Harvest of electrical energy from fermented microalgal residue using a microbial fuel cell

The application of microalgal biomass for fermentation has been highlighted as a means of producing a range of value-added biofuels and chemicals. On the other hand, the microalgal residue from the fermentation process still contains as much as 50% organic contaminants, which can be a valuable substrate for further bioenergy recovery. In this study, a microbial fuel cell and automatic external load control by maximum power point tracking (MPPT) were implemented to harvest the electrical energy from waste fermented microalgal residue (FMR). The MFC with MPPT produced the highest amount of energy (1.82 kJ/L) compared to the other MFCs with fixed resistances: 0.98 (1000 Ω), 1.16 (500 Ω), and 1.17 kJ/L (300 Ω). The MFC with MPPT also showed the highest maximum power density (88.6 mW/m²) and COD removal efficiency (620.0 mg COD/L removal with 85% removal efficiency). The implementation of MPPT gained an approximate 12.9% energy yield compared to the previous fermentation stage. These results suggest that FMR can be an appropriate feedstock for electrical energy recovery using MFCs, and the combined fermentation and MFC system improves significantly the energy recovery and treatment efficiency from FMR.     

Recent insights into microalgae-assisted microbial fuel cells for generating sustainable bioelectricity

Power generation from the renewable biomass sources using microbial fuel cell (MFC) has attracted significant attention in recent years, while chemical energy stored in microalgae biomass has efficiently been used for the sustainable production of biofuels and other valuable bioproducts since the decades. The usage of these photosynthetic organisms in MFC can enhance the efficiency of MFC and provide a cost-effective and renewable approach for the bio-generation of electricity. Microalgae are commonly incorporated either with anode or cathode compartment of MFC to generate electron or oxygen, respectively. Despite microalgae-assisted MFC (MA-MFC) would be more sustainable than using MFC alone, further developments in such systems are still required for improving its efficiency and achieving a real-world application on a large scale. In this context, understanding in bio-electrochemical mechanism of MA-MFC, including electrons shuttle and oxygen generation, is very important. Moreover, many factors can limit the efficiency and performances of MA-MFCs that are needed to optimize in further research efforts. This review presents a comprehensive insight into MA-MFC, including the recent developments and potential challenges in this promising bio-electricity generating system. Specifically, it focuses a critical discussion on the configurations of MA-MFC, key operating parameters affecting performances of MA-MFC, challenges and prospective research works for improving the overall energy output of MA-MFC.     

Enhancement of bio-hydrogen generation by spirulina via an electrochemical photo-bioreactor (EPBR)

The biological production of hydrogen by microalgae is considered as an advantageous process. However, its yields are sometimes limited. To go beyond this limit, the improvement of the H₂ generation rate by Spirulina was studied via an electrochemical photo-bioreactor (EPBR). This EPBR led to hydrogen evolution rates of up to 27.49 and 13.37 mol of H₂.d⁻¹.m⁻³ for the anode and cathode chambers, respectively, under 0.3 V voltage and ~2.5 mA current. These results represent about a 4-fold increase compared to the H₂ production rate recorded without the application of a voltage. This increase in bio-hydrogen production is correlated with a drop in the concentration of NADPH. The Electrochemical Sequential Batch Reactor (ESRB) provided a more interesting total production rate which was 2.65 m³ m⁻³ d⁻¹, compared to the batch mode, which gave 1.2 m³ m⁻³.d⁻¹. The results show, for the first time, the boosting effect of the voltage on the metabolism of H₂ production by the Spirulina strain.     

Avenues to the financial viability of microbial electrolysis cells [MEC] for domestic wastewater treatment and hydrogen production

We propose targets, based on real world data, necessary to design a financially viable microbial electrolysis cell (MEC) for the treatment of domestic wastewater. By reducing the cost of the anode and current collecting materials by 90%, a viable organic loading rate would be between 800 and 1,400g-COD/m³/d (2–3A/m²). The anode and current collector materials account for 94% of the total material costs; consequently, cost savings in any other material are moot. If the bioanode can be reused after 20 years, further, significant savings could be achieved. To develop targets we used real world data, for the first time, to evaluate the financial viability of MECs against the current predominant method of wastewater treatment: activated sludge. We modelled net present values for eight potential scenarios and the performances required for MECs to break-even.     

