Enhancement of energy recovery from caffeine wastewater in constructed wetland-microbial fuel cell through operating conditions.

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.

Exploring the potential of thermophilic anaerobic co-digestion between agro-industrial waste and water hyacinth: operational performance, kinetic study and degradation pathway.

Anaerobic co-digestion (co-AD) of agro-industrial waste, namely, palm oil mill effluent (POME) and sugarcane vinasse (Vn), with water hyacinth (WH) as co-substrate was carried out in two separate Anaerobic Suspended Growth Closed Bioreactors (ASGCBs) under thermophilic (55 °C) conditions. The highest chemical oxygen demand (COD) and soluble COD reduction in co-AD of POME-WH (78.61%, 78.86%) is slightly higher than co-AD of Vn-WH (75.75%, 78.24%). However, VFA reduction in co-AD of POME-WH (96.41%) is higher compared to co-AD of Vn-WH (85.94%). Subsequently, biogas production peaked at 13438 mL/day values and 16122 mL/day for co-AD of POME-WH and Vn-WH, respectively. However, the methane content was higher in the co-AD of POME-WH (72.04%) than in the co-AD of Vn-WH (69.86%). Growth yield (YG), maximum specific substrate utilization rate (rx,max) and maximum specific biomass growth rate (µmax) are higher in co-AD of POME-WH, as supported by the higher mixed liquor volatile suspended solids (MLVSS) and COD reduction efficiency compared to co-AD of Vn-WH. However, methane yield ([Formula: see text]) reported in the co-AD of POME-WH and Vn-WH are 0.2748 and 0.3112 L CH4/g CODreduction, respectively, which suggests that WH is a more suitable co-substrate for Vn compared to POME.

Chemical and biological combined treatment for sugarcane vinasse: selection of parameters and performance studies.

Sugarcane vinasse has been reported as a high strength industrial wastewater that could cause severe environmental pollution due to its complex and bio-refractory compounds. Thus, the combined coagulation and sequencing batch biofilm reactor (SBBR) system was employed for the sugarcane vinasse treatment. This study aims to determine the recommended conditions of various parameters under coagulation and SBBR and investigate the effectiveness of combined processes. First, the approach of the coagulation process could achieve the maximum COD reduction and decolorization efficiencies of 79.0 ± 3.4% and 94.1 ± 1.9%, respectively, under the recommended conditions. Next, SBBR as an integrated biofilm reactor showed excellent synergistic biodegradability, removing 86.6 ± 4.3% COD concentration and 94.6 ± 3.8% color concentration at 3.0 g·COD/L of substrate loading concentration. The kinetic studies of SBBR revealed that the first-order kinetic model was the best fit for COD reduction efficiency. In contrast, the second-order kinetic model was the best fit for decolorization efficiency. The SBBR reaction was further investigated by ultraviolet-visible spectrophotometry (UV-Vis). In the combined processes, SBBR followed by the coagulation process (SBBR-CP) showed greater COD reduction and decolorization efficiencies (97.5 ± 0.3 and 99.4 ± 0.1%) when compared to the coagulation process followed by SBBR (CP-SBBR). This study demonstrated the removal performance and potential application of the combined sequential process to produce effluent that can be reused for bioethanol production and fertigation. This finding provides additional insight for developing effective vinasse treatment using combined chemical and biological processes.

Transformation from biofiltration unit to hybrid constructed wetland-microbial fuel cell: Improvement of wastewater treatment performance and energy recovery.

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.

Degradation of Diazo Congo Red Dye by Using Synthesized Poly-Ferric-Silicate-Sulphate through Co-Polymerization Process.

