A microbial electrolysis cell (MEC) fully catalysed by microorganisms is an attractive technology because it incorporates the state-of-the-art concept of converting organic waste to hydrogen with less external energy input than conventional electrolysers. In this work, the impact of the anode feed mode on the production of hydrogen by the biocathode was studied. In the first part, three feed modes and MEC performance in terms of hydrogen production were evaluated. The results showed the highest hydrogen production under the continuous mode (14.6 ± 0.4), followed by the fed-batch (12.7 ± 0.4) and batch (0 L m-2 cathode day-1) modes. On one hand, the continuous mode only increased by 15% even though the hydraulic retention time (HRT) (2.78 h) was lower than the fed-batch mode (HRT 5 h). A total replacement (fed-batch) rather than a constant mix of existing anolyte and fresh medium (continuous) was preferable. On the other hand, no hydrogen was produced in batch mode due to the extensive HRT (24 h) and bioanode starvation. In the second part, the fed-batch mode was further evaluated using a chronoamperometry method under a range of applied cell voltages of 0.3-1.6 V. Based on the potential evolution at the electrodes, three main regions were identified depending on the applied cell voltages: the cathode activation (<0.8 V), transition (0.8-1.1 V), and anode limitation (>1.1 V) regions. The maximum hydrogen production recorded was 12.1 ± 2.1 L m-2 cathode day-1 at 1.0 V applied voltage when the oxidation and reduction reactions at the anode and cathode were optimal (2.38 ± 0.61 A m-2). Microbial community analysis of the biocathode revealed that Alpha-, and Deltaproteobacteria were dominant in the samples with >70% abundance. At the genus level, Desulfovibrio sp. was the most abundant in the samples, showing that these microbes may be responsible for hydrogen evolution.
The bioanode is important for a microbial electrolysis cell (MEC) and its robustness to maintain its catalytic activity affects the performance of the whole system. Bioanodes enriched at a potential of +0.2V (vs. standard hydrogen electrode) were able to sustain their oxidation activity when the anode potential was varied from -0.3 up to +1.0V. Chronoamperometric test revealed that the bioanode produced peak current density of 0.36A/m(2) and 0.37A/m(2) at applied potential 0 and +0.6V, respectively. Meanwhile hydrogen production at the biocathode was proportional to the applied potential, in the range from -0.5 to -1.0V. The highest production rate was 7.4L H2/(m(2) cathode area)/day at -1.0V cathode potential. A limited current output at the bioanode could halt the biocathode capability to generate hydrogen. Therefore maximum applied potential that can be applied to the biocathode was calculated as -0.84V without overloading the bioanode.
Metallic transition metal dichalcogenides (TMDs)1-8 are good catalysts for the hydrogen evolution reaction (HER). The overpotential and Tafel slope values of metallic phases and edges9 of two-dimensional (2D) TMDs approach those of Pt. However, the overall current density of 2D TMD catalysts remains orders of magnitude lower (~10-100 mA cm-2) than industrial Pt and Ir electrolysers (>1,000 mA cm-2)10,11. Here, we report the synthesis of the metallic 2H phase of niobium disulfide with additional niobium (2H Nb1+xS2, where x is ~0.35)12 as a HER catalyst with current densities of >5,000 mA cm-2 at ~420 mV versus a reversible hydrogen electrode. We find the exchange current density at 0 V for 2H Nb1.35S2 to be ~0.8 mA cm-2, corresponding to a turnover frequency of ~0.2 s-1. We demonstrate an electrolyser based on a 2H Nb1+xS2 cathode that can generate current densities of 1,000 mA cm-2. Our theoretical results reveal that 2H Nb1+xS2 with Nb-terminated surface has free energy for hydrogen adsorption that is close to thermoneutral, facilitating HER. Therefore, 2H Nb1+xS2 could be a viable catalyst for practical electrolysers.
