Comparative study of activity of cerium oxide at thermal reduction temperatures of 1300–1550 °C for solar thermochemical two-step water-splitting cycle

Thermochemical two-step water-splitting using CeO₂ (cerium oxide) particles was studied to examine oxygen and hydrogen productivity and repeatability at thermal reduction (T-R) temperatures of 1300–1550 °C and water decomposition (W-D) temperatures of 400–1000 °C for the production of hydrogen from water using concentrated solar radiation as the energy source. The temperature dependency of oxygen and hydrogen productivity and the cyclic repeatability of CeO₂ are reported in this paper. The characteristic features of CeO₂ particles in the thermochemical two-step water-splitting cycle are compared with the well-known highly active reactive mediums of zirconia-supported Ni-ferrites (NiFe₂O₄/m-ZrO₂ and NiFe₂O₄/c-YSZ) and unsupported NiFe₂O₄.     

Ferrite/zirconia-coated foam device prepared by spin coating for solar demonstration of thermochemical water-splitting

A Ferrite/zirconia foam device in which reticulated ceramic foam was coated with zirconia-supported Fe₃O₄ or NiFe₂O₄ as a reactive material was prepared by a spin-coating method. The spin-coating method can shorten the preparation period and reduce the coating process as compared to the previous wash-coating method. The foam devices were examined for hydrogen productivity and cyclic reactivity in thermochemical two-step water-splitting. The reactivity of these foam devices were studied for the thermal reduction of ferrite on a laboratory scale using a sun simulator to simulate concentrated solar radiation, while the thermally reduced foam devices were reacted with steam in another quartz reactor under homogeneous heating in an infrared furnace. The most reactive foam device, NiFe₂O₄/m-ZrO₂/MPSZ, was tested for successive two-step water-splitting in a windowed single reactor using solar-simulated Xe-beam irradiation with a power input of 0.4-0.7 kW_th. The production of hydrogen continued successfully in the 20 cycles that were demonstrated using the NiFe₂O₄/m-ZrO₂/MPSZ foam device. The NiFe₂O₄/m-ZrO₂/MPSZ foam device produced hydrogen at a rate of 1.1-4.6 cm³ per gram of device through 20 cycles and reached a maximum ferrite conversion of 60%.     

Thermochemical two-step water splitting cycles by monoclinic ZrO2-supported NiFe2O4 and Fe3O4 powders and ceramic foam devices

A thermochemical two-step water splitting cycle is examined for NiFe₂O₄ and Fe₃O₄ supported on monoclinic ZrO₂ (NiFe₂O₄/m-ZrO₂ and Fe₃O₄/m-ZrO₂) in order to produce hydrogen from water at a high-temperature. The evolution of oxygen and hydrogen by m-ZrO₂-supported ferrite powders was studied, and reproducible and stoichiometric oxygen/hydrogen productions were demonstrated through a repeatable two-step reaction. Subsequently, a ceramic foam device coated with NiFe₂O₄/m-ZrO₂ powder was made and examined as a water splitting device by the direct irradiation of concentrated Xe-light in order to simulate solar radiation. The reaction mechanism of the two-step water splitting cycle is associated with the redox transition of ferrite/wustite on the surface of m-ZrO₂. A hydrogen/oxygen ratio for these redox powder systems exhibited good reproducibility of approximately two throughout the repeated cycles. The foam device loaded NiFe₂O₄/m-ZrO₂ powder was also successful with respect to hydrogen production through 10 repeated cycles. A ferrite conversion of 24-76% was obtained over an irradiation period of 30 min.     

Two-step water splitting thermochemical cycle based on iron oxide redox pair for solar hydrogen production

This study deals with solar hydrogen production from the two-step iron oxide thermochemical cycle (Fe₃O₄/FeO). This cycle involves the endothermic solar-driven reduction of the metal oxide (magnetite) at high temperature followed by the exothermic steam hydrolysis of the reduced metal oxide (wustite) for hydrogen generation. Thermodynamic and experimental investigations have been performed to quantify the performances of this cycle for hydrogen production. High-temperature decomposition reaction (metal oxide reduction) was performed in a solar reactor set at the focus of a laboratory-scale solar furnace. The operating conditions for obtaining the complete reduction of magnetite into wustite were defined. An inert atmosphere is required to prevent re-oxidation of Fe(II) oxide during quenching. The water-splitting reaction with iron(II) oxide producing hydrogen was studied to determine the chemical kinetics, and the influence of temperature and particles size on the chemical conversion. A conversion of 83% was obtained for the hydrolysis reaction of non-stoichiometric solar wustite Fe_(1−y)O at 575 °C.     

