INTERNATIONAL JOURNAL OF HYDROGEN ENERGY

Multilayered TiCT MXene as a highly active electrocatalyst for hydrogen evolution reaction
Ragunath BS, Krishnaveni BS, Chinnathambi K, Natarajan V, Devaraj S and Sathya A
Two dimensional materials as electrocatalysts for hydrogen evolution reaction (HER) have recently gained significant interest. Here, we report the HER activity of multilayered MXene ( ) synthesized via hydrogen fluoride etching of the MAX phase. The layered morphology and the presence of both -O, -F based surface termination groups of the MXene resulted in a better HER activity with a low overpotential of 147 mV at a current density of 10 mA cm with a steeper Tafel slope of 80 mV dec. Interestingly, showed a two-fold increase in the HER activity under continuous operation (50 hr, 5,000 cycles) when compared with Pt/C, suggesting good stability and durability in hydrogen production at a high rate in an acidic medium.
Novel strategy in biohydrogen energy production from COVID - 19 plastic waste: A critical review
Dharmaraj S, Ashokkumar V, Chew KW, Chia SR, Show PL and Ngamcharussrivichai C
Usage of plastics in the form of personal protective equipment, medical devices, and common packages has increased alarmingly during these pandemic times. Though they have served as an excellent protection source in minimizing the coronavirus disease (COVID-19) spreading, they have still emerged as major environmental pollutants nowadays. These non-degradable COVID-19 plastic wastes (CPW) were treated through incineration and landfilling process, which may lead to either the release of harmful gases or contaminating the surrounding environment. Further, they can cause numerous health hazards to the human and animal populations. These plastic wastes can be efficiently managed through thermochemical processes like pyrolysis or gasification, which assist in degrading the plastic waste and also effectively convert them into useful energy-yielding products. The pyrolysis process promotes the formation of liquid fuels and chemicals, whereas gasification leads to syngas and hydrogen fuel production. These energy-yielding products can help to compensate for the fossil fuels depletion in the near future. There are many insights explained in terms of the types of reactors and influential factors that can be adopted for the pyrolysis and gasification process, to produce high efficient energy products from the wastes. In addition, advanced technologies including co-gasification and two-stage gasification were also reviewed.
Special issue for the XXI International Meeting of the Mexican Hydrogen Society
Ramos-Sánchez G and González-Huerta RG
Simultaneous synthesis of H, O, and N via an innovatory energy system in Coronavirus pandemic time: Design, techno-economic assessment, and optimization approaches
Wei H, Dai J, Maharik I, Ghasemi A, Mouldi A and Brahmia A
In this work, an innovative integrated system that is incorporated from solid oxide electrolysis cells and an oxygen separator membrane is assessed and optimized from the techno-economic aspects to respond to oxygen, hydrogen, and nitrogen demands for hospitals and other health care applications. Besides, a parametric comparison is conducted to apprehend the weights of parameters changes on the performance of criteria. Relying on the assessments, from the hydrogen production of 1 kg/s, 23.19 kg/s of oxygen, and 50.22 kg/s of nitrogen are produced. The parametric study shows that by raising the working temperature of the electrolyzer, the cell voltage variation has descending trend and the power consumption of the system is decreased by 19%. Finally, the results of multi-criteria optimization on the Pareto front reveal that in the optimal case, the system payback period is attained at about 5.32 years and the exergy efficiency of 92.47%, which are improved 16.6% and 16.2% compared to the base case, sequentially. Consequently, this system is proposed to consider as a cost-effective and reliable option towards its vital and valuable productions, in the pandemic period and after's.
The use of ultrapure molecular hydrogen enriched with atomic hydrogen in apparatuses of artificial lung ventilation in the fight against virus COVID-19
Zolotarenko AD, Zolotarenko AD, Veziroglu A, Veziroglu TN, Shvachko NA, Pomytkin AP, Gavrylyuk NA, Schur DV, Ramazanov TS and Gabdullin MT
COVID-19 is a disease caused by the SARS-CoV virus. It stands for severe acute respiratory syndrome, which affects the lungs. The process of replication and progression of the COVID-19 virus causes the formation of an excessive amount of reactive oxygen species and inflammation. Many studies have been carried out that have demonstrated that hydrogen has strong anti-inflammatory properties. It reduces hypotension and other symptoms by reducing inflammation and oxidative stress. Oxygen mixture, enriched with Hydrogen, - helps to reduce the resistance of the respiratory tract and frees up access to the pulmonary alveolus, which improves the penetration of oxygen into the lungs. Since hydrogen is an antioxidant, it helps to reduce the burden on the immune system, helps to maintain the body's health and its ability to quickly recover. When electrolysers are used to produce an oxygen-hydrogen mixture, alkaline mist and other impurities can enter the patient's lungs and cause poisoning and chemical burns. For this reason, the use of atomic hydrogen obtained from metal hydride sources for ventilation of the lungs will be more effective for treating COVID-19 than a molecular hydrogen-oxygen mixture from an electrolyzer. A functional diagram of a metal hydride source of atomic hydrogen to an artificial lung ventilator is shown. It is possible to create a series of hydrogen storage tanks of various capacities.