Microcystin-LR (MC-LR), which is one of the most commonly found microcystins (MCs) in fresh water, has been proved to be a potential tumour promoter and classified as 2B by the International Agency for Research on Cancer. MC-LR decomposition and inhibition of MC-LR production in Microcystis aeruginosa were investigated under electrolysis condition using an electrolysis cell consisting of Ti/Pt electrodes and Nafion membrane. The relationship between the decrease in MC-LR concentration and transcription of MC-LR synthesis gene clusters was determined by performing real-time reverse transcription polymerase chain reaction (RT-qPCR) to monitor changes in the levels of transcription encoding mcyB and mcyD (cDNA to DNA) in M. aeruginosa NIES 1086 under electrolysis condition and three different conditions (i.e. oxygenated, air aerated and unaerated) as controls. Cell density decreased from day 2 under electrolysis than under the three controls. Intracellular MC-LR concentration was approximately 33 fg cell-1 under electrolysis from days 4 to 8, while those in the other conditions ranged in 40-50 fg cell-1. The mcyB transcription continuously decreased from day 2 to nondetectable level in day 6 under electrolysis, while this transcription was stabilised under the three controls. This result suggested that oxidative stress, such as hydroxyl radicals, played an important role in the down-regulation of mcyB and mcyD gene transcription level and the MC-LR concentration and cell density of M. aeruginosa.
Pretreatment of microalgal biomass possessing rigid cell wall is a critical step for enhancing the efficiency of microalgal biorefinery. However, the conventional pretreatment processes suffer the drawbacks of complex processing steps, long processing time, low conversion efficiency and high processing costs. This significantly hinders the industrial applicability of microalgal biorefinery. The innovative electricity-aid pretreatment techniques serve as a promising processing tool to extensively enhance the release of intracellular substances from microalgae. In this review, application of electric field-based techniques and recent advances of using electrical pretreatments on microalgae cell focusing on pulsed electric field, electrolysis, high voltage electrical discharges and moderate electric field are reviewed. In addition, the emerging techniques integrating electrolysis with liquid biphasic flotation process as promising downstream approach is discussed. This review delivers broad knowledge of the present significance of the application of these methods focusing on the development of electric assisted biomolecules extraction from microalgae.
In this study, the zinc oxide (ZnO) layer was synthesised on the surface of Zn plates by three different techniques, i.e. electrolysis, hydrogen peroxide and heat treatment. The synthesised ZnO layers were characterised using scanning electron microscopy, X-ray diffraction, UV-visible diffuse reflectance and photoluminescence spectroscopy. The photocatalytic activity of the ZnO layer was further assessed against methylene blue (MB) degradation under UV irradiation. The photocatalytic degradation of MB was achieved up to 84%, 79% and 65% within 1 h for ZnO layers synthesised by electrolysis, heat and hydrogen peroxide treatment, respectively. The reusability results show that electrolysis and heat-treated ZnO layers have considerable photocatalytic stability. Furthermore, the results confirmed that the photocatalytic efficiency of ZnO was directly associated with the thickness and enlarged surface area of the layer. Finally, this study proved that the ZnO layers synthesised by electrolysis and heat treatment had shown better operational stability and reusability.
A new method of Standard Malaysian Rubber (SMR) process wastewater treatment was developed based on in situ hypochlorous acid generation. The hypochlorous acid was generated in an undivided electrolytic cell consisting of two sets of graphite as anode and stainless sheets as cathode. The generated hypochlorous acid served as an oxidizing agent to destroy the organic matter present in the SMR wastewater. For an influent COD concentration of 2960 mg/L at an initial pH 4.5+/-0.1, current density 74.5 mA/cm(2), sodium chloride content 3% and electrolysis period of 75 min, resulted in the following residual values pH 7.5, COD 87 mg/L, BOD(5) 60 mg/L, TOC 65 mg/L, total chlorine 146 mg/L, turbidity 7 NTU and temperature 48 degrees C, respectively. In the case of 2% sodium chloride as an electrolyte for the above said operating condition resulted in the following values namely: pH 7.2, COD 165 mg/L, BOD(5) 105 mg/L, TOC 120 mg/L, total chlorine 120 mg/L, turbidity 27 NTU and temperature 53 degrees C, respectively. The energy requirement were found to be 30 and 46 Wh/L, while treating 24 L of SMR wastewater at 2 and 3% sodium chloride concentration at a current density 74.5 mA/cm(2). The observed energy difference was due to the improved conductivity at high sodium chloride content.
