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%).
This study aimed to compare the performance of biofiltration, constructed wetland, and constructed wetland microbial fuel cell (CW-MFC). The transformation from a biofiltration unit to a hybrid CW-MFC was demonstrated with the advantages of improvement of wastewater treatment while generating electricity simultaneously. The introduction of plants to the upper region of the bioreactor enhanced the DO level by 0.8 mg/L, ammonium removal by 5 %, and COD removal by 1 %. The integration of electrodes and external circuits stimulated the degradation rate of organic matter in the anodic region (1 % without aeration and 3 % with aeration) and produced 5.13 mW/m3 of maximum power density. Artificial aeration improved the nitrification efficiency by 38 % and further removed the residual COD to an efficiency of 99 %. The maximum power density was also increased by 3.2 times (16.71 mW/m3) with the aid of aeration. In treating higher organic loading wastewater (3M), the maximum power density showed a significant increment to 78.01 mW/m3 (4.6-fold) and the COD removal efficiency was 98 %. The ohmic overpotential dominated the proportion of total loss (67-91 %), which could be ascribed to the low ionic conductivity. The reduction in activation and concentration loss contributed to the lower internal resistance with the additional aeration and higher organic loading. Overall, the transformation from biofiltration to a hybrid CW-MFC system is worthwhile since the systems quite resemble while CW-MFC could improve the wastewater treatment as well as recover energy from the treated wastewater.
The enhancement of up-flow constructed wetland-microbial fuel cell (UFCW-MFC) performance in energy retrieval from caffeine containing wastewater has been explored via various operating conditions (hydraulic retention time (HRT), multianode (MA), multicathode current collector (MC), external resistance). The anaerobic decaffeination and COD removal improved by 37 and 12% as the HRT extended from 1 to 5 d. The increment in contact time between the microbes and organic substrates promoted the degradation and contributed to higher power output (3.4-fold), CE (eightfold), and NER (14-16-fold). The MA and MC connections facilitated the electron transfer rate and the degradation rate of organic substrates in the multiple anodic zones, which enhanced the removal efficiency in the anaerobic compartment (Caffeine: 4.2%; COD: 7.4%) and led to higher electricity generation (Power: 4.7-fold) and energy recovery (CE: 1.4-fold; NER: 2.3-2.5-fold) compared to SA. The lower external resistance favored the growth of electrogens and induced higher electron flux, where the best treatment performance and electricity production was obtained when the external resistance approached the internal resistance. Overall, it was noteworthy that the optimum operating conditions were achieved with 5 d HRT, MA, and MC connection along with external resistance of 200 Ω, which significantly outperformed the initial conditions (1 d HRT, SA connection, and 1000 Ω) by 43.7 and 29.8% of caffeine and COD removal in the anaerobic compartment, respectively as well as 14-fold of power generation.
Significant progress has been made over the years to improve the stability and efficiency of rapidly evolving tin-based perovskite solar cells (PSCs). One powerful approach to enhance the performance of these PSCs is through compositional engineering techniques, specifically by incorporating a mixed cation system at the A-site and B-site structure of the tin perovskite. These approaches will pave the way for unlocking the full potential of tin-based PSCs. Therefore, in this study, a theoretical investigation of mixed A-cations (FA, MA, EA, Cs) with a tin-germanium-based PSC was presented. The crystal structure distortion and optoelectronic properties were estimated. SCAPS 1-D simulations were employed to predict the photovoltaic performance of the optimized tin-germanium material using different electron transport layers (ETLs), hole transport layers (HTLs), active layer thicknesses, and cell temperatures. Our findings reveal that EA0.5Cs0.5Sn0.5Ge0.5I3 has a nearly cubic structure (t = 0.99) and a theoretical bandgap within the maximum Shockley-Queisser limit (1.34 eV). The overall cell performance is also improved by optimizing the perovskite layer thickness to 1200 nm, and it exhibits remarkable stability as the temperature increases. The short-circuit current density (Jsc) remains consistent around 33.7 mA/cm2, and the open-circuit voltage (Voc) is well-maintained above 1 V by utilizing FTO as the conductive layer, ZnO as the ETL, Cu2O as the HTL, and Au as the metal back contact. This configuration also achieves a high fill factor ranging from 87 % to 88 %, with the highest power conversion efficiency (PCE) of 31.49 % at 293 K. This research contributes to the advancement of tin-germanium perovskite materials for a wide range of optoelectronic applications.
To enhance dye removal and energy recovery efficiencies in single-pair electrode photocatalytic fuel cell (PFC-AC), dual cathodes PFC (PFC-ACC) and dual photoanodes PFC (PFC-AAC) were established. Results revealed that PFC-AAC yielded the highest decolorization rate (1.44 h-1) due to the promotion of active species such as superoxide radical (•O2-) and hydroxyl radical (•OH) when the number of photoanode was doubled. The results from scavenging test and UV-Vis spectrophotometry disclosed that •OH was the primary active species in dye degradation of PFC. Additionally, PFC-AAC also exhibited the highest power output (17.99 μW) but the experimental power output was much lower than the theoretical power output (28.24 μW) due to the strong competition of electron donors of doubled photoanodes to electron acceptors at the single cathode and its high internal resistance. Besides, it was found that the increments of dye volume and initial dye concentration decreased the decolorization rate but increased the power output due to the higher amount of sacrificial agents presented in PFC. Based on the abovementioned findings and the respective dye intermediate products identified from gas chromatography-mass spectrometry (GC-MS), the possible degradation pathway of RR120 was scrutinized and proposed.