A novel three-step GeO2/GeO thermochemical water splitting cycle for solar hydrogen production

This investigation reports the thermodynamic exploration of a novel three-step GeO₂/GeO water splitting (WS) cycle. The thermodynamic computations were performed by using the data obtained from HSC Chemistry thermodynamic software. Numerous process parameters allied with the GeO₂/GeO WS cycle were estimated by drifting the thermal reduction ($T_H$) and water splitting temperature ($T_L$). The entire analysis was divided into two section: a) equilibrium analysis and b) efficiency analysis. The equilibrium analysis was useful to determine the $T_H$ and $T_L$ required for the initiation of the thermal reduction (TR) of GeO₂ and re-oxidation of GeO via WS reaction. Furthermore, the influence of $P_{O_2}$ on the $T_H$ required for the comprehensive dissociation of GeO₂ into GeO and O₂ was also studied. The efficiency analysis was conducted by drifting the $T_H$ and $T_L$ in the range of 2080 to 1280 K and 500–1000 K, respectively. Obtained results indicate that the minimum ${\dot{Q}}_{solar-cycle}=624.3\text{kW}$ and maximum ${\eta }_{solar-to-fuel}=45.7\text{\%}$ in case of the GeO₂/GeO WS cycle can be attained when the TR of GeO₂ was carried out at 1280 K and the WS reaction was performed at 1000 K. This ${\eta }_{solar-to-fuel}=45.7\text{\%}$ was observed to be higher than the SnO₂/SnO WS cycle (39.3%) and lower than the ZnO/Zn WS cycle (49.3%). The ${\dot{Q}}_{solar-cycle}$ can be further decreased to 463.9 kW and the ${\eta }_{solar-to-fuel}$ can be upsurged up to 61.5% by applying 50% heat recuperation.     

Solar hydrogen production via alkaline water electrolysis

Electricity generation via direct conversion of solar energy with zero carbon dioxide emission is essential from the aspect of energy supply security as well as from the aspect of environmental protection. Therefore, this paper presents a system for hydrogen production via water electrolysis using a 960 Wp solar power plant. The results obtained from the monitoring of photovoltaic modules mounted in pairs on a fixed, a single-axis and a dual-axis solar tracker were examined to determine if there is a possibility to couple them with an electrolyzer. Energy performance of each photovoltaic system was recorded and analyzed during a period of one year, and the data were monitored on an online software service. Estimated parameters, such as monthly solar irradiance, solar electricity production, optimal angle, monthly ambient temperature, and capacity factor were compared to the observed data. In order to get energy efficiency as high as possible, a novel alkaline electrolyzer of bipolar design was constructed. Its design and operating UI characteristic are described. The operating UI characteristics of photovoltaic modules were tuned to the electrolyzer operating UI characteristic to maximize production. The calculated hydrogen rate of production was 1.138 g per hour. During the study the system produced 1.234 MWh of energy, with calculated of 1.31 MWh , which could power 122 houses, and has offset 906 kg of carbon or an equivalent of 23 trees.     

Hydrogen production by a low-cost electrolyzer developed through the combination of alkaline water electrolysis and solar energy use

Electrolysis is a relatively simple process for obtaining hydrogen and can be combined with use of renewable energy sources, such as solar photovoltaic energy, for clean, sustainable gas production. This study designed a cylindrical electrolytic cell made of acrylic and 304 stainless steel electrodes to produce hydrogen. The electrolyte used was sodium hydroxide (NaOH 2–5 mol L^?1), and the direct current voltages applied were 2.0, 2.7, and 3.4 V. The maximum hydrogen production was achieved with 5.0 mol L^?1 NaOH and 3.4 V electric voltage. The system was connected to a photovoltaic panel of 20 W and exposed to solar radiation from 10 a.m. to 2 p.m. Approximately 2 L of hydrogen was produced within a period, and an average irradiance of 800.0 W m^?2 ± 60 W m^?2 was achieved. The system was stable throughout the tests.     

