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 by two-step thermochemical cycles: Evaluation of the activity of commercial ferrites

In this work, we report on the evaluation of the activity of commercially available ferrites with different compositions, NiFe₂O₄, Ni_0.5Zn_0.5Fe₂O₄, ZnFe₂O₄, Cu_0.5Zn_0.5Fe₂O₄ and CuFe₂O₄, for hydrogen production by two-step thermochemical cycles, as a preliminary study for solar energy driven water splitting processes. The samples were acquired from Sigma–Aldrich, and are mainly composed of a spinel crystalline phase. The net hydrogen production after the first reduction–oxidation cycle decreases in the order NiFe₂O₄ > Ni_0.5Zn_0.5Fe₂O₄ > ZnFe₂O₄ > Cu_0.5Zn_0.5Fe₂O₄ > CuFe₂O₄, and so does the H₂/O₂ molar ratio, which is regarded as an indicator of potential cyclability. Considering these results, the nickel ferrite has been selected for longer term studies of thermochemical cycles. The results of four cycles with this ferrite show that the H₂/O₂ molar ratio of every two steps increases with the number of cycles, being the total amount stoichiometric regarding the water splitting reaction. The possible use of this nickel ferrite as a standard material for the comparison of results is proposed.     

A comparative thermodynamic analysis of samarium and erbium oxide based solar thermochemical water splitting cycles

This paper reports a thermodynamic comparison between the samarium and erbium oxide based solar thermochemical water splitting cycles. These cycles are a two-step process in which the metal oxide is first thermally reduced into the pure metal, and the produced metal can be used to split water to produce H₂. The metal oxides can be reused for multiple cycles without consumption. The effect of water splitting temperature on various thermodynamic parameters which are essential to design the solar reactor system for the production of H₂ via water splitting reaction using the samarium and erbium oxides is studied in detail. The total amount of solar energy needed for the thermal reduction of samarium and erbium oxides is estimated. The amount of heat energy released by the water splitting reactor is calculated. Also, the cycle and solar-to-fuel energy conversion efficiency for both cycles are determined by employing heat recuperation. Obtained results indicate that the efficiencies associated with these cycles are comparable to the previously studies thermochemical cycles. It is observed that higher water splitting temperature favors towards higher efficiencies. At constant thermal reduction temperature = 2280 K, by employing 50% heat recuperation, the solar-to-fuel energy conversion efficiency for the samarium cycle (30.98%) is observed to be higher than erbium cycle (28.19%).     

A review on integrated thermochemical hydrogen production from water

Hydrogen production from water splitting is considered one of the most environmentally friendly processes for replacing fossil fuels. Among the various technologies to produce hydrogen from water splitting, thermochemical cycles using chemical reagents have the advantage of scale up compared to other specific facilities or geological conditions required. According to thermochemical processes using chemical redox reactions, 2-, 3-, 4-step thermochemical water splitting cycles can generate hydrogen more efficiently due to reducing temperatures. Increasing the number of cycles or steps of thermochemical hydrogen production could reduce the required maximum temperature of the facility. In addition, recently developed hybrid thermochemical processes combined with electricity or solar energy have been studied on a large scale because of the reduced cost of hydrogen production. Additionally, hybrid thermochemical water splitting combined with renewable energy can result in not only reducing the cost, but also increasing hydrogen production efficiency in terms of energy. As for a green energy, hydrogen production from water splitting using sustainable and renewable energy is significant to protect biological environment and human health. Additionally, hybrid thermochemical water splitting is conducive to large scale hydrogen production. This paper reviews the multi-step and highly developed hybrid thermochemical technologies to produce hydrogen from water splitting based on recently published literature to understand current research achievements.     

Comparative study of the activity of nickel ferrites for solar hydrogen production by two-step thermochemical cycles

In this work, we compare the activity of unsupported and monoclinic zirconia – supported nickel ferrites, calcined at two different temperatures, for solar hydrogen production by two-step water-splitting thermochemical cycles at low thermal reduction temperature. Commercial nickel ferrite, both as-received and calcined in the laboratory, as well as laboratory made supported NiFe₂O₄, are employed for this purpose. The samples leading to higher hydrogen yields, averaged over three cycles, are those calcined at 700 °C in each group (supported and unsupported) of materials. The comparison of the two groups shows that higher chemical yields are obtained with the supported ferrites due to better utilisation of the active material. Therefore, the highest activity is obtained with ZrO₂-supported NiFe₂O₄ calcined at 700 °C.     