The ability of poly-ferric-silicate-sulphate (PFSS) synthesized via a co-polymerization process has been applied for the removal of diazo Congo red dye. A novel degradation pathway of diazo Congo red dye by using PFSS is proposed based on LC-MS analysis. Diazo Congo red dye was successfully removed using synthesized PFSS at lower coagulant dosages and a wider pH range, i.e., 9 mg/L from pH 5 to 7, 11 mg/L at pH 9, and 50 mg/L at pH 11. The azo bond cleavage was verified by the UV-Vis spectra of diazo Congo red-loaded PFSS and FTIR spectra which showed disappearance of the peak at 1584 cm-1 for -N=N- stretching vibrations. The synchronized results of UV-Vis spectra, FTIR, and the LC-MS analysis in this study confirmed the significance of the Si and Fe bond in PFSS towards the degradation of diazo Congo red dye. The successfully synthesized PFSS coagulant was characterized by FTIR, SEM, TEM, and HRTEM analysis. From this analysis, it was proven that PFSS is a polycrystalline material which is favorable for the coagulation-flocculation process. Based on all these findings, it was established that synthesized PFSS can be employed as a highly efficient polymeric coagulant for the removal of dye from wastewater.

Intermolecular degradation of aromatic compound and its derivatives via combined sequential and hybridized process.

The under-treated wastewater, especially remaining carcinogenic aromatic compounds in wastewater discharge has been expansively reported, wherein the efficiency of conventional wastewater treatment is identified as the primary contributor source. Herein, the advancement of wastewater treatments has drawn much attention in recent years. In the current study, combined sequential and hybridized treatment of thermolysis and coagulation-flocculation provides a novel advancement for environmental emerging pollutant (EP) prescription. This research is mainly demonstrating the mitigation efficiency and degradation pathway of pararosaniline (PRA) hybridized and combined sequential wastewater treatment. Notably, PRA degradation dominantly via a linkage of reaction: thermal cleavage, deamination, silication and diazene reduction. Thermolysis acts as an initiator for the PRA decomposition through thermally induced bond dissociation energy (BDE) for molecular fragmentation whilst coagulation-flocculation facilitates the formation of organo-bridged silsesquioxane as the final degradation product. Different from conventional treatment, the hybridized treatment showed excellent synergistic degradability by removing 99% PRA and its EPs, followed by combined sequential treatment method with 86% reduction. Comprehensive degradation pathway breakdown of carcinogenic and hardly degradable aromatic compounds provides a new insight for wastewater treatment whereby aniline and benzene are entirely undetectable in effluent. The degradation intermediates, reaction derivatives and end products were affirmed by gas chromatography-mass spectrometry, Fourier transform infrared spectroscopy and ultraviolet-visible spectrophotometry (GC-MS, FTIR and UV-Vis). This finding provides valuable guidance in establishing efficient integrated multiple-step wastewater treatments.

Insights into the decolorization of mono and diazo dyes in single and binary dyes containing wastewater and electricity generation in up-flow constructed wetland coupled microbial fuel cell.

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%).

Kinetic model discrimination on the biogas production in thermophilic co-digestion of sugarcane vinasse and water hyacinth.

Co-digestion between sugarcane vinasse (Vn) and water hyacinth (WH) at various mixing ratios of 0:1, 1:0, 1:3, 3:1, and 1:1 was carried out under thermophilic conditions (55 °C) for 60 days. The effect of various mixing ratios on the pH changes, soluble chemical oxygen demand (sCOD) reduction, and cumulative biogas production was investigated. The first order, modified Gompertz, and logistic function kinetic models were selected to fit the experimental data. Model discrimination was conducted through the Akaike Information Criterion (AIC). The study revealed that co-digestion shows better performance compared to the mono-digestion of both substrates. Vn:WH mixing ratio 1:1 with inoculum to substrate ratio (ISR) of 0.38 g VSinoculum/g VSsubstrate is the most favorable ratio, achieving sCOD reduction efficiency and cumulative biogas production of 71.6% and 1229 mL, respectively. Model selection through AIC revealed that ratio 1:1 was best fitted to the logistic function kinetic model (R2 = 0.9897) with Ym and K values of 1232 mL and 31 mL/day, respectively.

Photocatalytic Degradation of Sugarcane Vinasse Using ZnO Photocatalyst: Operating Parameters, Kinetic Studies, Phytotoxicity Assessments, and Reusability.