NiS2 Co-catalyst decoration on CdLa2S4 nanocrystals for efficient photocatalytic hydrogen generation under visible light irradiation

NiS₂ nanoparticles as noble metal-free co-catalysts were deposited onto the CdLa₂S₄ nanocrystals through a hydrothermal process. The loading of NiS₂ co-catalyst resulted in remarkable enhancement for H₂ production over the CdLa₂S₄ photocatalyst under visible light irradiation. The optimal hybrid photocatalyst with 2 wt% NiS₂ loading exhibited a H₂ production rate of 2.5 mmol h⁻¹ g⁻¹, which was more than 3 times higher than that of the pristine CdLa₂S₄ photocatalyst. The promoted photocatalytic H₂ production by NiS₂-loading is attributed to the enhanced separation of photogenerated electrons and holes as well as the activation effect of NiS₂ for H₂ evolution.     

Techno-economic analysis for clean hydrogen production using solar energy under varied climate conditions

The paper discusses the feasibility of the use solar energy into hydrogen production using a photovoltaic energy system in the four main cities of Iraq. An off-grid photovoltaic system with a capacity of 22.0 kWp, an 8.0 kW alkaline electrolyser, a hydrogen compressor, and a hydrogen tank were simulated for one year in order to generate hydrogen. A mathematical model of the proposed system behavior is presented using MATLAB/Simulink, considering nine years from the 2021 to 2030 project span using hourly experimental weather data. The outcomes demonstrated that the annual hydrogen production ranged from 1713.92 kg up to 1891.12 kg, oxygen production ranged from 1199.74 to 1323.78 kg, and water consumption ranged from 7139.91 L to 7877.29 L. The hydrogen evaluated costs equal to $3.79/kg. The results show that the optimum site for solar hydrogen production systems can be established in the midwest of Iraq and in other cities with similar climates, especially those that get a lot of sunlight.     

Energy and exergy analyses of hydrogen production via solar-boosted ocean thermal energy conversion and PEM electrolysis

Energy and exergy analyses are reported of hydrogen production via an ocean thermal energy conversion (OTEC) system coupled with a solar-enhanced proton exchange membrane (PEM) electrolyzer. This system is composed of a turbine, an evaporator, a condenser, a pump, a solar collector and a PEM electrolyzer. Electricity is generated in the turbine, which is used by the PEM electrolyzer to produce hydrogen. A simulation program using Matlab software is developed to model the PEM electrolyzer and OTEC system. The simulation model for the PEM electrolyzer used in this study is validated with experimental data from the literature. The amount of hydrogen produced, the exergy destruction of each component and the overall system, and the exergy efficiency of the system are calculated. To better understand the effect of various parameters on system performance, a parametric analysis is carried out. The energy and exergy efficiencies of the integrated OTEC system are 3.6% and 22.7% respectively, and the exergy efficiency of the PEM electrolyzer is about 56.5% while the amount of hydrogen produced by it is 1.2 kg/h.     

Efficient solar hydrogen production by photocatalytic water splitting: From fundamental study to pilot demonstration

Photocatalytic water splitting with solar light is one of the most promising technologies for solar hydrogen production. From a systematic point of view, whether it is photocatalyst and reaction system development or the reactor-related design, the essentials could be summarized as: photon transfer limitations and mass transfer limitations (in the case of liquid phase reactions). Optimization of these two issues are therefore given special attention throughout our study. In this review, the state of the art for the research of photocatalytic hydrogen production, both outcomes and challenges in this field, were briefly reviewed. Research progress of our lab, from fundamental study of photocatalyst preparation to reactor configuration and pilot level demonstration, were introduced, showing the complete process of our effort for this technology to be economic viable in the near future. Our systematic and continuous study in this field lead to the development of a Compound Parabolic Concentrator (CPC) based photocatalytic hydrogen production solar rector for the first time. We have demonstrated the feasibility for efficient photocatalytic hydrogen production under direct solar light. The exiting challenges and difficulties for this technology to proceed from successful laboratory photocatalysis set-up up to an industrially relevant scale are also proposed. These issues have been the object of our research and would also be the direction of our study in future.     

Hydrogen photoproduction from hydrogen sulfide on Bi2S3 catalyst

Films of polycrystalline Bi₂S₃ have been prepared onto bismuth and platinum substrates by electrodeposition from an aqueous sulfide bath. The films were thin, uniform and well adhered. Bi₂S₃ is a direct band gap semiconductor with a value of 1.28 eV optimally matched with the solar spectrum. The photoelectrochemical study was undertaken for the generation of hydrogen by using illuminated n-Bi₂S₃ particles; it was found that hydrogen evolution depends highly on the synthesis method of powder. Impregnation of platinum onto Bi₂S₃ shows a production enhancement of about 25%. The most active photocatalyst, prepared by a solvent thermal process and loaded with Pt in 0.1 M S²⁻ alkaline electrolyte, yields 2.13×10⁻² ml mg⁻¹ of H₂ after 4 h of irradiation with the visible output of a 500 W halogen lamp.     