Monoclinic zirconia-supported Fe3O4 for the two-step water-splitting thermochemical cycle at high thermal reduction temperatures of 1400–1600 °C

Two-step thermochemical water-splitting using monoclinic ZrO₂-supported Fe₃O₄ (Fe₃O₄/m-ZrO₂) for hydrogen production was examined at high thermal reduction temperatures of 1400–1600 °C. After thermal reduction of Fe₃O₄/m-ZrO₂, the reduced sample was quenched in liquid nitrogen, and was subsequently subjected to the water-decomposition step at 1000 °C. Quenching of the solid sample was conducted for analysis of the chemical reactions, such as phase transitions, occurring at high-temperature. The hydrogen productivity of Fe₃O₄ on a m-ZrO₂ support and the conversion of Fe₃O₄ to FeO were significantly enhanced with higher thermal reduction temperatures. The Fe₃O₄-to-FeO conversion reached 60% when the Fe₃O₄/m-ZrO₂ was thermally reduced at 1600 °C. The phase transition of m-ZrO₂ support to tetragonal ZrO₂ (t-ZrO₂) did not occur during the thermal reduction at 1400–1500 °C, but it did proceed slightly at 1600 °C. Fe ions from Fe₃O₄ did not enter the ZrO₂ lattice during high-temperature thermal reduction. Thus, the Fe₃O₄ loaded on a m-ZrO₂ support can continuously contribute as a Fe₃O₄–FeO redox reactant for thermochemical water-splitting at high-temperatures of 1400–1600 °C.     

Reaction characteristics of two-step methane reforming over a Cu-ferrite/Ce–ZrO2 medium

Methane was reformed over a Cu-ferrite/ZrO₂ medium in a two-step process, consisting of a syn-gas production step and a water-splitting step. In the syn-gas production step, increase in Cu content in the Cu_xFe_3−xO₄/ZrO₂ medium suppressed carbon deposition and enhanced the reaction rate for stoichiometries of x ≤ 0.7. In the water-splitting step, the addition of Cu promoted the gasification of the deposited carbon. Furthermore, the addition of Ce as a binder in the Cu_0.7Fe_2.3O₄/Ce–ZrO₂ medium also improved reactivity in the syn-gas production step and yielded the highest reactivity when the molar ratio of Ce/Zr was 3/1. As a result of the co-addition of Cu and Ce, the Cu_0.7Fe_2.3O₄/Ce–ZrO₂ medium showed high durability, with a constant evolution of the synthesis gas and hydrogen in ten repeated cycles. It is thus expected that the Cu-ferrite/Ce–ZrO₂ medium is favourable for two-step methane reforming.     

Oxygen permeability and stability of dual-phase Ce0.85Pr0.15O2-δ-Pr0.6Sr0.4Fe0.9Al0.1O3-δ membrane for hydrogen production by water splitting

A series of dense xCe_0.85Pr_0.15O_2-δ (CP) -(100-x) Pr_0.6Sr_0·4Fe_0·9Al_0·1O_3-δ (PSFA) (x = 30, 40, 50, 60, 70) dual-phase oxygen transport membranes were successfully synthesized by sol-gel method. The feasibility of xCP-(100-x) PSFA membranes for hydrogen production by thermochemical water splitting was explored by testing in the thermochemical stability, oxygen permeability, hydrogen production efficiency, and performance degradation mechanism of these membranes. The results show that the thermochemical stability of xCP-(100-x) PSFA membranes is improved with the CP content increasing. The oxygen permeation model demonstrates that appropriate CP content is beneficial to reduce the permeation resistance of xCP-(100-x) PSFA membranes, and the reaction of surface exchange plays a major role in the oxygen transport process at 925 °C. The formation of Fe(SiO₃) and Sr₃Fe₂O₇ on the sweep side leads to the decline in hydrogen production rate. The 60CP-40PSFA membrane showed the best comprehensive performance with a hydrogen production retention rate of 90% and a stable hydrogen production rate of 0.99 ml cm^?2 min^?1 in the 100-h test cycle.     