Development and performance assessment of new solar and fuel cell-powered oxygen generators and ventilators for COVID-19 patients
Siddiqui O, Ishaq H and Dincer I
In this study, a new solar-based fuel cell-powered oxygenation and ventilation system is presented for COVID-19 patients. Solar energy is utilized to operate the developed system through photovoltaic panels. The method of water splitting is utilized to generate the required oxygen through the operation of a proton exchange membrane water electrolyser. Moreover, the hydrogen produced during water splitting is utilized as fuel to operate the fuel cell system during low solar availability or the absence of solar irradiation. Transient simulations and thermodynamic analyses of the developed system are performed by accounting for the changes in solar radiation intensities during the year. The daily oxygen generation is found to vary between 170.4 kg/day and 614.2 kg/day during the year. Furthermore, the amount of daily hydrogen production varies between 21.3 kg/day and 76.8 kg/day. The peak oxygen generation rate attains a value of 18.6 g/s. Moreover, the water electrolysis subsystem entails daily exergy destruction in the range of 139.9-529.7 kWh. The maximum efficiencies of the developed system are found to be 14.3% energetically and 13.4% exergetically.
Effect of simple interventions on the performance of a miniature MFC fed with fresh urine
Tremouli A, Greenman J and Ieropoulos I
The aim of the present study is to enhance the performance of a microbial fuel cell (MFC) design by making simple interventions. Specifically, terracotta "t" and mullite "m" ceramics are tested as membranes while carbon veil and carbon cloth are used as electrodes. In the case of "m" cylinders different dimensions are examined (m: ID 30 mm x height 11.5 mm; sm: ID 18 mm x height 18 mm). The units operated continuously with urine as the feedstock. The best performing is the sm type (60-100 μW), followed by the t type (40-80 μW) and the m type (20-40 μW). Polarisation experiments indicated that activated carbon on the anode enhances the power output (t: 423 μW, sm: 288 μW). Similarly, the increase of the surface area and the addition of stainless steel mesh on the cathode improves the power performance for the "sm" and the "t" units. Furthermore, it is shown that the design with the smaller internal diameter, performs better and is more stable through time.
Plasma gasification of the medical waste
Erdogan AA and Yilmazoglu MZ
In terms of infection control in hospitals, especially the Covid-19 pandemic that we are living in, it has revealed the necessity of proper disposal of medical waste. The increasing amount of medical waste with the pandemic is straining the capacity of incineration facilities or storage areas. Converting this waste to energy with gasification technologies instead of incineration is also important for sustainability. This study investigates the gasification characteristics of the medical waste in a novel updraft plasma gasifier with numerical simulations in the presence of the plasma reactions. Three different medical waste samples, chosen according to the carbon content and five different equivalence ratios (ER) ranging from 0.1 to 0.5 are considered in the simulations to compare the effects of different chemical compositions and waste feeding rates on hydrogen (H) content and syngas production. The outlet properties of a 10 kW microwave air plasma generator are used to define the plasma inlet in the numerical model and the air flow rate is held constant for all cases. Results showed that the maximum H production can be obtained with ER = 0.1 for all waste samples.
Significantly enhanced electrocatalytic activity of copper for hydrogen evolution reaction through femtosecond laser blackening
Li Z, Jalil SA, Singh SC, Li W, Wei X and Guo C
In this work, we report on the creation of a black copper via femtosecond laser processing and its application as a novel electrode material. We show that the black copper exhibits an excellent electrocatalytic activity for hydrogen evolution reaction (HER) in alkaline solution. The laser processing results in a unique microstructure: microparticles covered by finer nanoparticles on top. Electrochemical measurements demonstrate that the kinetics of the HER is significantly accelerated after bare copper is treated and turned black. At -0.325 V (v.s. RHE) in 1 M KOH aqueous solution, the calculated area-specific charge transfer resistance of the electrode decreases sharply from 159 Ω cm for the untreated copper to 1 Ω cm for the black copper. The electrochemical surface area of the black copper is measured to be only 2.4 times that of the untreated copper and therefore, the significantly enhanced electrocatalytic activity of the black copper for HER is mostly a result of its unique microstructure that favors the formation and enrichment of protons on the surface of copper. This work provides a new strategy for developing high-efficient electrodes for hydrogen generation.