That water may not be an inert medium was indicated by the presence at water's interfaces a negatively charged solute free zone of several hundred microns in thickness called the exclusion zone (EZ). Further evidence was demonstrated by Ovchinnikova's experiments (2009) showing that water can store and release substantial amount of charge. We demonstrate that the charge storage capacity of water arises from highly stable large-scale ionic structures with measurable charge imbalances and discrete levels of charge density. We also show evidence that the charge zones formation requires ionic solutes, and their formation correlate to large change in conductivity, by as much as 250%. Our experiments indicate that large-scale structuring plays a pivotal role in electrolysis and conductivity in ionic solution. We propose that water is an electrochemically active medium and present a new model of electrolysis and conductivity in ionic solution.
Microbial electrolysis cells (MECs) are perceived as a potential and promising innovative biotechnological tool that can convert carbon-rich waste biomass or wastewater into hydrogen (H2) or other value-added chemicals. Undesired methane (CH4) producing H2 sinks, including methanogens, is a serious challenge faced by MECs to achieve high-rate H2 production. Methanogens can consume H2 to produce CH4 in MECs, which has led to a drop of H2 production efficiency, H2 production rate (HPR) and also a low percentage of H2 in the produced biogas. Organized inference related to the interactions of microbes and potential processes has assisted in understanding approaches and concepts for inhibiting the growth of methanogens and profitable scale up design. Thus, here in we review the current developments and also the improvements constituted for the reduction of microbial H2 losses to methanogens. Firstly, the greatest challenge in achieving practical applications of MECs; undesirable microorganisms (methanogens) growth and various studied techniques for eliminating and reducing methanogens activities in MECs were discussed. Additionally, this extensive review also considers prospects for stimulating future research that could help to achieve more information and would provide the focus and path towards MECs as well as their possibilities for simultaneously generating H2 and waste remediation.
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).
This study presented the implementation of a small-scale (50 W) solar energy harvesting system coupled with an electrolyzer and proton exchange membrane (PEM) fuel cell. The energy from the solar panel would be utilized by the electrolyzer to produce hydrogen gas. The hydrogen gas would be used, in turn, by the PEM fuel cell to generate electricity which supports both DC and AC load. Excess energy from the solar panel is also used to charge the lead-acid backup battery. Analysis of the system showed that 400 mL of hydrogen gas could be produced within every 17 minutes in optimal conditions; between 11 am until 4 pm with bright sunlight. For every 400 mL of hydrogen gas, the PEM fuel cell could sustain continuous operation of a 5V 500 mA DC load for 95 seconds. Theoretically, more than 7000 mL of hydrogen gas could be produced within 5 hours in strong sunlight, which could power up a 50 mA and 500 mA load for 4.7 hours and 28 minutes respectively, during evening or night operations. The proposed system could complement the traditional battery-based storage system while remaining as a clean source of energy production.