Two-step water-splitting at 1273–1623 K using yttria-stabilized zirconia-iron oxide solid solution via co-precipitation and solid-state reaction

Reactive ceramics are investigated for potential use in a rotary-type solar reactor. The two-step water-splitting process, which consists of O₂-releasing (MO_oxidized=MO_reduced+1/2O₂) and H₂-generation (MO_reduced+H₂O(g)=MO_oxidized+H₂) reactions with yttria-stabilized zirconia (YSZ)-iron oxide solid solutions prepared by co-precipitation and solid-state reaction, is examined at temperatures of 1623 K for O₂ release and 1273 K for H₂ generation. The YSZ-iron oxide solid solutions with a single phase are obtained at mole ratios lower than 15% and 20% of iron ions to total cations (Fe³⁺, Zr⁴⁺, Y³⁺) by co-precipitation and the solid-state reaction, respectively. The two-step water-splitting process using YSZ-iron oxide solid solutions prepared by both preparation methods are repeated successfully. The amount of O₂ gas evolved per weight of the sample (ml/g) is observed to increase with the iron content of the YSZ-iron oxide solid solution because of the high reactivity of iron ions in the solid solution. The maximum amounts of H₂ and O₂ gases evolved in the two-step water-splitting process with the YSZ-iron oxide solid solution were 0.89 and 1.2 ml/g, respectively.     

A low-temperature electro-thermochemical water-splitting cycle for hydrogen production based on LiFeO2/Fe redox pair

The thermochemical water-splitting cycles have been paid more attention in recent years because they directly convert thermal energy into stored chemical energy as H₂. However, most thermochemical cycles require extremely high temperatures as well as a temperature switch between reduction and oxidation steps, which are the main obstacles for their development. Herein, we introduced an electrochemical reaction into the thermochemical cycle and established a novel two-step water-splitting cycle based on LiFeO₂/Fe redox pair. The two-step water-splitting process involves a cyclic operation of electrochemical reduction and water-splitting steps. The feasibility of the water-splitting cycle for the hydrogen production was thermodynamically and experimentally investigated. A mechanism of hydrogen production based on LiFeO₂/Fe redox pair was developed. Compared with the traditional high-temperature thermochemical cycles, the electrochemical reduction and water-splitting steps of the process can be isothermally operated in the same cell at a relatively low temperature of 500 °C. The main advantages of the cycle are not only easily available heat sources without involvement of the associated engineering and materials issues, but also without any temperature swings. This is a promising method to achieve water splitting for hydrogen production in the future.     

La(1−x)SrxMnO3−δ perovskites as redox materials for the production of high purity hydrogen

Materials of the perovskite structure and of the general formula La_1−xSr_xMnO₃ (x = 0, 0.3, 0.7) are investigated as redox catalysts for the two-step steam reforming of methane towards the production of high purity hydrogen. During the activation step, methane is oxidized with lattice oxygen to carbon dioxide and carbon monoxide, while oxygen is withdrawn from the material until a maximum deficiency level which depends on the strontium content and the reaction temperature. During the reaction step water is splitted to gaseous hydrogen and lattice oxygen that fills the oxygen vacancies. It appeared that, after the achievement of a characteristic oxygen deficiency level, La_1−xSr_xMnO₃ materials exhibit good activity for the water-splitting reaction. The activity is further found to be proportional to the oxygen vacancy concentration. At high activity levels, initial water conversions per 15 μmol pulse of up to 70% are achieved at 1000 °C. The cumulatively produced hydrogen during the water-splitting step, per injected water, increases with increasing strontium content, reaching a production of 60 μmol H₂ per 500 μmol water passed over 200 mg La_0.3Sr_0.7MnO₃ at 1273 K and no coke formation. The materials exhibit stable behavior after eight successive oxidation–reduction cycles. The relations between the redox behavior and the material defect chemistry are discussed. Finally the energy efficiency of the process, future prospects and ways for its optimization are discussed.     

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.     

