Cycle For Hydrogen Production Research Articles

A comparative exergoenvironmental assessment of thermochemical copper-chlorine cycles for sustainable hydrogen production

Hydrogen is one of the highly promising clean solutions to address the concerns of energy security in the future given the rapid rate of depletion of naturally occurring hydrocarbon sources. However, it is of immense importance that hydrogen is obtained through sources that ensure sustainability. Thermochemical water-splitting processes are among such routes of hydrogen production that are both sustainable and environmentally benign. Thus, this study focuses on assessing the copper-chlorine thermochemical cycles that are among the more promising cycles of the chlorine family in terms of efficiency and cost-effectiveness. Moreover, this study considers a comparative exergoenvironmental evaluation of the four variants of the copper-chlorine cycle that vary in the number and the nature of steps. A comparison in this regard is carried out between the various steps of each cycle in terms of the component-associated environmental impact rates and environmental impact rates of energy transfer as well as the overall environmental impacts of all cycles. In addition, a comparison of the global warming potential of hydrogen synthesized through utilizing various electricity sources is also performed. Based on our evaluations, hydrolysis and electrolysis are the common steps in the five-step cycle, the four-step cycle, and the three-step cycle configuration 1 yielding the highest component-associated environmental impact rates and environmental impact rates of energy transfer, respectively. Conversely, in the three-step cycle configuration 2, the electrolysis and thermal decomposition steps yield the highest corresponding values, respectively. In addition, the three-step cycle configuration 2 (4,869 mPts/h) and the five-step cycle (3,194 mPts/h) have the highest and the lowest component-associated environmental impact rates, respectively while the five-step (530,694 mPts/h) and the four-step (248,050 mPts/h) cycles result in the highest and the lowest environmental impact rates of energy transfer, respectively.

A review of methane-driven two-step thermochemical cycle hydrogen production

Solar thermochemical cycling is a promising approach to utilizing solar energy to produce H2 and CO, which can be further synthesized into liquid fuels via Fischer-Tropsch reactions, making storage and transportation easier. Despite the potential high theoretical efficiency, factors such as the high temperature and low oxygen partial pressure required for the reduction restrict the large-scale application of this technology. In the near-to-medium term, in order to accelerate the popularization and application of this technology, according to Le Chatelier's principle, the assisted reduction of methane can greatly reduce the demand for high-temperature materials and ultra-low oxygen partial pressure. However, the addition of methane will also bring additional challenges, such as carbon emissions and carbon deposition. Reducing the influence of factors such as material sintering and irreversible loss on system efficiency in the experiment will be essential for the development of this technology. This paper focuses on the methane-driven two-step thermochemical cycle hydrogen production process, summarizes its reaction mechanism, thermodynamic analysis, kinetic analysis, oxygen carrier material doping, and experimental research in detail, and comprehensively analyzes the effect of material properties and irreversible loss on the system. According to thermodynamic and kinetic analysis, rational selection and doping of metal oxygen carrier materials can effectively reduce the reaction temperature, improve gas production rates, and enhance structural stability. Analyzing and trying to reduce various irreversible losses of the system, such as reradiation energy loss, conduction energy loss, etc., and taking appropriate heat recovery measures will help to improve the system efficiency of the actual cycle. This paper would be valuable for the development of this technology and for achieving the goal of carbon neutrality.

Performance evaluation of the Fe–Cl and Mg–Cl cycle for hydrogen production of the minor actinide fuelled PACER fusion blanket