ABSTRACT: Photocatalytic degradation performance is highly related to optimized operating parameters such as initial concentration, pH value, and catalyst dosage. In this study, the impact of various parameters on the photocatalytic degradation of anaerobically digested vinasse (AnVE) has been determined through decolourization and chemical oxygen demand (COD) reduction efficiency using zinc oxide (ZnO) photocatalyst. In this context, the application of photocatalytic degradation in treating sugarcane vinasse using ZnO is yet to be explored. The COD reduction efficiency and decolourization achieved 83.40% and 99.29%, respectively, under the conditions of 250 mg/L initial COD concentration, pH 10, and 2.0 g/L catalyst dosage. The phytotoxicity assessment was also conducted to determine the toxicity of AnVE before and after treatment using mung bean (Vigna radiata). The reduction of root length and the weight of mung bean indicated that the sugarcane vinasse contains enormous amounts of organic substances that affect the plant's growth. The toxicity reduction in the AnVE solution can be proved by UV-Vis absorption spectra. Furthermore, the catalyst recovery achieved 93% in the reusability test. However, the COD reduction efficiency and decolourization were reduced every cycle. It was due to the depletion of the active sites in the catalyst with the adsorption of organic molecules. Thus, it can be concluded that the photocatalytic degradation in the treatment of AnVE was effective in organic degradation, decolorization, toxicity reduction and can be reused after the recovery process.

Haldane-Andrews substrate inhibition kinetics for pilot scale thermophilic anaerobic degradation of sugarcane vinasse.

A pilot scale anaerobic degradation of sugarcane vinasse was carried out at various hydraulic retention time (HRT) in the Anaerobic Suspended Growth Closed Bioreactor (ASGCB) under thermophilic temperature. The performance and kinetics were evaluated through the Haldane-Andrews model to investigate the substrate inhibition potential of sugarcane vinasse. All parameters show great performance between HRT 35 and 25 days: chemical oxygen demand (COD) reduction efficiency (81.6 to 86.8%), volatile fatty acids (VFA) reduction efficiency (92.4 to 98.5%), maximum methane yield (70%) and maximum biogas production (19.35 L/day). Furthermore, steady state values from various HRT were obtained in the kinetic evaluation for: rXmax (1.20 /day), Ks (19.95 gCOD/L), Ki (7.00 gCOD/L) and [Formula: see text] (0.33 LCH4/gCOD reduction). This study shows that anaerobic degradation of sugarcane vinasse through ASGCB could perform well at high HRT and provides a low degree of substrate inhibition as compared to existing studies from literature.

Revealing the influences of functional groups in azo dyes on the degradation efficiency and power output in solar photocatalytic fuel cell.

In this study, the degradation efficiency and electricity generation of the azo dyes affected by the functional groups and molecular structure in a solar photocatalytic fuel cell (PFC) system were investigated and discussed in detail. Four different azo dyes such as, Acid Orange 7 (AO7), Acid Red 18 (AR18), Reactive Black 5 (RB5), Reactive Red 120 (RR120) with different molecular structure were evaluated. The degradation efficiency of AO7, AR18, RB5 and RR120 achieved 5.6 ± 0.3%, 11.1 ± 0.6%, 41.9 ± 0.9% and 52.1 ± 1.3%, respectively, after 6 h irradiated under solar light. In addition, the maximum power density, Pmax for AO7, AR18, RB5 and RR120 was 0.0269 ± 0.01, 0.111 ± 0.03, 1.665 ± 0.67 and 4.806 ± 1.79 mW cm-2, respectively. Meanwhile, the concentration of COD for AO7, AR18, RB5 and RR120 reduced to 16 ± 0.1, 10 ± 0.3, 7 ± 0.6 and 3 ± 0.9 mg L-1, respectively. The concentration ratio of benzene / naphthalene, benzene / azo bond and naphthalene / azo bond, respectively, was analyzed to investigate the impact of the functional groups over photodegradation of the azo dyes in PFC. Electron releasing groups (-OH and -NH2) and electron withdrawing groups (-SO3Na) which attached to the naphthalene or benzene ring also played a pivotal role in the degradation mechanism.