Proton-exchange membrane fuel cell ionomer hydration model using finite volume method

In this paper a dynamic membrane electrode assembly water transport model, based on the Finite Volume Method, is presented. The purpose of this paper is to provide an accessible and reproductible model capable of real time simulation. To this aim, a detailed explanation is provided regarding the equations and methods used to compute the physical-based fuel cell model. Additionally, the model is purposely developed using basic code (on Matlab?), to not be limited to a single programming language. Two phase water transport through multi-gaseous porous media (electrodes), interfacial transport, as well as diffusion, convection, and electro-osmosis within the polymer are considered. The main novelty relies in the restructuring of all equations into a single implicit system, which can iteratively be resolved through LU decomposition. This computationally efficient method allows the model to be capable of real-time simulation, by displaying the membrane water content profile evolution on a 3D figure. For nominal PEMFC operating conditions, a dry membrane reaches 35% of its final water concentration value after 2 s, and fully converges after 20 s. The final water content profile displays an 18% gradient (9 and 11 molecules per sulfonic acid sites on the anode and cathode sides, respectively). To calibrate and validate this model, mass transfer (flowmeter) and electrical (ohmmeter) methods have been applied.     

Co-generation of hydrogen and electricity from biodiesel process effluents

In this study, we apply a short-term voltage (0.2–0.8 V) to both crude glycerol (CG) and an anaerobic digestion (AD) effluent in a single-chamber microbial fuel cell (MFC) for power production. This improves the bioelectrogenesis in both CG (in MFC-1) and the AD effluent (in MFC-2), but higher power generation is attained in MFC-2. The use of domestic and synthetic wastewaters in the AD process leads to the generation of 195 and 350 mL H₂/L-medium, respectively. MFC-2 performs better than MFC-1 in terms of both voltage generation and chemical oxygen demand (COD) reduction. The application of 0.8 V yields a power density of 311 mW/m² (1.94 times higher than that of the control (160 mW/m²)). In addition, MFC-2 exhibits a 70% COD removal at 0.8 V, which decreases to 56% at 0.2 V. Thus, the application of a short-term voltage in MFC can stimulate both bioelectrogenesis and COD removal.     

Determination of fuel utilisation and recirculated gas composition in dead-ended PEMFC systems

This work presents a fundamental theory and methods for understanding the gas composition dynamics in PEMFC anode fuel supply compartments operated dead-ended with recirculation. The methods are applied to measurement data obtained from a PEMFC system operated with a 1 kW short stack.We show how fuel utilisation and stack efficiency, two key factors determining how well a fuel supply system performs, are coupled through the anode gas composition.The developed methods allow determination of the anode fuel supply molar balance, giving access to the membrane crossover rates and the extent of recirculated gas exchanged to fresh fuel during a purge. A methane tracer gas is also evaluated for estimating fuel impurity enrichment ratios.The above theory and methods may be applied in modelling and experimental research activities related to defining hydrogen fuel quality standards, as well as for developing more efficient and robust PEMFC system operation strategies.     

Characteristics and performance of the Co–CeO2 catalyst as a function of the promoter (La,Pr, and Zr) used in high temperature water gas shift reaction

The catalysts used to facilitate the water gas shift reaction (WGSR) are generally harmful to the environment. Therefore, catalysts that have high activity and stability in WGSR and do not pollute the environment need to be fabricated. Herein, three promoters (La, Pr, and Zr) are added into Co–CeO₂ (CoCe) catalyst to improve catalytic performance in a high temperature WGSR to produce high-purity hydrogen from waste-derived synthesis gas. Various techniques are employed to confirm the changes in the properties that affect the catalytic performance. The catalytic reaction is performed at a high gas hourly space velocity to screen the performance of the promoted CoCe catalysts. The CoCeZr catalyst shows the highest CO conversion (X_CO = 88% at 450 °C) due to its high Co dispersion and oxygen vacancy resulting from the addition of Zr to the CoCe catalyst; thus, it is most suitable for use in high temperature WGSR.     