Thermochemical processes used to produce clean hydrogen (H2) on a large scale by utilizing renewable energy and nuclear power sources are considered one of the most environmentally friendly strategies. In this study, the neutronic performance and hydrogen production potential of the PACER fusion blanket have been investigated during the operation period. Firstly, neutronic calculations have been performed to produce an electrical energy of 1000 MW from fusion explosions of 8.36 TJ to be repeated every 40 min with Monte Carlo Calculation Method (MCNP). Minor actinide flouride (MA) fuel out of the nuclear waste of LWRs with volume fractions of 2% have been mixed homogenously in the Flibe coolant. Tritium breeding ratio (TBR) at startup is calculated as 1.27. TBR and energy multiplication factor (M) decrease gradually. TBR >1.05 can be kept over 7 years for a self-sustained reactor. The M due to higher fissionable fuel content in the molten salt computes as 3.3 at initial. The burn up exceeds ∼800 GWd/tM at the end of operation period. Secondly, the potential of hydrogen production for four step iron chloride (Fe–Cl) and three step magnesium chloride (Mg–Cl) thermochemical cycles of the hydrogen unit PACER fusion blanket. The ratio of thermal power (1 − ψ), total thermal power (Phpf) and rate of mass flow of hydrogen (m˙H2) depends on M for Fe–Cl, Mg–Cl (option I) and Mg–Cl (option II) thermochemical cycle have been presented. The ratio of thermal power (1 − ψ) for Fe–Cl, Mg–Cl (option I) and Mg–Cl (option II) have been obtained as 0.6494, 0.131 and 0.095 whereas, total thermal power (Phpf) have been computed as 5298.8, 3608.43 and 3488.925 MW, respectively, at start up. The produced of hydrogen amount for Fe–Cl, Mg–Cl (option I) and Mg–Cl (option II) have been calculated as ∼ 534.65; ∼1236.82 and ∼806.03 kg/year, respectively, at startup.

Negative net global warming potential hydrogen production through biomass gasification combined with chemical looping: Environmental and economic assessments

The integration of biomass gasification (BG) with chemical looping hydrogen production (CLHP) offers one prospective approach for green hydrogen production. The environmental and economic assessments are conducted to evaluated the sustainable performance of the BG-CLHP system during the hydrogen production cycle (HPC). The results showed that the environmental impacts of BG-CLHP are concentrated in freshwater aquatic ecotoxicity (FAETP), human toxicity (HTP), and acidification (AP). The BG-CLHP system can provide a more cost-competitive hydrogen supply solution for hydrogen refueling stations compared the offshore wind or photovoltaic (PV) powered electrolysis, given the same hydrogen production target. For global warming potential (GWP) and cost, the BG-CLHP demonstrates excellent integrated performance with GWP values of −15.13 and −17.00 kg CO2, eq/kg H2, for the Air case and Oxygen case, and the costs of 3.05 and 2.82 $/kg H2, respectively, and sensitivity analysis reveals that the CLHP stage is the primary contributor to GWP. Compared with existing hydrogen production routes, BG-CLHP can still be improved in terms of costs and the technical maturity, however, the excellent negative GWP properties of BG-CLHP make it will play a more important role in future large-scale hydrogen production.

Liquid-Liquid Phase Separation-Mediated Photocatalytic Subcellular Hybrid System for Highly Efficient Hydrogen Production.

Plant chloroplasts have a highly compartmentalized interior, essential for executing photocatalytic functions. However, the construction of a photocatalytic reaction compartment similar to chloroplasts in inorganic-biological hybrid systems (IBS) has not been reported. Drawing inspiration from the compartmentalized chloroplast and the phenomenon of liquid-liquid phase separation, herein, a new strategy is first developed for constructing a photocatalytic subcellular hybrid system through liquid-liquid phase separation technology in living cells. Photosensitizers and in vivo expressed hydrogenases are designed to coassemble within the cell to create subcellular compartments for synergetic photocatalysis. This compartmentalization facilitates efficient electron transfer and light energy utilization, resulting in highly effective H2 production. The subcellular compartments hybrid system (HM/IBSCS) exhibits a nearly 87-fold increase in H2 production compared to the bare bacteria/hybrid system. Furthermore, the intracellular compartments of the photocatalytic reactor enhance the system's stability obviously, with the bacteria maintaining approximately 81% of their H2 production activity even after undergoing five cycles of photocatalytic hydrogen production. The research brings forward visionary prospects for the field of semi-artificial photosynthesis, offering new possibilities for advancements in areas such as renewable energy, biomanufacturing, and genetic engineering.