Reactive ceramics of CeO2–MOx (M=Mn,Fe, Ni,Cu) for H2 generation by two-step water splitting using concentrated solar thermal energy

The addition of MO_x (M: di- or tri-valent transition metal ion) into cerium dioxide (CeO₂) enhanced the ability of CeO₂ for the oxygen (O₂)-releasing reaction at lower temperature and swift hydrogen (H₂)-generation reaction. CeO₂–MO_x (M=Mn, Fe, Ni, Cu) reactive ceramics having high melting points were synthesized with the combustion method from their nitrates for solar H₂ production. The prepared CeO₂–MO_x samples were solid solutions between CeO₂ and MO_x with the fluorite structure through the X-ray diffractometry measurement. Two-step water-splitting reactions with CeO₂–MO_x reactive ceramics proceeded at 1573–1773 K for the O₂-releasing step and at 1273 K for the H₂-generation step by irradiation of infrared image furnace as a solar simulator. The amounts of O₂ evolved in the O₂-releasing reaction with CeO₂–MO_x increased with an increase in the reaction temperature. The amounts of H₂ evolved in the H₂-generation reaction with CeO₂–MO_x systems except for M=Cu were more than that of CeO₂ system after the O₂-releasing reaction at the temperatures of 1673 and 1773 K. The amounts of H₂ evolved in the H₂-generation reaction with CeO₂–MnO and CeO₂–NiO systems were more than those of CeO₂–Fe₂O₃, CeO₂–CuO and CeO₂ systems after the O₂-releasing reaction at the temperature of 1573 K. The amounts of evolved H₂ after the O₂-releasing reaction at the temperature of 1773 K in cm³ per gram of CeO₂–MO_x were 0.975–3.77 cm³/g. The O₂-releasing reaction at 1673 K and H₂-generation reaction at 1273 K with CeO₂–Fe₂O₃ proceeded with repetition of 4 times stoichiometrically.     

Thermochemical two-step water splitting by ZrO2-supported NixFe3−xO4 for solar hydrogen production

A thermochemical two-step water-splitting cycle using a redox metal oxide was examined for Ni(II) ferrites or Ni_xFe_3−xO₄ (0  x  1) for the purpose of converting solar high-temperature heat to hydrogen. The Ni(II) ferrite was decomposed to Ni-doped wustite (Ni_yFe_1−yO) at 1400 °C under an inert atmosphere in the first thermal-reduction step of the cycle; it was then reoxidized with steam to generate hydrogen at 1000 °C in the second water-decomposition step. Although nondoped Fe₃O₄ powders formed a nonporous, dense mass of iron oxide by the fusion of FeO and its subsequent solidification after the thermal-reduction step, Ni(II)–ferrite powders were converted into a porous, soft mass after the step. This was probably because Ni doping in the FeO phase raised the melting point of wustite above 1400 °C. Supporting the Ni(II) ferrites on m-ZrO₂ (monoclinic zirconia) alleviated the high-temperature sintering of iron oxide; as a result, the supported ferrites exhibited greater reactivity and assisted the repeatability of the cyclic water splitting process as compared to the unsupported ferrites. The reactivity increased with the doping value x, and was maximum at x = 1.0 in the Ni_xFe_3−xO₄/m-ZrO₂ system.     

A technical and economical assessment of hydrogen production potential from solar energy in Morocco

