synthetic azo dye Reactive Black 5 (RB5) and real textile wastewater. Morphology and structural phase of the synthesized CuO were analyzed using scanning electron microscopy (SEM) and X-ray diffraction (XRD), respectively. Several operating parameters had been investigated such as light irradiation, initial dye concentration, and pH of azo dye solution within 6 h of irradiation time. The lowest initial concentration of RB5 (10 mg L-1) achieved 100% color removal compared to the highest initial concentration (40 mg L-1) which only achieved 77.1% color removal within 6 h of irradiation time. The influence of external resistance was significant in electricity generation but trivial in dye degradation efficiency. The external resistance of 6000 Ω yielded highest maximum power density, with Pmax of 0.2631 μW cm-2, followed by 1000 Ω (0.2196 μW cm-2) and 8000 Ω (0.1587 μW cm-2), respectively. The real textile wastewater with dilution ratio (DR) 1:6 yielded the highest energy conversion efficiency, η (3.62%), followed by DR 1:4 (3.19%) and DR 1:2 (1.96%), respectively.
This study demonstrated the effectiveness of single chamber up-flow membrane-less microbial fuel cell (UFML-MFC) in wastewater treatment concurrently with bioelectricity generation. The objectives of this study were to examine the effect of influent substrate concentration (0.405 g/L, 0.810 g/L, 1.215 g/L, 1.620 g/L), anode distributions (11 cm, 17 cm, 23 cm ) and surface morphologies for biofilm formation on the performance of wastewater treatment and power generation. The optimum performance was obtained with substrate concentration of 0.810 g/L. The COD removal efficiency, output voltage, internal resistance, power density and current density obtained were 84.64%, 610 mV, 200 Ω, 162.59 mW/m2 and 468.74 mA/m2, respectively. The Coulombic Efficiency (CE), Normalized Energy Recovery (NERS and NERv) were 1.03%, 789.38 kWh/kg COD and 22.56 kWh/m3, respectively. The results also indicate that the output voltage and power generation obtained in a continuous up-flow MFC were higher with A3 (23 cm), which is of larger electrodes spacing followed by A2 (17 cm) and A1 (11 cm) caused by the enrichment of anaerobic microbial population at A1.
Escalating global water pollution exacerbated by textile-dyeing wastewater (TDW) poses significant environmental and health concerns due to the insufficient treatment methods being utilized. Thus, it is imperative to implement more effective treatment solutions to address such issues. In this research, different environmentally-friendly strategies involving effluent recirculation (ER) and Rubia cordifolia plant-derived purpurin electron mediator (EM) were introduced to enhance the treatment of real TDW and bioelectricity generation performance of an anti-gravity flow microbial fuel cell (AGF-MFC). The results revealed that optimum performance was achieved with a combination of hydraulic retention time (HRT) of 48 h with a recirculation ratio of 1, where the reduction efficiency of biochemical oxygen demand (BOD5), chemical oxygen demand (COD), ammonium (NH4+), nitrate (NO3-), sulphate (SO42-), ammonia nitrogen (NH3-N), colour and turbidity were 82.17 %, 82.15 %, 85.10 %, 80.52 %, 75.91 %, 59.52 %, 71.02 % and 93.10 %, respectively. In terms of bioelectricity generation performance, AGF-MFC showed a maximum output voltage and power density of 404.72 mV and 65.16 mW/m2, respectively. Moreover, the results also signified that higher treatment performance of TDW was obtained with natural purpurin from Rubia cordifolia plant than synthetic purpurin as EM. The reduced reactivity of highly stable synthetic purpurin EM for mediating the electron transfer was a contributing factor to the outperformance of plant-derived purpurin. Additionally, detailed electron-mediating mechanisms of purpurin were proposed to unravel the underlying electron transfer pathway involved in AGF-MFC. This research offers insight into the development of more sustainable solutions for managing TDW, and consequently reducing environmental pollution.
This study demonstrated a successful operation of up-flow constructed wetland-microbial fuel cell (UFCW-MFC) in wastewater treatment and energy recovery. The goals of this study were to investigate the effect of circuit connection, organic loading rates, and electrode spacing on the performance of wastewater treatment and bioelectricity generation. The average influent of COD, NO3(-) and NH4(+) were 624 mg/L, 142 mg/L, 40 mg/L, respectively and their removal efficiencies (1 day HRT) were 99%, 46%, and 96%, respectively. NO3(-) removal was relatively higher in the closed circuit system due to lower dissolved oxygen in the system. Despite larger electrode spacing, the voltage outputs from Anode 2 (A2) (30 cm) and Anode 3 (A3) (45 cm) were higher than from Anode 1 (A1) (15 cm) as a result of insufficient fuel supply to A1. The maximum power density and Coulombic efficiency were obtained at A2, which were 93 mW/m(3) and 1.42%, respectively.