Construction of Au/ZnWO4/CdS Ternary Photocatalysts with Oxygen Vacancy Modification for Efficient Photocatalytic Hydrogen Production

AbstractRational design and optimization of the photocatalyst architecture, aimed at effectively enhancing light absorption and accelerating charge separation and transfer, can lead to the accomplishment of sustainable photocatalytic hydrogen production. In this study, a ternary system of Au/ZnWO4/CdS is prepared with oxygen vacancy modification through a combination of hydrothermal, chemical precipitation, and photochemical deposition methods. The addition of CdS and Au nanoparticles significantly enhances the light absorption range of ZnWO4 (ZWO) and creates more active sites for hydrogen production. The type‐II engineered heterojunction, in combination with Au as a cocatalyst, is a viable and efficient method for enhancing the separation and transport of electron–hole pairs, thereby facilitating the effective precipitation of hydrogen through photocatalysis. 5A10ZC exhibits a hydrogen production rate of 5483.62 µmol g−1 h−1, which is 167 times higher than that of unmodified ZWO and 29 times higher than that of pure CdS. In addition, it exhibits excellent cycle stability in the hydrogen production cycle stability test. The photoelectrochemical test results show that the construction of the system improves the separation and transfer efficiency of photogenerated carriers. This study provides a new inspiration for the construction of high‐performance photocatalytic materials.

A study on integrated HTR-PM driven hydrogen production using thermochemical cycles

This present study aims to design a nuclear-based hydrogen production system by using the three- and four-step magnesium-chloride cycles, and compares the three-step magnesium-chloride cycle integrated nuclear-based system and the four-step magnesium-chloride cycle integrated nuclear-based system. Within the scope of this study, four units of high-temperature gas-cooled-pebble bed modular nuclear reactor are employed, where a total of 1 GW thermal energy (heat) is secured from these four reactors. All of the heat generated by the reactors is used to drive the power generation and hydrogen production cycles. The proposed system, along with its cycles and processes, are examined by using mass, energy, entropy, and exergy balance equations. The modeling and simulations for the three- and four-step magnesium-chloride cycles are carried out via the Aspen Plus software package. The results are compared for two hydrogen production methods, and sensitivity analysis is assessed for various steam/MgCl2 ratios, as well as different reactor temperatures and pressures for each reaction in the cycles. While the three-step magnesium-chloride cycle integrated nuclear-based system produces 2.43 kg/s hydrogen, 2.13 kg/s hydrogen is produced by the four-step magnesium-chloride cycle integrated nuclear-based system. As a consequence of this present study, energy and exergy efficiencies are calculated as 54.2% and 60.9% for the three-step magnesium-chloride cycle, while these values are 48.0% and 54.0% for the four-step magnesium-chloride cycle. Additionally, while the energy and exergy efficiencies of the three-step magnesium-chloride cycle integrated overall system are 29.2% and 40.3%, these values are 25.6% and 35.2% for the four-step magnesium-chloride cycle integrated system, respectively.

Multi-injection downdraft moving bed reactor for hydrolysis in thermochemical hydrogen production

This paper investigates a downdraft multi-injection moving bed reactor (MBR) for the hydrolysis reaction in the copper-chlorine (Cu–Cl) thermochemical cycle for hydrogen production. The numerical modelling is conducted for a variety of system configurations of the MBR, with a focus on reducing the energy requirement of the reactor while achieving high conversion rates. Several design variables are investigated, including reactor volume, injection point location, and quantity of steam injection. The numerical predictions show an approximate 23% increase in CuCl2 conversion for the multi-injection MBR compared to a single injection design. A maximum conversion of 66.5% is predicted through design parameter variations. Asymptotic behavior for the quantity of injection locations with respect to conversion extent is presented for several different steam to copper ratios. The results and new insights in this paper suggest opportunities for conversion improvement and steam to copper ratio reduction in the hydrolysis reactor through the MBR design.

An integrated alkali metal thermoelectric converter with sodium hydroxide thermoelectric water splitter and organic Rankine cycle for efficient power and hydrogen production

This study proposes the integration of the NaOH thermochemical water splitting cycle with both an alkali metal thermoelectric converter and an organic Rankine cycle. The objective of the proposed model is to enhance the overall efficiency by utilizing the waste heat generated by the NaOH thermochemical water splitting process and redirecting the heat from the alkali metal thermoelectric converter using bypass when hydrogen demand is low.Performance parameters such as system efficiency, system power, hydrogen production, AMTEC power production, and ORC power production were examined in the study. The results indicated an increase in power and hydrogen production with higher hot-end temperatures, along with an overall reduction in system efficiency for low values of load resistance. The system achieved a maximum efficiency of 53.37%.The system efficiency reached its peak at an AMTEC hot end temperature of 1173 °C, achieving 53.37 % efficiency at an RL value of 1.01 O. When the system operates at its maximum AMTEC power production, the AMTEC modules supply 12.81 kW, while the ORC generates 5.57 kW, and the hydrogen compressor consumes 0.13 kW. The total electrical power generation is 18.38 kW. The findings also indicate that the utilization of the bypass led to a reduction in hydrogen production while increasing the power output of the organic Rankine cycle.