In this study, a techno-economic analysis of the capacity of Morocco to produce hydrogen from solar energy has been conducted. For this reason, a Photovoltaic-electrolyze system was selected and the electricity and hydrogen production were simulated for 76 sites scattered all over the country. The Global Horizontal Irradiation (GHI) data used for the simulation were extracted from the CAMS-Rad satellite database and meteorological stations at ground level.Before simulations, the accuracy of the GHI values from the satellite dataset has been checked, and their uncertainties was calculated against accurate data measured in-situ. After that, the simulated values of the hydrogen mass were interpolated using a GIS software to create a Hydrogen production map of Morocco. Finally, an economical investigation of electricity and hydrogen production costs has been conducted by calculating the $LCOE$ and $LC{O}_{H_2}$.Results show that the satellite dataset has a mean average deviation of 6.8% which is a very acceptable error rang. Also, it was found that Morocco have a high potential for hydrogen production, with a daily annual production that varies between 6489 and 8308 Tons/km². Moreover, the cost of electricity and hydrogen production in the country are in the range of 0.077–0.099 $/kWh and 5.79–4.64 $/Kg respectively.The findings of this study are with high importance as they provide an overall perspective of the country potential of hydrogen production for policy makers and investors, and it was motivated by the lack of information on the subject in the literature since it's, at the best of our knowledge, the first study assessing the hydrogen production from solar for the whole country.     

Pristine and Se-/In-doped TlAsS2 enhance the solar energy-driven water splitting for hydrogen generation

The enhanced photocatalytic performance of Se-/In-doped TlAsS₂ to generate hydrogen from water splitting is investigated based on the first-principle density functional theory calculation with meta-GGA + TPSS. Three structures, namely, pristine TlAsS₂ and substitutions of S with Se and Tl with In, are considered. Their geometrical lattices are fully optimized and their electronic and optical properties are calculated to evaluate the photocatalytic efficiency for hydrogen generation. Results show that the three structures can be used for solar energy photocatalysis to generate hydrogen from water splitting. Moreover, the Se- and In-doped atoms can strengthen the absorption coefficient within the visible light range. Therefore, these structures are promising catalysts for generating hydrogen from water splitting through solar energy photocatalysis.     

Integrated fossil fuel and solar thermal systems for hydrogen production and CO2 mitigation

In most current fossil-based hydrogen production methods, the thermal energy required by the endothermic processes of hydrogen production cycles is supplied by the combustion of a portion of the same fossil fuel feedstock. This increases the fossil fuel consumption and greenhouse gas emissions. This paper analyzes the thermodynamics of several typical fossil fuel-based hydrogen production methods such as steam methane reforming, coal gasification, methane dissociation, and off-gas reforming, to quantify the potential savings of fossil fuels and CO₂ emissions associated with the thermal energy requirement. Then matching the heat quality and quantity by solar thermal energy for different processes is examined. It is concluded that steam generation and superheating by solar energy for the supply of gaseous reactants to the hydrogen production cycles is particularly attractive due to the engineering maturity and simplicity. It is also concluded that steam-methane reforming may have fewer engineering challenges because of its single-phase reaction, if the endothermic reaction enthalpy of syngas production step (CO and H₂) of coal gasification and steam methane reforming is provided by solar thermal energy. Various solar thermal energy based reactors are discussed for different types of production cycles as well.     

Photocatalytic water splitting for hydrogen production on Au/KTiNbO5

Gold nanoparticles were deposited on potassium titanoniobate, KTiNbO₅ using deposition-precipitation (DP), conventional impregnation (IMP) and photodeposition method in order to improve photocatalytic hydrogen production from water splitting. The effect of synthesis pH value of a HAuCl₄ aqueous solution used in the DP process on the morphology of gold nanoparticles, optical property and photocatalytic activity of water splitting under UV light irradiation was investigated. These catalysts were characterized by powder X-ray diffraction patterns (XRD), inductively coupled plasma mass spectrometry (ICP-MS), UV–visible spectroscopy (UV–vis), and Transmission Electron Microscopy (TEM). The Au/KTiNbO₅ catalysts prepared by the DP method consisted of a good metal–semiconductor interface which allowed for a much higher efficient electron-hole separation. The 0.63 wt% Au/KTiNbO₅ catalyst prepared by the DP method at pH = 10 showed a uniform dispersion of gold nanoparticles with an average gold particle size of 4.2 nm and exhibited an ultra-high photocatalytic water splitting activity (3522 μmol g⁻¹ h⁻¹), about 47 times higher than that exhibited by the KTiNbO₅ photocatalyst.     