Low-temperature water-splitting by sodium redox reaction

Thermochemical water-splitting by sodium redox reactions was investigated from material science point of view as a future hydrogen production method. The reaction system consists of three separate reactions, which are hydrogen generation by NaOH-Na reaction, metal separation by thermolysis of Na₂O, and oxygen generation by hydrolysis of Na₂O₂. Although the current techniques of thermochemical water-splitting required a temperature higher than 800 °C for whole reaction cycle, the sodium system was able to be operated below only 400 °C by using nonequilibrium techniques to control the entropy of the chemical reactions. Therefore, this system should be recognized as a potential water-splitting technique that can widely utilize any heat sources in contrast to the conventional methods.     

Novel twin reactor for separate evolution of hydrogen and oxygen in photocatalytic water splitting

Photocatalytic water splitting with separate H₂ and O₂ evolution is crucial because it eliminates the explosion potential and hydrogen-purification cost. A novel twin reactor was designed to separate the evolution of hydrogen and oxygen in photocatalytic water splitting under visible light. A modified Nafion membrane was employed to segregate the two photocatalysts in the twin reactor so that hydrogen and oxygen can be evolved separately. Conventional Z-scheme catalysts, Pt/SrTiO₃:Rh and WO₃, were used as hydrogen-photocatalyst and oxygen-photocatalyst, respectively. Fe²⁺ and Fe³⁺ were added in the reaction solution as electron-transfer mediator. The ratio of evolved H₂ and O₂ was in agreement with the stoichiometric ratio (2:1) of hydrogen and oxygen of water. An average hydrogen generation rate of 1.59 μmol/g-h was achieved in the twin-reactor system, which was twice as much as that in the conventional Z-scheme system. The improved H₂ yield was due to the prevention of the water-splitting backward reaction in the twin reactor.     

Synthesis and rate performance of Fe3O4-based Cu nanostructured electrodes for Li ion batteries

Fe₃O₄-based Cu nanostructured electrodes for Li ion batteries are fabricated by a two-step electrochemical process, and characterized with scanning electron microscopy, X-ray diffraction, and electrochemical experiments. It is found that the electrochemical performance is closely related to the Fe₃O₄ morphology. The nanostructured electrodes with 1 min Fe₃O₄ deposition exhibit a large specific discharge capacity, i.e. 1342.23 mAh g⁻¹ in the first cycle and 1003.94 mAh g⁻¹ in the 34th. After extended Fe₃O₄ electroplating, Fe₃O₄ particles will fill the spaces between the Cu nanorods and coalesce on the top of the Cu nanorod arrays, which is detrimental to achieve high specific reversible capacities and good rate capability. Moreover, the nanostructured electrodes demonstrate significantly enhanced cycling performance due to the introduction of Cu nanorod arrays as the current collector, especially as compared to the planar electrodes where Fe₃O₄ is electrodeposited directly onto planar Cu surfaces.     

Novel two-step thermochemical cycle for hydrogen production from water using germanium oxide: KIER 4 thermochemical cycle

This paper proposes a novel two-step thermochemical cycle for hydrogen production from water using germanium oxide. The thermochemical cycle is herein referred to as KIER 4. KIER 4 consists of two reaction steps: the first is the decomposition of GeO₂ to GeO at approximately 1400–1800 °C, the second is hydrogen production by hydrolysis of GeO below 700 °C. A 2nd-law analysis was performed on the KIER 4 cycle and a maximum exergy conversion efficiency was estimated at 34.6%. Thermodynamic analysis of GeO₂ decomposition and hydrolysis of GeO confirmed the possibility of this cycle. To demonstrate the cycle, the thermal reduction of GeO₂ was performed in a TGA with mass-spectroscopy. Results suggest GeO₂ decomposition and oxygen gas evolution. To confirm the thermal decomposition of GeO₂, the effluent from GeO₂ decomposition was quenched, filtered and analyzed. SEM analysis revealed the formation of nano-sized particles. XRD analysis for the condensed-filtered particles showed the presence of Ge and GeO₂ phases. The result can be explained by thermodynamic instability of GeO. It is believed that GeO gas disproportionates to ½Ge and ½GeO₂ during quenching. 224 ml hydrogen gas per gram of reduced GeO₂ was produced from the hydrolysis reaction.     