Natural aloe vera derived Pt supported N-doped porous carbon: A highly durable cathode catalyst of PEM fuel cell

Evolution of highly durable electrocatalyst for oxygen reduction reaction (ORR) is the most critical barrier in commercializing polymer electrolyte membrane fuel cell (PEMFC). In this work, Pt deposited N-doped mesoporous carbon derived from Aloe Vera is developed as an efficient and robust electro catalyst for ORR. Due to its high mesoporous nature, the aloe vera derived carbon (AVC) play a very vital role in supporting Pt nanoparticles (NPs) with N-doping. After doping N into AVC, more defects are created which facilitates uniform distribution of Pt NPs leading to more active sites towards ORR. Pt/N-AVC shows excellent ORR activity when compared with commercial Pt/C and showing a half wave potential (E_1/2–0.87 V Vs. RHE) and reduction potential (E_red ~ 0.72 V Vs. RHE) towards ORR. Even after 30,000 potential cycles, Pt/N-AVC shows in its E_1/2 only ~5 mV negative shift and lesser agglomeration of Pt NPs is seen in the catalyst. In membrane electrode assembly (MEA) fabrication, Pt/N-AVC as a cathode catalyst in a PEMFC fixture and performance were studied. The Pt/N-AVC shows good performance, which proves the potential application of this naturally available bio derived carbon, which serves as an excellent high durable support material in PEMFC. All these features show that the Pt/N-AVC is the most stable, efficient and suitable candidate for ORR catalyst.     

Techno-economic feasibility of power to gas–oxy-fuel boiler hybrid system under uncertainty

One of the main challenges associated with utilisation of the renewable energy is the need for energy storage to handle its intermittent nature. Power-to-Gas (PtG) represents a promising option to foster the conversion of renewable electricity into energy carriers that may attend electrical, thermal, or mechanical needs on-demand. This work aimed to incorporate a stochastic approach (Artificial Neural Network combined with Monte Carlo simulations) into the thermodynamic and economic analysis of the PtG process hybridized with an oxy-fuel boiler (modelled in Aspen Plus^®). Such approach generated probability density curves for the key techno-economic performance indicators of the PtG process. Results showed that the mean utilisation of electricity from RES, accounting for the chemical energy in SNG and heat from methanators, reached 62.6%. Besides, the probability that the discounted cash flow is positive was estimated to be only 13.4%, under the set of conditions considered in the work. This work also showed that in order to make the mean net present value positive, subsidies of 68 €/MW_elh are required (with respect to the electricity consumed by PtG process from RES). This figure is similar to the financial aids received by other technologies in the current economic environment.     

Enhancing resistance of carbon deposition and reaction stability over nickel loaded fibrous silica-alumina (Ni/FSA) for dry reforming of methane

Syngas production from the dry reforming of methane is now the most extensively utilized method for removing massive amounts of greenhouse emissions. Effective solutions towards the utilization of greenhouse gases such as CO₂ and CH₄ are scarce, except for power generation in the energy sector, which is a major source of CO₂. Herein, dry reforming of methane was experimented for the first time using an effective catalytic system composed of 5% Ni fibrous silica-alumina (FSA) that was successfully fabricated using a hydrothermal method. The characterization results from XRD, FESEM mapping, TEM, BET,XRF, FTIR, H₂-TPR, TGA/DTA, and Raman spectra demonstrated that Ni/FSA is composed of orderly Ni dispersion, small particles of Ni, robust basic sites, and high oxygen vacancies which enhanced the catalytic efficiency. The synthesized Ni/FSA also reduced coke formation and had long-term stability with no evidence of inactivation during and after the catalytic cycles. The superior activity of Ni/FSA was manifested in the high conversion rates of CH₄ and CO₂ at 97% and 92% respectively, with a H₂:CO ratio of ≈ 1. The stability of Ni/FSA was also sustained over 30 h of operation at 800 °C. The findings of the Raman, TEM, and TGA/DTA tests revealed that the spent Ni/FSA catalysts did not exhibit graphitic carbon or metal sintering in significant amounts when compared to commercial Ni–Si/Al catalysts.     

Polyaniline@N-doped macroporous carbon foam as self-supporting anodes for microbial fuel cells

The inefficient extracellular electron transfer (EET) is detrimental to power generation and waste degradation in microbial fuel cells (MFCs). Herein, we report a self-supporting anode for MFCs prepared by graphitization of steamed bread slices followed by in-situ polymerization to fabricate polyaniline@N-doped macroporous carbon foam (PANI@NMCF). The natural nitrogen-containing wheat flour was fermented and carbonized to form NMCF with a high specific surface area of 818.1 m² g^?1. After the NMCF surface modified by PANI, the enhanced hydrophilicity and conductivity of the PANI@NMCF anode would facilitate microbial adhesion, biofilm formation, and electron transfer. The surface improvements enhance the EET process for high-performance MFCs, including a short startup time of 21.7 h, high maximum output power density of 1160 ± 17 mW m^?2, and decolourisation efficiency of 88.6 ± 1.2% for 36 h. The chemical oxygen demand removal efficiency was about 84.6 ± 1.1% at end of the operating cycles. This work provides a good foundation for our future development of carbon-based electrode materials for energy conversion and storage devices.     