CO2 and H2O reduction by solar thermochemical looping using SnO2/SnO redox reactions: Thermogravimetric analysis

The thermochemical dissociation of CO₂ and H₂O from reactive SnO nanopowders is studied via thermogravimetry analysis. SnO is first produced by solar thermal dissociation of SnO₂ using concentrated solar radiation as the high-temperature energy source. The process targets the production of CO and H₂ in separate reactions using SnO as the oxygen carrier and the syngas can be further processed to various synthetic liquid fuels. The global process thus converts and upgrades H₂O and captured CO₂ feedstock into solar chemical fuels from high-temperature solar heat only, since the intermediate oxide is not consumed but recycled in the overall process. The objective of the study was the kinetic characterization of the H₂O and CO₂ reduction reactions using reactive SnO nanopowders synthesized in a high-temperature solar chemical reactor. SnO conversion up to 88% was measured during H₂O reduction at 973 K and an activation energy of 51 ± 7 kJ/mol was identified in the temperature range of 798-923 K. Regarding CO₂ reduction, a higher temperature was required to reach similar SnO conversion (88% at 1073 K) and the activation energy was found to be 88 ± 7 kJ/mol in the range of 973-1173 K with a CO₂ reaction order of 0.96. The SnO conversion and the reaction rate were improved when increasing the temperature or the reacting gas mole fraction. Using active SnO nanopowders thus allowed for efficient and rapid fuel production kinetics from H₂O and CO₂.     

Photon-absorption-based explanation of ultrasonic-assisted solar photochemical splitting of water to improve hydrogen production

The ultrasonic-assisted solar photochemical splitting of water had been explored in recent years to enhance hydrogen production efficiency. In this study, a photon-absorption-based study was conducted to investigate the mechanism of the ultrasonic-assisted solar photochemical splitting of water. An elaborate test bench for temperature-controlled, ultrasonic-assisted solar photochemical water splitting was designed, set up, and tested. A comparison of the hydrogen production between the ultrasonic-assisted and conventional solar photochemical splitting of water was carried out. The effective nanoparticle size before and after ultrasonic vibration, as well as after solar photocatalysis, was analyzed. Furthermore, the spectral absorptivity of the nanofluids before and after ultrasonic vibration, as well as after solar photocatalysis, was investigated by both experimental and numerical methods. The investigation indicated that the improved particle dispersion in the solution prepared by ultrasonication allowed the absorbance of more incoming sunlight. The amount of hydrogen produced by the ultrasonic-assisted hydrogen production was 3.45 times that of conventional solar photochemical splitting of water without pre-ultrasonicated. Besides, an effective spectral absorptivity coefficient was proposed as a modified measure of spectral absorptivity. In addition, the optimal particle diameter was optimized using the Monte Carlo ray tracing method to identify the best light absorption performance.     

Evaluation and calculation on the efficiency of a water electrolysis system for hydrogen production

With the help of the typical model of a water electrolysis hydrogen production system, which mainly includes the electrolysis cell, separator, and heat exchangers, three expressions of the system efficiency in literature are compared and evaluated, from which one reasonable expression of the efficiency is chosen and directly used to analyze the performance of a water electrolysis hydrogen production system under different operation conditions. Several new configurations of a water electrolysis system are put forward and the problem how to calculate the efficiencies of these configurations is solved. Moreover, a solid oxide steam electrolyzer system (SOSES) for hydrogen production is taken as an example to expound that the different configurations of a water electrolysis system should be adopted for different operation conditions. The results obtained here may provide some guidance for the optimum design and operation of water electrolysis systems for hydrogen production.     

Thermochemical two-step water splitting by internally circulating fluidized bed of NiFe2O4 particles: Successive reaction of thermal-reduction and water-decomposition steps

Thermochemical two-step water splitting using a redox system of iron-based oxides or ferrites is a promising process for producing hydrogen without CO₂ emission by the use of high-temperature solar heat as an energy source and water as a chemical source. In this study, thermochemical hydrogen production by two-step water splitting was demonstrated on a laboratory scale by using a single reactor of an internally circulating fluidized bed. This involved the successive reactions of thermal-reduction (T-R) and water-decomposition (W-D). The internally circulating fluidized bed was exposed to simulated solar light from Xe lamps with an input power of 2.4-2.6 kW_th for the T-R step and 1.6-1.7 kW_th for the subsequent W-D step. The feed gas was switched from an inert gas (N₂) in the T-R step to a gas mixture of N₂ and steam in the W-D step. NiFe₂O₄/m-ZrO₂ and unsupported NiFe₂O₄ particles were tested as a fluidized bed of reacting particles, and the production rate and productivity of hydrogen and the reactivity of reacting particles were examined.