Effect of silica-core gold-shell nanoparticles on the kinetics of biohydrogen production and pollutant hydrogenation via organic acid photofermentation over enhanced near-infrared illumination
Ji Y, Sultan MA, Kim DY, Meeks N, Hastings JT and Bhattacharyya D
A biological photoinduced fermentation process provides an alternative to traditional hydrogen productions. In this study, biohydrogen production was investigated at near IR region coupled to a near-field enhancement by silica-core gold-shell nanoparticles (NPs) over a range of acetate concentrations (5-40 mM) and light intensities (11-160 W/m). The kinetic data were modeled using modified Monod equations containing light intensity effects. The yields of H and CO produced per acetate were determined as 2.31 mol-H/mol-Ac and 0.83 mol-CO/mol-Ac and increased to 4.38 mmol-H/mmol-Ma and 2.62 mmol-CO/mmol-Ma when malate was used. Maximum increases in H and CO productions by 115% and 113% were observed by adding NPs without affecting the bacterial growth rates (6.1-8.2 mg-DCM/L/hour) while the highest hydrogen production rate was determined as 0.81 mmol/L/hour. Model simulations showed that the energy conversion efficiency increased with NPs concentration but decreased with the intensity. Complete hydrogenation application was demonstrated with toxic 2-chlorobiphenyl using Pd catalysts.
The adherence-associated Fdp fasciclin I domain protein of the biohydrogen producer is regulated by the global Prr pathway
Jeong EL, Broad SJ, Moody RG and Phillips-Jones MK
Expression of encoding a fasciclin I domain protein important for adherence in the hydrogen-producing bacterium was investigated under a range of conditions to gain insights into optimization of adherence for immobilization strategies suitable for H production. The promoter was linked to a reporter and expressed in wild type and in PRRB and PRRA mutant strains of the Prr regulatory pathway. Expression was significantly negatively regulated by Prr under all conditions of aerobiosis tested including anaerobic conditions (required for H production), and aerobically regardless of growth phase, growth medium complexity or composition, carbon source, heat and cold shock and dark/light conditions. Negative regulation by Prr was reflected in cellular levels of translated Fdp protein. Since Prr is required directly for nitrogenase expression, we propose optimization of Fdp-based adherence in for immobilized biohydrogen production by inactivation of the PrrA binding site(s) upstream of .
Is the H economy realizable in the foreseeable future? Part III: H usage technologies, applications, and challenges and opportunities
Nazir H, Muthuswamy N, Louis C, Jose S, Prakash J, Buan MEM, Flox C, Chavan S, Shi X, Kauranen P, Kallio T, Maia G, Tammeveski K, Lymperopoulos N, Carcadea E, Veziroglu E, Iranzo A and M Kannan A
Energy enthusiasts in developed countries explore sustainable and efficient pathways for accomplishing zero carbon footprint through the H economy. The major objective of the H economy review series is to bring out the status, major issues, and opportunities associated with the key components such as H production, storage, transportation, distribution, and applications in various energy sectors. Specifically, Part I discussed H production methods including the futuristic ones such as photoelectrochemical for small, medium, and large-scale applications, while Part II dealt with the challenges and developments in H storage, transportation, and distribution with national and international initiatives. Part III of the H economy review discusses the developments and challenges in the areas of H application in chemical/metallurgical industries, combustion, and fuel cells. Currently, the majority of H is being utilized by a few chemical industries with >60% in the oil refineries sector, by producing grey H by steam methane reforming on a large scale. In addition, the review also presents the challenges in various technologies for establishing greener and sustainable H society.
Scaling up self-stratifying supercapacitive microbial fuel cell
Walter XA, Santoro C, Greenman J and Ieropoulos I
Self-stratifying microbial fuel cells with three different electrodes sizes and volumes were operated in supercapacitive mode. As the electrodes size increased, the equivalent series resistance decreased, and the overall power was enhanced (small: ESR = 7.2 Ω and P  = 13 mW; large: ESR = 4.2 Ω and P  = 22 mW). Power density referred to cathode geometric surface area and displacement volume of the electrolyte in the reactors. With regards to the electrode wet surface area, the large size electrodes (L-MFC) displayed the lowest power density (460 μW cm) whilst the small and medium size electrodes (S-MFC, M-MFC) showed higher densities (668 μW cm and 633 μW cm, respectively). With regard to the volumetric power densities the S-MFC, the M-MFC and the L-MFC had similar values (264 μW mL, 265 μW mL and 249 μW cm, respectively). Power density normalised in terms of carbon weight utilised for fabricating MFC cathodes-electrodes showed high output for smaller electrode size MFC (5811 μW g-C- and 3270 μW g-C- for the S-MFC and L-MFC, respectively) due to the fact that electrodes were optimised for MFC operations and not supercapacitive discharges. Apparent capacitance was high at lower current pulses suggesting high faradaic contribution. The electrostatic contribution detected at high current pulses was quite low. The results obtained give rise to important possibilities of performance improvements by optimising the device design and the electrode fabrication.