Safety Analysis of the Hydrolysis Reactor in the Cu-Cl Thermochemical Hydrogen Production Cycle—Part 1: Methodology and Selected Top Events

In this paper, IEC 61511 was used to evaluate the hazards and risks associated with the continuous operation of the hydrolysis reactor system in the copper-chlorine thermochemical hydrogen production cycle, with a specific focus on the application of automated active safety systems and safety integrated systems. The analysis presented herein was performed using a speculative but representative hydrolysis piping and instrumentation diagram (P&ID) for the hydrolysis reaction, which was based on currently published systems as well as experience with experimental hydrolysis reactors. This analysis was then used to inform the design of a set of automated safety systems that provide the redundant operation of critical devices and can bring the hydrolysis to a safe shutdown state if needed.

Thermodynamic and environmental performance of a Kalina-based multigeneration cycle with biomass ancillary firing for power, water and hydrogen production

The performance of a Kalina-based multigeneration cycle for power, water, and hydrogen production is investigated from thermo-environmental, sustainability, and thermo-economic perspectives. The plant comprises a gas turbine (GT), Kalina cycle (KC), and vapor absorption system (VAS) as the bottoming cycle and an integrated domestic water heater and proton-electron membrane (PEM) electrolyzer for hydrogen production. The system's models were simulated with Engineering Equation Solver (EES) codes. The results indicate a net energy efficiency of 53.48% and exergy efficiencies of 50.05 %, with an additional 30,178 kW of products from the bottoming cycles. The GT contributed approximately 85.81 % of the overall exergy destruction. The system's exergo-thermal index (ETI) stood at 1.713, with the GT only having an ETI of 2.106. Similarly, the exergetic sustainability index (ESI) of the multigeneration plant was not greater than 2.04. The exergoeconomic analysis shows a low average energy cost from the GT, estimated at 0.836 $/GJ, compared to the Kalina subsystem, which stood at 6.53 $/GJ. The thermodynamic and cost evaluation of the system demonstrates substantial benefits from the plant, which kept the hydrogen production rate at 0.1524 kg/hr.

Experimental study and modelling of continuous SO2-depolarized electrolysis in hybrid sulfur cycle for hydrogen production

SO2-depolarized electrolysis (SDE) is the key process in the hybrid sulfur cycle for green hydrogen production, but the detailed SDE characteristics including products generation, current efficiency variation, and side reactions are unclear. Herein, a continuous SDE process was experimentally conducted and theoretically modelled. The H2 and H2SO4 production was accelerated and the current efficiency for both electrodes was improved with a proper increase in current density (50−100 mA/cm2) or temperature (293−318 K), but further increasing current density to 150 mA/cm2 or temperature to 333 K led to a negative trend because of the anode corrosion or declined SO2 solubility. The increasing initial H2SO4 concentration (10−40 wt%) facilitated the cathodic H2 production and current efficiency, while negatively influenced the anodic SO2 conversion. The parasitic reactions occurred at cathode consumed H2 and resulted to the cathodic current efficiency well below 100%. A rigorous mathematical regression model correlating the production rates of H2 and H2SO4 with current density, temperature, and initial H2SO4 concentration was developed, and combined with the analysis of variance, current density was suggested the biggest factor affecting products generation in SDE process. These findings demonstrate a practical avenue for efficient SO2 conversion and H2 production in SDE process of hybrid sulfur cycle.