Solar thermochemical ZnO/ZnSO4 water splitting cycle for hydrogen production

In this paper, solar reactor efficiency analysis of the solar thermochemical two-step zinc oxide–zinc sulfate (ZnO–ZnSO₄) water splitting cycle. In step-1, the ZnSO₄ is thermally decomposed into ZnO, SO₂, and O₂ using solar energy input. In step-2, the ZnO is re-oxidized into ZnSO₄ via water splitting reaction producing H₂. The ZnSO₄ is recycled back to the solar reactor and hence can be re-used in multiple cycles. The equilibrium compositions associated with the thermal reduction and water-splitting steps are identified by performing HSC simulations. The effect of Ar towards decreasing the required thermal reduction temperature is also explored. The total solar energy input and the re-radiation losses from the ZnO–ZnSO₄ water splitting cycle are estimated. Likewise, the amount of heat energy released by different coolers and water splitting reactor is also determined. Thermodynamic calculations indicate that the cycle (η_cycle) and solar-to-fuel energy conversion efficiency (η_{solar-to-fuel}) of the ZnO–ZnSO₄ water splitting cycle are equal to 40.6% and 48.9% (without heat recuperation). These efficiency values are higher than previously investigated thermochemical water splitting cycles and can be increased further by employing heat recuperation.     

Analysis of the yield and production cost of large-scale electrolytic hydrogen from different solar technologies and under several Moroccan climate zones

The objective of this paper is to conduct an analysis of the green hydrogen production by the mean of water electrolysis from different solar energy systems and under different climate conditions in Morocco. To this end, simulation of four solar power plants configurations -with a nominal capacity of 100 MW_e from different technologies (fixed PV, 1 axis tracking PV, 2 axis tracking PV, and Stirling Dish) coupled with a PEM electrolyzer has been done. For the sake of precision, 3 years average of high quality meteorological data measured in-situ and at 5 different locations were used as simulation inputs. To have an idea about the potential of Morocco in the green hydrogen production market, we benchmarked the simulation results against the ones from Almeria, Spain and Stellenbosch, South Africa. Results show that for almost all sites, the 1 axis tracking PV system is the optimal technology -from techno-economic aspect-for green Hydrogen production in Morocco, even though the 2 axis tracking PV systems can generate the highest amounts of hydrogen (~4500 Tons/year), the fixed PV has the lowest LCOH₂ (5.8 $/Kg) and the Stirling Dish is the most efficient one (~12%). Besides, Morocco can be considered as a very competitive country for green hydrogen production (especially for PV technology) with an LCO_H2 of 5.57 $/Kg, against 5,96$/Kg in Southern Spain and 6,51$/Kg for south Africa.     

Two-step thermochemical electrolysis: An approach for green hydrogen production

Electrolysis and thermochemical water splitting are approaches to produce green hydrogen that use either an electrical potential (electrolysis) or a chemical potential (thermochemical water splitting) to split water. Electrolysis is technologically mature when applied at low temperatures, but it requires large quantities of electrical energy. In contrast to electrolysis, thermochemical water splitting uses thermal energy, as thermal energy can typically be supplied at a lower unit cost than electrical energy using concentrating solar power. Thermochemical water splitting, however, typically suffers from high thermal losses at the extremely high process temperatures required, substantially increasing the total energy required. We show how, by combining electrical and chemical potentials, a novel and cost-efficient water splitting process can be envisioned that overcomes some of the challenges faced by conventional electrolysis and thermochemical water splitting. It uses a mixed ionic and electronic conducting perovskite with temperature-dependent oxygen non-stoichiometry as an anode in an electrolyzer. If solar energy is used as the primary source of all energy required in the process, the cost of the energy required to produce hydrogen could be lower than in high-temperature electrolysis by up to 7%.     

A review on solar energy-based indirect water-splitting methods for hydrogen generation

The distinguish generation methods regarding hydrogen generation using solar energy as a triggering agent are discussed in this paper, specifically indirect techniques. Two broadly classified processes are direct and indirect. The Direct processes exhibit high thermal efficiency, but their low conversion efficiency, maximum heat dissipation, and the lack of readily available heat resistive materials in abundance put the indirect processes relatively on the higher rank. The indirect methods include bio photolysis, thermochemical, photolysis, and electrolysis. There are promising features of indirect ways. Bio-photolysis provides zero pollution; the photolysis method reduces the carbon footprint in the environment; Thermochemical is meritorious in low electricity consumption due to high heat generation in the process; Electrolysis proves its worth in negligible pollution and considerable efficiency. The energy and exergy efficiency for hydrogen yielding are compared, and it is found that electrolysis has the highest energy and exergy efficiency. In terms of raw material availability, thermochemical ranks very low as compared to photolysis (abundant solar energy), bio-photolysis (a readily available bio-agent), and electrolysis (electrolytic agents to carry out the process).     

Improved kinetic model for water splitting thermochemical cycles using Nickel Ferrite

In a previous work of the authors (AIChE Journal 2013; 59(4): 1213-1225) on the characterization of the performance of redox material compositions during two-step thermochemical splitting of water, it was observed that fitting of the obtained hydrogen and oxygen concentration profiles with a reaction model based on simple first order reaction rates could describe adequately only the first part of the evolution curves. This suggested that more complicated reaction models taking into account the structure of the redox material are needed to describe the whole extent of the experimental data. Based on the above, a minimum set of experiments for water splitting thermochemical cycles over a Nickel-ferrite was deigned and performed involving an increased duration of the reaction steps. A new extended model was derived for the water splitting and thermal reduction reactions, which considers two oxygen storage regions of the redox material communicating to each other by a solid state diffusion mechanism. The inclusion of two state variables instead of one has a significant effect on the reaction dynamics and renders the model capable to explain the dynamics of the convergence of the thermochemical cycles to a periodic steady state, observed experimentally in the previous work.     