Hydroxylammonium nitrate (HAN) is a promising green propellant because of its low toxicity, high volumetric specific impulse, and reduced development cost. Electrolytic decomposition of HAN is an efficient approach to prepare it for further ignition and combustion. This paper describes the investigation of a co-electrolysis effect on electrolytic decomposition of HAN-fuel mixtures using stainless steel-platinum (SS-Pt) electrodes. For the first time, different materials were utilized as electrodes to alter the cathodic reaction, which eliminated the inhibition effect and achieved a repeatable and consistent electrolytic decomposition of HAN solution. Urea and methanol were added as fuel components in the HAN-fuel mixtures. When the mass ratio of added urea ≥20%, the electrolytic decomposition of a HAN-urea ternary mixture achieved 67% increment in maximum gas temperature (Tgmax) and 185% increment in overall temperature increasing rate over the benchmark case of HAN solution. The co-electrolysis of urea released additional electrons into the mixtures and enhanced the overall electrolytic decomposition of HAN. In contrast, the addition of methanol did not improve the Tgmax but only increased the overall temperature increasing rate. This work has important implications in the development of an efficient and reliable electrolytic decomposition system of HAN and its mixtures for propulsion applications.
This study investigated the effects of different parameters on the removal efficiencies of organic and inorganic pollutants in landfill leachate treatment by electrolysis. Different parameters were considered such as the electric potential (e.g., 24, 40 and 60 V), hydraulic retention time (HRT) (e.g., 40, 60, 80, 100 and 120 min), sodium chloride (NaCl) concentration (e.g., 1, 3, 5 and 7%), pH (e.g., 3, 7 and 9), electrodes materials [e.g., aluminum (Al) and iron (Fe)] and distance between electrodes (e.g., 1, 2 and 3 cm). The best operational condition of electrolysis was then recommended. The electric potential of 60 V with HRT of 120 min at 5% of NaCl solution using Al as anode and Fe as cathode (kept at a distance of 3 cm) was the most efficient condition which increased the removal efficiencies of various parameters such as turbidity, salinity, total suspended solids (TSS), total dissolved solids (TDS), biochemical oxygen demand (BOD), chemical oxygen demand (COD) and heavy metals (e.g., Zn and Mn). The higher removal percentages of many parameters, especially COD (94%) and Mn (93%) indicated that the electrolysis is an efficient technique for multi-pollutants (e.g., organic, inorganic and heavy metals) removal from the landfill leachate.
Using solar-powered water electrolysis systems for hydrogen generation is a key decision for the development of a sustainable hydrogen economy. A facile approach is presented in the present investigation to improve the solar-powered photoelectrochemical performance of water electrolysis systems by synthesising well-aligned and highly ordered TiO₂ nanotube films without bundling through the electrochemical anodisation technique. Herein, geometrical calculations were conducted for all synthesised TiO₂ nanotubes, and determination of the aspect ratio (AR) and geometric surface area factor (G) was achieved. On the basis of the collected data, well-aligned TiO₂ nanotubes with an AR of approximately 60 and G of approximately 400 m² ·g-1 were successfully formed in an electrolyte mixture of ethylene glycol with 0.3 wt% NH4F and 5 wt% H₂O₂ at 40 V for 60 min. The nanotubes were subsequently annealed at 400 °C to form anatase-phase TiO₂ nanotube films. The resultant well-aligned and highly ordered TiO₂ nanotube films exhibited a photocurrent density of 1.5 mA · cm-2 due to a large number of photo-induced electrons moving along the tube axis and perpendicular to the Ti substrate, which greatly reduces interfacial recombination losses.
Highly reactive zinc metal was prepared by electrolysis of a N,N-dimethylformamide (DMF) solution containing naphthalene and a supporting electrolyte in a one-compartment cell fitted with a platinum cathode and a zinc anode. This highly reactive electrogenerated zinc (EGZn/Naph) was used for transformation of ethyl 2-bromoacrylate into the corresponding organozinc compound, which can not be achieved by the use of usual zinc metals. Reaction of the organozinc compounds thus prepared with various aryl halides in the presence of 5 mol% of palladium catalyst gave the corresponding cross-coupling products in high yields. These cross-coupling reactions were successfully applied to a synthesis of the precursor of anti-inflammatory agents such as ibuprofen, naproxen, cicloprofen and suprofen.