Chemical looping gasification of biomass char for hydrogen-rich syngas production via Mn-doped Fe2O3 oxygen carrier

Because of its low cost, an iron-based oxygen carrier is a promising candidate for hydrogen-rich syngas production from the chemical looping gasification of biomass. However, it needs modification from a reactivity point of view. In this study effect of Mn doping on Fe₂O₃ has been investigated for hydrogen-rich syngas production from biomass char at different temperatures (700–900 °C) and steam flow rates (60–100 μL/min). Several techniques (XRD, XPS, BET, and TPR-H₂) have been utilized to characterize fresh and spent oxygen carriers. The result demonstrated Mn-doing boosted the redox activity and the amount of oxygen vacancies, which increased hydrogen gas generation. Hydrogen production displayed different behavior across temperatures due to detecting Fe₂O₃ and MnFeO₃ phases for spent oxygen carriers. For the Fe₂O₃ oxygen carrier hydrogen gas yield is 1.67 Nm³/kg which is due to reduction of Fe₂O₃ phase to Fe₃O₄. However, the MnFe₂O₄ spinel phase detected in the spent MnFeO₃ oxygen carrier is a reason for improving hydrogen gas yield to 1.84 Nm³/kg. Change reaction temperature from 900 °C to 850 °C reduced hydrogen gas yield from 1.84 Nm³/kg to 1.83 Nm³/kg for with MnFeO₃ oxygen carrier. Regarding different steam flows, the proper flow rates that can maintain the formed phases and obtained best hydrogen gas yield are 80 and 90 μL/min, respectively. Meanwhile, the best hydrogen gas yield (2.21Nm³/kg) are obtained with MnFeO₃ oxygen carrier at optimum conditions (850 °C and 90 μL/min).     

Dissociation of magnetite in a solar furnace for hydrogen production. Tentative production evaluation of a 1000 kW concentrator from small scale (2 kW) experimental results

For experiment results obtained in a 2 kW solar concentrator, the FeO production by thermal dissociation of magnetite (Fe₃O₄) was extrapolated to the 1000 kW solar furnace of Odeillo, France. If this reaction is used in a two step thermochemical water splitting cycle, one can expect an extrapolated value of 137 m³ day^?1 hydrogen production when Fe₃O₄ is dissocated at 2090 K, under an inert atmosphere, during 0.5 min and cooled down by a splat cooling quench technique.     

Hydrogen production via water splitting process in a molten-salt fusion breeder

This study presents the hydrogen production and fissile breeding potentials of Force-Free Helical Reactor (FFHR) fueled with the molten-salt mixtures. The sulfur–iodine (S–I) thermochemical water-splitting and high-temperature electrolysis cycles, which are the most promising water-splitting cycles, are selected to produce large-scale and pure hydrogen. The XSDRNPM/SCALE4.4a neutron transport code is used for the neutronic calculations. The analyses have been performed individually for four different molten-salt mixtures, (pure FLiBe, mixture of FLiBe and ThF₄, mixture of FLiBe and UF₄, and mixture of FLiBe, ThF₄ and ²³³UF₄). The numerical results bring out that the considered molten-salt fusion breeder reactor has a high neutronic performance and can produce a considerable amount of the hydrogen production (up to 40 kg/s), as well as the fissile fuel (up to 2.5 tons/yr).     

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.     

Hydrogen production by redox of bimetal cation-modified iron oxide

Pure hydrogen can be stored and supplied directly to polymer electrolyte fuel cell by the redox of iron oxide: Fe₃O₄ + 4H₂ → 3Fe + 4H₂O and 4H₂O + 3Fe → Fe₃O₄ + 4H₂. Four bimetal-modified samples were prepared by impregnation. The hydrogen storage properties of the samples were investigated. The result shows that the Fe₂O₃–Mo–Al sample presented the most excellent catalytic activity and cyclic stability. H₂ forming temperature and H₂ forming rate could be surprisingly decreased and enhanced, respectively. The average H₂ forming temperature at the rate of 250 μmol min⁻¹·Fe-g⁻¹ for Fe₂O₃–Mo–Al in the first 4 cycles could be decreased from 469 °C before the addition of Mo–Al to 273 °C after the addition of Mo–Al. The reason for it may be that the Mo–Al additive in the sample can prevent from the sintering of the particles and accelerate the H₂O decomposition due to Mo taking part in the redox reaction. The average storage capacity of Fe₂O₃–Mo–Al was up to 4.68 wt%.