A solution to renewable hydrogen economy for fuel cell buses - A case study for Zhangjiakou in North China
Zhang G, Zhang J and Xie T
Fuel cell vehicles fueled with renewable hydrogen is recognized as a life-cycle carbon-free option for the transport sector, however, the profitability of the H pathway becomes a key issue for the FCV commercialization. By analyzing the actual data from the Zhangjiakou fuel cell transit bus project, this research reveals it is economically feasible to commercialize FCV in areas with abundant renewable resources. Low electricity for water electrolysis, localization of H supply, and curtailed end price of H refueling effectively reduce the hydrogen production, delivery and refueling cost, and render a chance for the profitability of refueling stations. After the fulfillment of the intense deployment of both vehicles and hydrogen stations for the 2022 Winter Olympics, the H pathway starts to make a profit thereafter. The practices in the Zhangjiakou FCB project offer a solution to the hydrogen economy, which helps to break the chicken-egg dilemma of vehicles and hydrogen infrastructure.
Response of ceramic microbial fuel cells to direct anodic airflow and novel hydrogel cathodes
Winfield J, Greenman J and Ieropoulos I
The presence of air in the anode chamber of microbial fuel cells (MFCs) might be unavoidable in some applications. This study purposely exposed the anodic biofilm to air for sustained cycles using ceramic cylindrical MFCs. A method for improving oxygen uptake at the cathode by utilising hydrogel was also trialled. MFCs only dropped by 2 mV in response to the influx of air. At higher air-flow rates (up to 1.1 L/h) after 43-45 h, power did eventually decrease because chemical oxygen demand (COD) was being consumed (up to 96% reduction), but recovered immediately with fresh feedstock, highlighting no permanent damage to the biofilm. Two months after the application of hydrogel to the cathode chamber, MFC power increased 182%, due to better contact between cathode and ceramic surface. The results suggest a novel way of improving MFC performance using hydrogels, and demonstrates the robustness of the electro-active biofilm both during and following exposure to air.
Self-stratifying microbial fuel cell: The importance of the cathode electrode immersion height
Walter XA, Santoro C, Greenman J and Ieropoulos I
Power generation of bioelectrochemical systems (BESs) is a very important electrochemical parameter to consider particularly when the output has to be harvested for practical applications. This work studies the effect of cathode immersion on the performance of a self-stratified membraneless microbial fuel cell (SSM-MFC) fuelled with human urine. Four different electrolyte immersion heights, i.e. , , and fully submerged were considered. The SSM-MFC performance improved with increased immersion up to . The output dropped drastically when the cathode was fully submerged with the conditions becoming fully anaerobic. SSM-MFC with submerged cathode had a maximum power output of 3.0 mW followed by 2.4 mW, 2.0 mW, and 0.2 mW for the , and fully submerged conditions. Durability tests were run on the best performing SSM-MFC with cathode immersed and showed an additional increase in the electrochemical output by 17% from 3.0 mW to 3.5 mW. The analysis performed on the anode and cathode separately demonstrated the stability in the cathode behaviour and in parallel an improvement in the anodic performance during one month of investigation.
Carbon-coated cobalt molybdenum oxide as a high-performance electrocatalyst for hydrogen evolution reaction
Xu N, Cao G, Gan L, Chen Z, Zang M, Wu H and Wang P
Synthesis of high-performance and cost-effective catalysts towards the hydrogen evolution reaction (HER) is critical in developing electrochemical water-splitting as a viable energy conversion technique. For non-precious metal Co- and Ni-based catalysts, hydroxides were found to form on the surface of the catalysts under alkaline environments and benefit the catalytic performance, whereas there is limited systematic study on the explicit influence of hydroxides on the electrocatalytic mechanism and performance of these catalysts. Herein, we report a close correlation observed between the amount of the surface hydroxides formed and the resulting electrocatalytic performance of a Co-Mo-O nanocatalyst through careful comprehensive structural and property characterizations. We found that an appropriate amount of hydroxide can be moderated by simply coating the catalyst surface with carbon shells to optimize the catalytic properties. As a result, a carbon-coated Co-Mo-O nanocatalyst was successfully developed and is among the best reported non-precious HER catalysts with a superior electrocatalytic activity and outstanding durability for the HER under alkaline environment. First-principles calculations were further conducted to probe the nature of the active sites and the role of hydroxides in the Co-Mo-O@C/NF catalyst towards the HER.