In recent years, calcium phosphate-base composites, such as hydroxyapatite (HA) and carbonate apatite (CA) have been considered desirable and biocompatible coating layers in clinical and biomedical applications such as implants because of the high resistance of the composites. This review focuses on the effects of voltage, time and electrolytes on a calcium phosphate-base composite layer in case of pure titanium and other biomedical grade titanium alloys via the plasma electrolytic oxidation (PEO) method. Remarkably, these parameters changed the structure, morphology, pH, thickness and crystallinity of the obtained coating for various engineering and biomedical applications. Hence, the structured layer caused improvement of the biocompatibility, corrosion resistance and assignment of extra benefits for Osseo integration. The fabricated layer with a thickness range of 10 to 20 μm was evaluated for physical, chemical, mechanical and tribological characteristics via XRD, FESEM, EDS, EIS and corrosion analysis respectively, to determine the effects of the applied parameters and various electrolytes on morphology and phase transition. Moreover, it was observed that during PEO, the concentration of calcium, phosphor and titanium shifts upward, which leads to an enhanced bioactivity by altering the thickness. The results confirm that the crystallinity, thickness and contents of composite layer can be changed by applying thermal treatments. The corrosion behavior was investigated via the potentiodynamic polarization test in a body-simulated environment. Here, the optimum corrosion resistance was obtained for the coating process condition at 500 V for 15 min in Ringer solution. This review has been summarized, aiming at the further development of PEO by producing more adequate titanium-base implants along with desired mechanical and biomedical features.
Microalgae are the most promising sources of protein, which have high potential due to their high-value protein content. Conventional methods of protein harnessing required multiple steps, and they are generally complex, time consuming, and expensive. Currently, the study of integration methods for microalgae cell disruption and protein recovery process as a single-step process is attracting considerable interest. This study aims to investigate the novel approach of integration method of electrolysis and liquid biphasic flotation for protein extraction from wet biomass of Chlorella sorokiniana CY-1 and obtaining the optimal operating conditions for the protein extraction. The optimized conditions were found at 60% (v/v) of 1-propanol as top phase, 250 g/L of dipotassium hydrogen phosphate as bottom phase, crude microalgae loading of 0.1 g, air flowrate of 150 cc/min, flotation time of 10 min, voltage of 20 V and electrode's tip touching the top phase of LBEF. The protein recovery and separation efficiency after optimization were 23.4106 ± 1.2514% and 173.0870 ± 4.4752%, respectively. Comparison for LBEF with and without the aid of electric supply was also conducted, and it was found that with the aid of electrolysis, the protein recovery and separation efficiency increased compared to the LBEF without electrolysis. This novel approach minimizes the steps for overall protein recovery from microalgae, time consumption, and cost of operation, which is beneficial in bioprocessing industry.
Palm oil mill effluent (POME) is highly polluting wastewater generated from the palm oil milling process. Palm oil mill effluent was used as an electrolyte without any additive or pretreatment to perform electrocoagulation (EC) using electricity (direct current) ranging from 2 to 4 volts in the presence of aluminum electrodes with a reactor volume of 20 L. The production of hydrogen gas, removal of chemical oxygen demand (COD), and turbidity as a result of electrocoagulation of POME were determined. The results show that EC can reduce the COD and turbidity of POME by 57 and 62%, respectively, in addition to the 42% hydrogen production. Hydrogen production was also helpful to remove the lighter suspended solids toward the surface. The production of Al(OH)XHO at the aluminum electrode (anode) was responsible for the flocculation-coagulation process of suspended solids followed by sedimentation under gravity. The production of hydrogen gas from POME during EC was also compared with hydrogen gas production by electrolysis of tap water at pH 4 and tap water without pH adjustment under the same conditions. The main advantage of this study is to produce hydrogen gas while treating POME with EC to reduce COD and turbidity effectively.