Chemistry of the iron-chlorine thermochemical cycle for hydrogen production utilizing industrial waste heat

This research presents an inventive thermochemical cycle that utilizes a reaction between iron and HCl acid for hydrogen production. The reaction occurs spontaneously at room temperature, yielding hydrogen and a FeCl2 solution as a by-product. Exploring the thermal decomposition of the FeCl2 by-product revealed that, at conditions suitable for utilization of low-temperature industrial waste heat (250 °C), chlorine gas formation can be circumvented. Instead, the resulting by-product is HCl, which is readily soluble in water, facilitating direct reuse in subsequent cycles. The utilization of low-temperature industrial heat not only optimizes resource utilization and reduces operational costs but also aligns with environmentally sustainable production processes. From the kinetic studies the activation energy was calculated to be 45 kJ/mol and kinetics curves were constructed. They showed significant kinetics at room temperature and above but rapid decrease towards lower temperatures. This is important to consider during real-scale technology optimization. The theoretical overall energy efficiency of the cycle, with 100% and 70% heat recuperation, was calculated at 68.8% and 44.8%, respectively. In practical implementation, considering the efficiency of DRI iron reduction technology and free waste heat utilization, the cycle achieved a 41.7% efficiency. Beyond its energy storage capabilities, the Iron-chlorine cycle addresses safety concerns associated with large-scale hydrogen storage, eliminating self-discharge, reducing land usage, and employing cost-effective storage materials. This technology not only facilitates seasonal energy storage but also establishes solid-state energy reserves, making it suitable for balancing grid demands during winter months using excess renewable energy accumulated in the summer.

Process modelling and assessment of thermochemical sulfur-iodine cycle for hydrogen production considering Bunsen reaction kinetics

Thermochemical sulfur-iodine (SI) cycle is one of the large-scale, clean, and efficient hydrogen production routes. The Bunsen reaction process is always simulated by a stoichiometric reaction, without considering the realistic Bunsen reaction kinetic process. Herein, a user-defined Fortran module concerning Bunsen reaction kinetics was developed and embedded into a continuous stirred tank reactor (RCSTR), and then a SI flowsheet with 100 L/h hydrogen production was modelled. The key parameter optimization, mass and energy balance were analyzed, the internal heat exchange network was created using the pinch point temperature difference analysis and the principle of energy cascade utilization, along with thermal efficiency evaluation. Bunsen reaction process reaches equilibrium after a period, which is consistent with experiments. The increase of H2SO4 decomposition ratio is beneficial to reduce the energy consumption of system. Increase in temperature has less effect on increasing the equilibrium decomposition ratio of HI. The theoretical thermal efficiency of system reaches 14.0-57.4% considering the recovery of exothermic heat. This work provides a theoretical basis for the optimization of SI cycle.

Continuous multiphase Bunsen reactor of iodine-sulfur thermochemical water splitting cycles for hydrogen production: Experimental, Modelling and Design Insights

Thermochemical water splitting cycles (TWSCs) hold promise for sustainable H2 production in future energy systems, with Iodine-Sulfur (IS) and Nickel-Iodine-Sulfur (NIS) processes standing out as efficient options. The core of both these processes lies in the Bunsen reaction, underscoring the need to identify optimal operational conditions and plant solutions for this crucial reaction section. Thus, in this study, a continuous counter-current flow Bunsen reactor fed with 5 NL h−1 of SO2 was constructed and tested. An inventive aspect was the introduction of solid I2 pellets from the top to enhance saturation at the liquid-liquid interface between sulfuric and hydriodic product phases, promoting segregation. This ingenious design achieved nearly complete SO2 conversion and optimal H2SO4 and HI concentrations in the respective product phases, while avoiding undesirable byproduct formation. The study further advanced the modelling of the experimental reactor by employing innovative kinetic and liquid-liquid equilibrium description approaches, and demonstrating exceptional validation accuracy of R2 = 0.9988. Additionally, with the aim of obtaining design charts as a potential tool for Bunsen reactor design, a microscopic model describing the gas phase trend along bubble or packed Bunsen-type reactors was developed. The model’s dimensionless analysis revealed a characteristic times ratio (Bu) comprehensively describing all the phenomena occurring to the gas phase within the Bunsen reaction section, and identified an optimal Bu value of 0.4 for pure SO2 gas inlet. Overall, the study's innovative strategies and models contribute significantly to the advancement of Bunsen reactor engineering.