Hydrofluoroolefin-based mixed refrigerant for enhanced performance of hydrogen liquefaction process

Hydrogen has the highest gravimetric energy density of all fuels; however, it has a low volumetric energy density, unfavorable for storage and transportation. Hydrogen is usually liquefied to meet the bulk transportation needs. The exothermic interconversion of its spin isomers is an additional activity to an already energy-intensive process. The most significant temperature drop occurs in the precooling cycle (between ?150 °C and up to ?180 °C) and consumes more than 50% of the required energy. To reduce the energy consumption and improve the exergy efficiency of the hydrogen liquefaction process, a new high-boiling component, Hydrofluoroolefin (HFO-1234yf), is added to the precooled mixed refrigerant. As a result, the specific energy consumption of precooling cycle reduces by 41.8%, from 10.15 kWh/kg_LH2 to 5.90 kWh/kg_LH2, for the overall process. The exergy efficiency of the proposed case increases by 43.7%; however, the total equipment cost is also the highest. The inflated cost is primarily due to the added ortho-to-para hydrogen conversion reactor, boosting the para-hydrogen concentration. From the perspective of bulk storage and transportation of liquid hydrogen, the simplicity of design and low energy consumption build a convincing case for considering the commercialization of the process.     

A remarkable increase in the adsorbed H2 amount: Influence of pore size distribution on the H2 adsorption capacity of Fe-BTC

Here we show the crucial role of ultramicropores on the adsorbed H₂ amount. By synthesizing Fe-BTCs via a perturbation assisted nanofusion synthesis strategy and by the control of textural porosity via Fe:BTC ratio, BET surface area (1312 m²/g), total pore volume (1.41 cm³/g), and H₂ adsorption capacity (1.10 wt% at 7.6 bar and 298 K) were enhanced by 1.6, 3.1, and 2.6 times, respectively. The reported BET surface area, and the total pore volume are the highest of those reported for Fe-BTC, to date. The enhanced H₂ adsorption capacity of Fe-BTC-3 is attributed to the ultramicropores present in its pore structure. Presence of ultramicropores maximizes van der Waals potential, and the adsorbed H₂ amount increases. By the perturbation assisted nanofusion synthesis strategy and the control over textural porosity, an Fe-BTC that possesses a H₂ adsorption capacity higher than those of reported MOFs with higher BET surface areas has been reported.     

Pd-decorated CNT as sensitive material for applications in hydrogen isotopes sensing - Application as gas sensor

Applicability of multiwall carbon nanotubes (MWCNTs) decorated with palladium nanoparticles as sensitive layer in a resistive microsensor for identification of hydrogen isotopes, Deuterium (²H) and Protium (¹H), has been demonstrated. Palladium nanoparticles were anchored on the MWCNTs surface via a chemical process involving micellization, from a precursor chloride solution, in high ultrasonic density field. Pd-MWCNTs are quasi-aligned between the interdigitated gold electrodes of a SiO₂ substrate by drop casting and di-electrophoretic alignment in Tetrahydrofuran (THF) and Nafion solution. The morphostructural characterization of the sensitive material has been carried out through SEM, TEM and Raman spectroscopy and its gas sensing properties were evaluated using electrical measurements performed on a series of isotope concentrations (ranging from 0.1% up to 1%, and from 1% to 4%, value to which hydrogen becomes explosive) diluted in argon, to observe the evolution of the sensor sensibility. The two hydrogen isotopes have different behaviors related to the adsorption on the Pd-MWCNT, which is well observed in the resistance change. Therefore, the sensor based on Pd-MWCNTs could be a viable solution to be integrated in systems for hydrogen leakage detection.     

Investigation of Ni-coated-steel-meshes as alternative anode contact material to nickel in an SOFC stack

Solid oxide fuel cell is a promising technology to convert renewable energy sources to electricity electrochemically at high efficiencies, thus an important applied research topic worldwide. The in-house developed so-called F-stack-design aims at stationary applications and can achieve a very long lifetime. However, since production costs should be reduced, one research focus lies on finding suitable less expensive materials. Therefore, alternatives for the benchmark Ni-mesh as anode contacting element in the stack were studied. Several types of Ni-coated-steels were tested in a stack. After 3000 h of operation the different anode contact materials are compared with the Ni-mesh in terms of microstructure as well as chemical composition. A discussion of the results is given.     