Optimizing the operational strategy of a solar-driven reactor for thermochemical hydrogen production

In this paper the operational strategy of a pilot plant for regenerative hydrogen production based on two-step thermochemical redox cycles is investigated with focus on optimal operational parameters for highest solar-to-fuel efficiency. The current plant consists of a solar driven large-scale 250 kW thermochemical inert gas reactor using ceria as reactive material for water splitting and an efficient fluid heat recovery system.Here we analyse the most important process conditions, which are operating temperatures, mass flow rates and duration times for both steps in the cycle. A highly accurate and detailed simulation model combined with well-suited optimization routines reveals new insights in most efficient operational strategies. Within the optimization material and technical limits of the used components are considered, thereby yielding reliable practical results.Optimal operational parameters are found by using a temperature swing strategy with corresponding solar-to-fuel plant efficiency determined by up to 1.1%.     

Enhanced photocatalytic hydrogen production over In-rich (Ag–In–Zn)S particles

The ratio of ZnS to AgInS₂ is usually adjusted to tune the band gaps of this quaternary (Ag–In–Zn)S semiconductor to increase photocatalytic activity. In this study, the [Zn]/[Ag] ratio was kept constant. The hydrogen production rate was enhanced by increasing the content of indium sulfide. Compared to the steady H₂ evolution rate obtained with equal moles of indium and silver ([In]/[Ag] = 1, 0.64 L/m² h), that obtained with In-rich photocatalyst ([In]/[Ag] = 2, 3.75 L/m² h) is over 5.86 times higher. The number of nanostep structures, on which the Pt cocatalysts were loaded by photodeposition, increased with the content of indium. The indium-rich samples did not induce phase separation between Ag_xIn_xZn_yS_2x+y and AgIn₅S₈, instead forming a single-phase solid solution. Although the photocatalytic activity decreased slightly for bare In-rich photocatalysts, Pt loading played a critical role in the hydrogen production rate. This study demonstrates the significant effect of In₂S₃ on this unique (Ag–In–Zn)S photocatalyst.     

0D, 1D and 2D nanomaterials for visible photoelectrochemical water splitting. A Review

Global energy problems of the 21st century have led to the search for alternative energy sources, among which is hydrogen produced via photoelectrochemical solar water splitting. Photo-electrochemical water splitting using semiconductor nanostructured materials is a progressive method for producing hydrogen. The unique electronic, mechanical, surface and optical properties of nanomaterials make it possible to create photocatalysts with complex structures of energy zones, allowing the use of a wide range of sunlight and exerting a positive effect on absorption and scattering of sunlight. This review contains a detailed analysis of current studies aimed at improving the efficiency of photocatalytic systems by using 0D, 1D and 2D nanostructures. Special attention is paid to the mechanisms of photocatalytic water splitting to produce hydrogen with the help of various nanostructures.     

Estimation of electrolytic hydrogen production potential in Venezuela from renewable energies

An initial estimation of the potential for hydrogen (H₂) production in Venezuela is made, obtained by water electrolysis using electricity from renewable sources, taking advantage of the great potential of the country for solar, wind and mini hydro energies. For the first two, its potential maps is obtained from insolation and wind speed maps, respectively, prepared from satellite data, and for mini-hydro, the potential is obtained from documentary information. To calculate the amount of H₂ to produce is used the Higher Heating Value, considering the electrolytic system overall efficiency of 75%, including power requirements of the electrolyzer, auxiliary equipment, and system losses. In addition, in the calculation of usable renewable potential are excluded land areas under special administration, marine, lake and urban areas, and other limitations are considered concerning energy conversion efficiencies and useful areas available for the location of the different renewable technologies.     

Investigation of hydrogen production potential from different natural water sources in Turkey

Hydrogen production from the electrolysis of water by sea or lake waters used as electrolyte plays a crucial role in providing sustainable hydrogen production. Production of hydrogen from these natural sources is highly utilized from small scale to complex applications due to water resources' inconsumable potential. In this study, the hydrogen production potential of Turkey's different regions such as the Black Sea, Aegean Sea, Marmara Sea, Mediterranean Sea, Lake Van, Ağcaşar Dam, Yeşilırmak, and Kızılırmak rivers are investigated. Solar energy potential values are used as the current sources for simulating their renewable energy hydrogen production values. According to the results, higher hydrogen production rates are obtained from the Marmara and Lake Van regions. It is concluded that the hydrogen production potential is highly dependent on the pH values of the water source and the salinity rate of seawater that is descending from the Mediterranean Sea to the Black Sea region. Besides, solar radiation, sunshine duration, and water temperature are the other essential factors. Moreover, Mediterranean Sea water (Içel-Anamur) has about 23% higher hydrogen production than Lake Van and has the most increased hydrogen production by 80 L m^-2 in May and June.     

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.