Single chambered up-flow membrane-less microbial fuel cell (UFML MFC) was developed to study the feasibility of the bioreactor for decolorization of Acid Orange 7 (AO7) and electricity generation simultaneously. The performance of UFML MFC was evaluated in terms of voltage output, chemical oxygen demand (COD) and color removal efficiency by varying the concentration of AO7 in synthetic wastewater. The results shown the voltage generation and COD removal efficiency decreased as the initial AO7 concentration increased; this indicates there is electron competition between anode and azo dye. Furthermore, there was a phenomenon of further decolorization at cathode region which indicates the oxygen and azo dye are both compete as electron acceptor. Based on the UV-visible spectra analysis, the breakdown of the azo bond and naphthalene compound in AO7 were confirmed. These findings show the capability of integrated UFML MFC in azo dye wastewater treatment and simultaneous electricity generation.
Photocatalytic fuel cell (PFC) is a potential wastewater treatment technology that can generate electricity from the conversion of chemical energy of organic pollutants. An immobilized ZnO/Zn fabricated by sonication and heat attachment method was applied as the photoanode and Pt/C plate was used as the cathode of the PFC in this study. Factors that affect the decolorization efficiency and electricity generation of the PFC such as different initial dye concentrations and pH were investigated. Results revealed that the degradation of Reactive Green 19 (RG19) was enhanced in a closed circuit PFC compared with that of a opened circuit PFC. Almost 100% decolorization could be achieved in 8 h when 250 mL of 30 mg L(-1) of RG19 was treated in a PFC without any supporting electrolyte. The highest short circuit current of 0.0427 mA cm(-2) and maximum power density of 0.0102 mW cm(-2) was obtained by PFC using 30 mg L(-1) of RG19. The correlation between dye degradation, conductivity and voltage output were also investigated and discussed.
The objective of this study is to determine the reduction efficiency of Chemical Oxygen Demand (COD) as well as the removal of color and Amaranth dye metabolites by the Aerobic-anaerobic Baffled Constructed Wetland Reactor (ABCW). The ABCW reactor was planted with common reed (Phragmite australis) where the hydraulic retention time (HRT) was set to 1 day and was fed with synthetic wastewater with the addition of Amaranth dye. Supplementary aeration was supplied in designated compartments of the ABCW reactor to control the aerobic and anaerobic zones. After Amaranth dye addition the COD reduction efficiency dropped from 98 to 91% while the color removal efficiency was 100%. Degradation of azo bond in Amaranth dye is shown by the UV-Vis spectrum analysis which demonstrates partial degradation of Amaranth dye metabolites. The performance of the baffled unit is due to the longer pathway as there is the up-flow and down-flow condition sequentially, thus allowing more contact of the wastewater with the rhizomes and micro-aerobic zones.
This study demonstrated the potential of single chamber up-flow membrane-less microbial fuel cell (UFML-MFC) in wastewater treatment and power generation. The purpose of this study was to evaluate and enhance the performance under different operational conditions which affect the chemical oxygen demand (COD) reduction and power generation, including the increase of KCl concentration (MFC1) and COD concentration (MFC2). The results showed that the increase of KCl concentration is an important factor in up-flow membrane-less MFC to enhance the ease of electron transfer from anode to cathode. The increase of COD concentration in MFC2 could led to the drop of voltage output due to the prompt of biofilm growth in MFC2 cathode which could increase the internal resistance. It also showed that the COD concentration is a vital issue in up-flow membrane-less MFC. Despite the COD reduction was up to 96%, the power output remained constrained.
The role of azo dye Reactive Black 5 (RB5) as an electron donor and/or electron acceptor could be distinguished in dual chamber of photocatalytic fuel cell (PFC). The introduction of RB5 in anode chamber increased the voltage generation in the system since degradation of RB5 might produce electrons which also would transfer through external circuit to the cathode chamber. The removal efficiency of RB5 with open and closed circuit was 8.5% and 13.6%, respectively and removal efficiency for open circuit was low due to the fact that recombination of electron-hole pairs might happen in anode chamber since without connection to the cathode, electron cannot be transferred. The degradation of RB5 in cathode chamber with absence of oxygen showed that electrons from anode chamber was accepted by dye molecules to break its azo bond. The presence of oxygen in cathode chamber would improve the oxygen reduction rate which occurred at Platinum-loaded carbon (Pt/C) cathode electrode. The Voc, Jsc and Pmax for different condition of ultrapure water at cathode chamber also affected their fill factor. The transportation of protons to cathode chamber through Nafion membrane could decrease the pH of ultrapure water in cathode chamber and undergo hydrogen evolution reaction in the absence of oxygen which then increased degradation rate of RB5 as well as its electricity generation.