Thermodynamic analysis on CSP integrated cerium oxide (CeO2 − CeO1.72/1.83) water splitting cycle for hydrogen production

Solar thermochemical CeO2-based H2O splitting cycle was thermodynamically analyzed to ascertain the optimal thermal reduction (TH) and re-oxidation (TL) temperatures and evaluate the solar-to-fuel conversion efficiency (ηsolar−to−fuel) of the cycle. The equilibrium composition of CeO2, CeO1.72,CeO1.83 and O2 exhibited that the thermal reduction initiated at 1400 K thereby attaining 100 % TR at 2734 K. The observed variations in Gibbs free energy (ΔG) correspond to the feasibility of the re-oxidation step of CeO1.83 and CeO1.72 at 1050 K and 1200 K respectively. It was reported that the absorption efficiency of solar reactor (ηabs−solar−reactor−WS) decreases from 95.6 % to 37 %, as the TH increases from 1400 K to 2734 K. The results show that ηsolar−to−fuel reached the maximum value of 7.45 % for CeO1.72 and 7.69 % for CeO1.83 at 61.72 % TR of CeO2 without heat recuperation. Further, the ηsolar−to−fuel attained the maximum value of 14.92 % and 13.54 % for CeO1.83 and CeO1.72, respectively at the %TR of CeO2 of 80 % with 50 % heat recuperation. The solar-to-fuel conversion efficiency (ηsolar−to−fuel) further can be increased with the optimization of oxygen partial pressure (PO2) and molar flow rate of reduction regents (Ar or N2).

HI decomposition over the HI-100 test apparatus at a hydrogen production rate over 100 L/h

Studies on the iodine-sulfur (IS) thermochemical cycle for hydrogen production has been carried out since about 2005 by the Institute of Nuclear and New Energy Technology, Tsinghua University, China. The HI decomposition occupies the important position of hydrogen generation in the IS cycle. In this paper, the HI-100 test apparatus with a H2 production rate of 100 L/h was constructed and the HI decomposition was tested. First, the process and components for HI decomposition were designed. Then, the key components, including the feed tank, evaporator, gas heater, adiabatic reactor, condenser, and gas-liquid separator were made of industrial materials. After building this apparatus, the sealing test, heating water test, and HI decomposition have been conducted. The stable hydrogen production operation of more than 100 L/h had been achieved for 5 h, the maximum hydrogen production reached approximately 130 L/h, and the hydroiodic acid decomposition rate maintained about 22 %. The test results provide the design and experimental guidance for further amplification of HI decomposition for hydrogen production by the IS cycle.

Evaluating the influence of Ar/N2 flow rate and pressure on the conversion efficiency of a solar-assisted Fe2O3 – FeO WS cycle for hydrogen production: A thermodynamic approach

A thermodynamic analysis is carried out to evaluate the effects of oxygen partial pressure (PO2) and molar flow rate of reduction agents (m˙N2/Ar) on the performance of Fe2O3−FeO solar thermochemical cycle (STC|Fe2O3−FeO). The chemical equilibrium and efficiency analysis parameters such as enthalpy, Gibbs free energy and entropy are calculated as a function of thermal dissociation temperature (TH). The chemical equilibrium analysis suggests that the thermal dissociation step is feasible above 1250 K while the re-oxidation step is practicable at 550 K. The efficiency analysis revealed that the highest value of conversion efficiency (ηsolar−to−fuel) reached up to 44.42% for N2 based cycle and 45.46% for Ar based cycle without using the recuperation technique. However, the conversion efficiency (ηsolar−to−fuel) attained the highest value of 57.84% for N2 based cycle and 59.14% for Ar based cycle with 50% heat recuperation.

Molten salt heat exchanger design for the thermolysis reactor in the Cu–Cl cycle of hydrogen production

The thermochemical copper–chlorine (Cu–Cl) cycle is known as a promising method for producing clean hydrogen. Due to the high-temperature environment of the thermolysis reactor, there are commercialization challenges with regard to the heat exchanger design. In this study, a new design for the heat exchanger used in the thermolysis reactor of a 4-step Cu–Cl cycle is presented, aiming to achieve the required temperature distribution of 430 °C–550 °C. A design methodology is developed for the heat exchanger along with an iterative algorithm for the sizing problem. The final design of this study has decreased the T* (representative of the temperature range) by 51 % compared to the previous designs, with the improvement techniques resulting in increasing the heat exchanger effectiveness and thermal performance factor by 15 % and 138 % and decreasing average TD (representative of the temperature dispersal) by 61 %. The achieved operating temperature ranges from 431.3 °C to 539.0 °C.

Thermodynamic assessment of thermochemical cycle for hydrogen production based on water decomposition with binary copper chlorine couple

Thermodynamic assessment of thermochemical cycle for hydrogen production based on water decomposition with binary copper chlorine couple