HRT control as a strategy to enhance continuous hydrogen production from sugarcane juice under mesophilic and thermophilic conditions in AFBRs

The objective of this study was to evaluate the effects of hydraulic retention time (HRT) (8–1 h) on H₂ production from sugarcane juice (5000 mg COD L⁻¹) in mesophilic (30 °C, AFBR-30) and thermophilic (55 °C, AFBR-55) anaerobic fluidized bed reactors (AFBRs). At HRTs of 8 and 1 h in AFBR-30, the H₂ production rates were 60 and 116 mL H₂ h⁻¹ L⁻¹, the hydrogen yields were 0.60 and 0.10 mol H₂ mol⁻¹ hexose, and the highest bacterial diversities were 2.47 and 2.34, respectively. In AFBR-55, the decrease in the HRT from 8 to 1 h increased the hydrogen production rate to 501 mL H₂ h⁻¹ L⁻¹ at the HRT of 1 h. The maximum hydrogen yield of 1.52 mol H₂ mol⁻¹ hexose was observed at the HRT of 2 h and was associated with the lowest bacterial diversity (0.92) and highest bacterial dominance (0.52).     

A new side-looking at the dark fermentation of sugarcane vinasse: Improving the carboxylates production in mesophilic EGSB by selection of the hydraulic retention time and substrate concentration

In recent years, a lot of scientific effort has been put into reusing the energy potential of sugarcane vinasse by dark fermentation. However, the findings so far indicate that new pathways need to be followed. In this context, this study assessed the effect of hydraulic retention time (HRT, from 24 to 1 h) on vinasse fermentation (10, 20, and 30 g COD L^?1) in three mesophilic expanded granular sludge bed reactors (EGSB). The carbohydrate conversion remained above 60% at all organic loading rates applied. The maximum hydrogen production rate (8.77 L day^?1 L^?1) was obtained for 720 kg COD m^?3 day^?1 and associated to the lactate-acetate pathway. The highest productivities of propionic, acetic, and butyric acids were 3.11, 1.68, and 2.45 g L^?1 h^?1, respectively, at a HRT of 1 h. At this HRT, the degrees of acidification remained between 54% and 76% in all EGSB reactors. This research provides insights for carboxylate production from sugarcane vinasse and suggests applying the EGSB setup in the acidogenic stage of two-stage processes.     

New cyanobacterial strains for biohydrogen production

Under certain conditions, cyanobacteria can switch from photosynthesis to hydrogen production, which is a good energy carrier. However, the biological diversity of hydrogen-releasing cyanobacteria has a great unexplored potential. This study is aimed to investigate the ability of new strains of cyanobacteria Cyanobacterium sp. IPPAS B-1200, Dolichospermum sp. IPPAS B-1213, and Sodalinema gerasimenkoae IPPAS B-353 to release H₂ and to evaluate the effects of photosystem II inhibitor 3-(3,4-dichlorphenyl)-1,1-dimethylurea (DCMU) on H₂ production under light and dark conditions. The results showed that cultures treated with DCMU produced several times more H₂ than untreated cells. The highest rate of H₂ photoproduction of 4.24 μmol H₂ (mg Chl a h)^?1 was found in a Dolichospermum sp. IPPAS B-1213 culture treated with 20 μM DCMU.     

Novel sonochemical synthesis of Zn2V2O7 nanostructures for electrochemical hydrogen storage

Although utilization of diverse classes of metal oxides as hydrogen storage materials has been reported, but there is still a major need to introduce efficient materials. Herein, mesoporous Zn₂V₂O₇ nanostructures were produced by a new sonochemical method using hydrazine, zinc nitrate, and ammonium vanadate as the starting reagents and then annealed at 700 °C. Prior to annealing, Zn₃V₃O₈ was produced in the presence of ultrasonic waves, whereas in the absence of ultrasonic waves, Zn₂(VO₄)₂ was the major product. In fact, ultrasonic waves interfered with the reaction mechanism and reduced V⁵⁺ to V⁴⁺ and V³⁺. Because of the proper composition and structure of these nanostructures, they were used for electrochemical storage of hydrogen. Storage of over 2899 mAh/g after 20 cycles by flower-like nanostructures revealed their high capability. The results also showed that morphology affects efficiency such that three-dimensional spherical nanostructures had a storage capacity of 2247 mAh/g after 20 cycles.