This study explored the influence of azo dye concentration, salinity (with and without aeration) and nitrate concentration on bioelectricity generation and treatment performance in the up-flow constructed wetland-microbial fuel cell (UFCW-MFC) system. The decolourisation efficiencies were up to 91% for 500 mg/L of Acid Red 18 (AR18). However, the power density declined with the increment in azo dye concentration. The results suggest that the combination of salinity and aeration at an optimum level improved the power performance. The highest power density achieved was 8.67 mW/m2. The increase of nitrate by 3-fold led to decrease in decolourisation and power density of the system. The findings revealed that the electron acceptors (AR18, nitrate and anode) competed at the anodic region for electrons and the electron transfer pathways would directly influence the treatment and power performance of UFCW-MFC. The planted UFCW-MFC significantly outweighed the plant-free control in power performance.
This study investigates the role of plant (Elodea nuttallii) and effect of supplementary aeration on wastewater treatment and bioelectricity generation in an up-flow constructed wetland-microbial fuel cell (UFCW-MFC). Aeration rates were varied from 1900 to 0mL/min and a control reactor was operated without supplementary aeration. 600mL/min was the optimum aeration flow rate to achieve highest energy recovery as the oxygen was sufficient to use as terminal electron acceptor for electrical current generation. The maximum voltage output, power density, normalized energy recovery and Coulombic efficiency were 545.77±25mV, 184.75±7.50mW/m3, 204.49W/kg COD, 1.29W/m3 and 10.28%, respectively. The variation of aeration flow rates influenced the NO3- and NH4+ removal differently as nitrification and denitrification involved conflicting requirement. In terms of wastewater treatment performance, at 60mL/min aeration rate, UFCW-MFC achieved 50 and 81% of NO3- and NH4+ removal, respectively. E. nuttallii enhanced nitrification by 17% and significantly contributed to bioelectricity generation.
Reactive green 19, acid orange 7 and methylene blue are employed as the organic pollutants in this work. A photocatalytic fuel cell is constructed based on the idea of immobilizing zinc oxide onto zinc photoanode and platinum loaded carbon cathode, both evaluated under sunlight and ultraviolet irradiation, respectively. Influence of light and dye structures on the performance of photocatalytic fuel cell are examined. With reactive green 19, 93% and 86% of color removal are achieved after 8 h of photocatalytic fuel cell treatment under sunlight and ultraviolet irradiation, respectively. The decolorization rate of diazo reactive green 19 is higher than acid orange 7 (monoazo dye) when both dyes are treated by photocatalytic fuel cell under sunlight and ultraviolet irradiation, as the electron releasing groups (-NH-triazine) allow reactive green 19 easier to be oxidized. Comparatively, acid orange 7 is less favorable to be oxidized. The degradation of methylene blue is enhanced under sunlight irradiation due to the occurrence of self-sensitized photodegradation. When methylene blue is employed in the photocatalytic fuel cell under sunlight irradiation, the short circuit current (0.0129 mA cm-2) and maximum power density (0.0032 mW cm-2) of photocatalytic fuel cell greatly improved.
Complete degradation of azo dye has always been a challenge due to the refractory nature of azo dye. An innovative hybrid system, constructed wetland-microbial fuel cell (CW-MFC) was developed for simultaneous azo dye remediation and energy recovery. This study investigated the effect of circuit connection and the influence of azo dye molecular structures on the degradation rate of azo dye and bioelectricity generation. The closed circuit system exhibited higher chemical oxygen demand (COD) removal and decolourisation efficiencies compared to the open circuit system. The wastewater treatment performances of different operating systems were ranked in the decreasing order of CW-MFC (R1 planted-closed circuit) > MFC (R2 plant-free-closed circuit) > CW (R1 planted-open circuit) > bioreactor (R2 plant-free-open circuit). The highest decolourisation rate was achieved by Acid Red 18 (AR18), 96%, followed by Acid Orange 7 (AO7), 67% and Congo Red (CR), 60%. The voltage outputs of the three azo dyes were ranked in the decreasing order of AR18 > AO7 > CR. The results disclosed that the decolourisation performance was significantly influenced by the azo dye structure and the moieties at the proximity of azo bond; the naphthol type azo dye with a lower number of azo bond and more electron-withdrawing groups could cause azo bond to be more electrophilic and more reductive for decolourisation. Moreover, the degradation pathway of AR18, AO7 and CR were elucidated based on the respective dye intermediate products identified through UV-Vis spectrophotometry, high-performance liquid chromatography (HPLC), and gas chromatograph-mass spectrometer (GC-MS) analyses. The CW-MFC system demonstrated high capability of decolouring azo dyes at the anaerobic anodic region and further mineralising dye intermediates at the aerobic cathodic region to less harmful or non-toxic products.