The reaction of wastewater treatment and power generation of single chamber microbial fuel cell against substrate concentration and anode distributions.

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.

Constructed wetland-microbial fuel cell for azo dyes degradation and energy recovery: Influence of molecular structure, kinetics, mechanisms and degradation pathways.

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.

Performance of the hybrid growth sequencing batch reactor (HG-SBR) for biodegradation of phenol under various toxicity conditions.

Hybrid growth microorganisms in sequencing batch reactors have proven effective for treating the toxic compound phenol, but the toxicity effect under different toxicity conditions has rarely been discussed. Therefore, the performance of the HG-SBR under toxic, acute and chronic organic loading can provide the overall operating conditions of the system. Toxic organic loading (TOL) was monitored during the first 7hr while introducing 50mg/L phenol to the system. The system was adversely affected with the sudden introduction of phenol to the virgin activated sludge, which caused a low degradation rate and high dissolved oxygen consumption during TOL. Acute organic loading (AOL) had significant effects at high phenol concentrations (600, 800 1000mg/L). The specific oxygen uptake rate (SOUR) gradually decreased to 4.9mg O2/(g MLVSS·hr) at 1000mg/L of phenol compared to 12.74mg O2/(g MLVSS·hr) for 200mg/L of phenol. The HG-SBR was further monitored during chronic organic loading (COL) over 67days. The effects of organic loading were more apparent at 800mg/L and 1000mg/L phenol concentrations, as the removal range was between 22%-30% and 18%-46% respectively, which indicated the severe effects of COL.

Enhancement of simultaneous batik wastewater treatment and electricity generation in photocatalytic fuel cell.

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.

Exploring the relationship between molecular structure of dyes and light sources for photodegradation and electricity generation in photocatalytic fuel cell.

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.

Up-flow constructed wetland-microbial fuel cell for azo dye, saline, nitrate remediation and bioelectricity generation: From waste to energy approach.

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.

Sustainable green technology on wastewater treatment: The evaluation of enhanced single chambered up-flow membrane-less microbial fuel cell.

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.

Reactive Black 5 as electron donor and/or electron acceptor in dual chamber of solar photocatalytic fuel cell.

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.

Degradation reaction of Diazo reactive black 5 dye with copper (II) sulfate catalyst in thermolysis treatment.

The theme of present research demonstrates performance of copper (II) sulfate (CuSO4) as catalyst in thermolysis process to treat reactive black 5 (RB 5) dye. During thermolysis without presence of catalyst, heat was converted to thermal energy to break the enthalpy of chemical structure bonding and only 31.62% of color removal. With CuSO4 support as auxiliary agent, the thermally cleaved molecular structure was further destabilized and reacted with CuSO4. Copper ions functioned to delocalize the coordination of π of the lone paired electron in azo bond, C=C bond of the sp2 carbon to form C-C of the sp3 amorphous carbon in benzene and naphthalene. Further, the radicals of unpaired electrons were stabilized and RB 5 was thermally decomposed to methyl group. Zeta potential measurement was carried out to analyze the mechanism of RB 5 degradation and measurement at 0 mV verified the critical chemical concentration (CCC) (0.7 g/L copper (II) sulfate), as the maximum 92.30% color removal. The presence of copper (II) sulfate catalyst has remarkably increase the RB 5 dye degradation as the degradation rate constant without catalyst, k1 is 6.5224 whereas the degradation rate constant with catalyst, k2 is 25.6810. This revealed the correlation of conversion of thermal energy from heat to break the chemical bond strength, subsequent fragmentation of RB 5 dye molecular mediated by copper (II) sulfate catalyst. The novel framework on thermolysis degradation of molecular structure of RB 5 with respect to the bond enthalpy and interfacial intermediates decomposition with catalyst reaction were determined.