Electricity and catholyte production from ceramic MFCs treating urine
Merino Jimenez I, Greenman J and Ieropoulos I
The use of ceramics as low cost membrane materials for Microbial Fuel Cells (MFCs) has gained increasing interest, due to improved performance levels in terms of power and catholyte production. The catholyte production in ceramic MFCs can be attributed to a combination of water or hydrogen peroxide formation from the oxygen reduction reaction in the cathode, water diffusion and electroosmotic drag through the ion exchange membrane. This study aims to evaluate, for the first time, the effect of ceramic wall/membrane thickness, in terms of power, as well as catholyte production from MFCs using urine as a feedstock. Cylindrical MFCs were assembled with fine fire clay of different thicknesses (2.5, 5 and 10 mm) as structural and membrane materials. The power generated increased when the membrane thickness decreased, reaching 2.1 ± 0.19 mW per single MFC (2.5 mm), which was 50% higher than that from the MFCs with the thickest membrane (10 mm). The amount of catholyte collected also decreased with the wall thickness, whereas the pH increased. Evidence shows that the catholyte composition varies with the wall thickness of the ceramic membrane. The possibility of producing different quality of catholyte from urine opens a new field of study in water reuse and resource recovery for practical implementation.
Elimination of Rubisco alters the regulation of nitrogenase activity and increases hydrogen production in Rhodospirillum rubrum
Wang D, Zhang Y, Welch E, Li J and Roberts GP
Nitrogenase not only reduces atmospheric nitrogen to ammonia, but also reduces protons to hydrogen (H(2)). The nitrogenase system is the primary means of H(2) production under photosynthetic and nitrogen-limiting conditions in many photosynthetic bacteria, including Rhodospirillum rubrum. The efficiency of this biological H(2) production largely depends on the nitrogenase enzyme and the availability of ATP and electrons in the cell. Previous studies showed that blockage of the CO(2) fixation pathway in R. rubrum induced nitrogenase activity even in the presence of ammonium, presumably to remove excess reductant in the cell. We report here the re-characterization of cbbM mutants in R. rubrum to study the effect of Rubisco on H(2) production. Our newly constructed cbbM mutants grew poorly in malate medium under anaerobic conditions. However, the introduction of constitutively active NifA (NifA*), the transcriptional activator of the nitrogen fixation (nif) genes, allows cbbM mutants to dissipate the excess reductant through the nitrogenase system and improves their growth. Interestingly, we found that the deletion of cbbM alters the posttranslational regulation of nitrogenase activity, resulting in partially active nitrogenase in the presence of ammonium. The combination of mutations in nifA, draT and cbbM greatly increased H(2) production of R. rubrum, especially in the presence of excess of ammonium. Furthermore, these mutants are able to produce H(2) over a much longer time frame than the wild type, increasing the potential of these recombinant strains for the biological production of H(2).
Space-based bacterial production of hydrogen
Tennakoon CL, Bhardwaj RC and Bockris JO
This paper deals with the electrochemical production of hydrogen by depolarizing the oxygen evolution reaction using human feces and urine, which contains 30-40% bacteria and yeast. The electroactivity of graphite, tungsten carbide, perovskite and RuO2-coated Ebonex (Ti4O7) as anode materials are compared. The scale-up of the process in a laboratory-scale three-dimensional packed bed cell is discussed.
Sustainable application of pecan nutshell waste: Greener synthesis of Pd-based nanocatalysts for electro-oxidation of methanol
Hidalgo AIC, Aguirre MR, Valenzuela E, Gomez JYV, Dávila AC, Varma RS and Sánchez VHR
Palladium-based electrocatalysts are widely used in alkaline direct alcohol fuel cells. The synthesis and characterization of carbon-supported bimetallic nanoparticles (NP) of AuPd and AgPd is described using pecan nutshell extract () which serves as both, reducing and the stabilizing agent. This environmentally friendly route generates bimetallic NP for a wide range of applications, including electrocatalysis; since particularly AuPd NP proved to be a potentially suitable electrode material for alkaline direct methanol fuel cells. The electrocatalytic activity of these nanomaterials was comparable to commercially available Pd/C 1% in the electro-oxidation of methanol in alkaline media.