The photocatalytic fuel cell (PFC) system was developed in order to study the effect of several operating parameters in degradation of Reactive Black 5 (RB5) and its electricity generation. Light irradiation, initial dye concentration, aeration, pH and cathode electrode are the operating parameters that might give contribution in the efficiency of PFC system. The degradation of RB5 depends on the presence of light irradiation and solar light gives better performance to degrade the azo dye. The azo dye with low initial concentration decolorizes faster compared to higher initial concentration and presence of aeration in PFC system would enhance its performance. Reactive Black 5 rapidly decreased at higher pH due to the higher amount of OH generated at higher pH and Pt-loaded carbon (Pt/C) was more suitable to be used as cathode in PFC system compared to Cu foil and Fe foil. The rapid decolorization of RB5 would increase their voltage output and in addition, it would also increase their Voc, Jsc and Pmax. The breakage of azo bond and aromatic rings was confirmed through UV-Vis spectrum and COD analysis.
Monoazo and diazo dyes [New coccine (NC), Acid orange 7 (AO7), Reactive red 120 (RR120) and Reactive green 19 (RG19)] were employed as electron acceptors in the abiotic cathode of microbial fuel cell. The electrons and protons generated from microbial organic oxidation at the anode which were utilized for electrochemical azo dye reduction at the cathodic chamber was successfully demonstrated. When NC was employed as the electron acceptor, the chemical oxygen demand (COD) removal and dye decolourisation efficiencies obtained at the anodic and cathodic chamber were 73±3% and 95.1±1.1%, respectively. This study demonstrated that the decolourisation rates of monoazo dyes were ∼50% higher than diazo dyes. The maximum power density in relation to NC decolourisation was 20.64mW/m2, corresponding to current density of 120.24mA/m2. The decolourisation rate and power output of different azo dyes were in the order of NC>AO7>RR120>RG19. The findings revealed that the structure of dye influenced the decolourisation and power performance of MFC. Azo dye with electron-withdrawing group at para substituent to azo bond would draw electrons from azo bond; hence the azo dye became more electrophilic and more favourable for dye reduction.
In this study, a membraneless photocatalytic fuel cell with zinc oxide loaded carbon photoanode and platinum loaded carbon cathode was constructed to investigate the impact of dissolved oxygen on the mechanism of dye degradation and electricity generation of photocatalytic fuel cell. The photocatalytic fuel cell with high and low aeration rate, no aeration and nitrogen purged were investigated, respectively. The degradation rate of diazo dye Reactive Green 19 and the electricity generation was enhanced in photocatalytic fuel cell with higher dissolved oxygen concentration. However, the photocatalytic fuel cell was still able to perform 37% of decolorization in a slow rate (k = 0.033 h-1) under extremely low dissolved oxygen concentration (approximately 0.2 mg L-1) when nitrogen gas was introduced into the fuel cell throughout the 8 h. However, the change of the UV-Vis spectrum indicates that the intermediates of the dye could not be mineralized under insufficient dissolved oxygen level. In the aspect of electricity generation, the maximum short circuit current (0.0041 mA cm-2) and power density (0.00028 mW cm-2) of the air purged photocatalytic fuel cell was obviously higher than that with nitrogen purging (0.0015 mA cm-2and 0.00008 mW cm-2).
The objective of this study was to investigate several operating parameters, such as open circuit, different external resistance, pH, supporting electrolyte, and presence of aeration that might enhance the degradation rate as well as electricity generation of batik wastewater in solar photocatalytic fuel cell (PFC). The optimum degradation of batik wastewater was at pH 9 with external resistor 250 Ω. It was observed that open circuit of PFC showed only 17.2 ± 7.5% of removal efficiency, meanwhile the degradation rate of batik wastewater was enhanced to 31.9 ± 15.0% for closed circuit with external resistor 250 Ω. The decolorization of batik wastewater in the absence of photocatalyst due to the absorption of light irradiation by dye molecules and this process was known as photolysis. The degradation of batik wastewater increased as the external resistor value decreased. In addition, the degradation rate of batik wastewater also increased at pH 9 which was 74.4 ± 34.9% and at pH 3, its degradation rate was reduced to 19.4 ± 8.7%. The presence of aeration and sodium chloride as supporting electrolyte in batik wastewater also affected its degradation and electricity generation. The maximum absorbance of wavelength (λmax) of batik wastewater at 535 nm and chemical oxygen demand gradually decreased as increased in irradiation time; however, batik wastewater required prolonged irradiation time to fully degrade and mineralize in PFC system.
A novel sustainable hybrid system of photocatalytic fuel cell (PFC) and Fenton process is an alternative wastewater treatment technology for energy-saving and efficient treatment of organic pollutants. The electrons generated from PFC photoanode are used to produce H2O2 in the Fenton reactor and react with the in situ generation of Fe2+ from sacrificial iron for hydroxyl radical formation. In this study, the effect of different initial Amaranth dye concentrations on degradation and electricity generation were investigated. ZnO/Zn photoanode was prepared by anodizing method and characterized by X-ray diffraction (XRD) and scanning electron microscope (SEM). Results revealed that the maximum power density (9.53 mW/m2) and current density (0.0178 mA/m2) were achieved at 10 mg/L of Amaranth. The correlation between dye degradation, voltage output, and kinetic photocatalytic degradation were also investigated and discussed.
This study investigated the effect of different supporting electrolyte (Na2SO4, MgSO4, NaCl) in degradation of Reactive Black 5 (RB5) and generation of electricity. Zinc oxide (ZnO) was immobilized onto carbon felt acted as photoanode, while Pt-coated carbon paper as photocathode was placed in a single chamber photocatalytic fuel cell, which then irradiated by UV lamp for 24 h. The degradation and mineralization of RB5 with 0.1 M NaCl rapidly decreased after 24-h irradiation time, followed by MgSO4, Na2SO4 and without electrolyte. The voltage outputs for Na2SO4, MgSO4 and NaCl were 908, 628 and 523 mV, respectively, after 24-h irradiation time; meanwhile, their short-circuit current density, J SC, was 1.3, 1.2 and 1.05 mA cm(-2), respectively. The power densities for Na2SO4, MgSO4 and NaCl were 0.335, 0.256 and 0.245 mW cm(-2), respectively. On the other hand, for without supporting electrolyte, the voltage output and short-circuit current density was 271.6 mV and 0.055 mA cm(-2), respectively. The supporting electrolyte NaCl showed greater performance in degradation of RB5 and generation of electricity due to the formation of superoxide radical anions which enhance the degradation of dye. The mineralization of RB5 with different supporting electrolyte was measured through spectrum analysis and reduction in COD concentration.
The treatment of single and binary azo dyes, as well as the effect of the circuit connection, aeration, and plant on the performance of UFCW-MFC, were explored in this study. The decolorization efficiency of Remazol Yellow FG (RY) (single dye: 98.2 %; binary dye: 92.3 %) was higher than Reactive Black 5 (RB5) (single: 92.3 %; binary: 86.7 %), which could be due to monoazo dye (RY) requiring fewer electrons to break the azo bond compared to the diazo dye (RB5). In contrast, the higher decolorization rate of RB5 in binary dye indicated the removal rate was affected by the electron-withdrawing groups in the dye structure. The closed circuit enhanced about 2% of color and 4% of COD removal. Aeration improved the COD removal by 6%, which could be contributed by the mineralization of intermediates. The toxicity of azo dyes was reduced by 11-26% and the degradation pathways were proposed. The dye removal by the plants was increased with a higher contact time. RB5 was more favorable to be uptook by the plant as RB5 holds a higher partial positive charge. 127.39 (RY), 125.82 (RB5), and 58.66 mW/m3 (binary) of maximum power density were generated. The lower power production in treating the binary dye could be due to more electrons being utilized for the degradation of higher dye concentration. Overall, the UFCW-MFC operated in a closed circuit, aerated, and planted conditions achieved the optimum performance in treating binary azo dyes containing wastewater (dye: 87-92%; COD: 91%) compared to the other conditions (dye: 83-92%; COD: 78-87%).