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.     

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.     

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.     

Water splitting for hydrogen production with ferrites

The water splitting reaction by a thermo-chemical cycle using ferrites was investigated for H₂ production. In the first step (activation step), ferrites were thermally reduced at 1200 °C to form an oxygen-deficient ferrite. In the second step (water splitting step), the activated ferrites were oxidized by water at 800 °C to produce hydrogen. Among the prepared ferrites, Ni-ferrite was found to be the most suitable for H₂ production. NiFe₂O₄ produced an average of 0.442 cm³/g cycle of H₂. The H₂ productivity of the Ni-ferrite was much higher than that of the other ferrites at the same temperature. XRD showed that the crystal structure of NiFe₂O₄ during the redox reaction was not changed during the repeated cycles, indicating that NiFe₂O₄ was an excellent material in terms of structural stability and durability.     

Evaluation of temperature characteristics of high-efficiency InGaP/InGaAs/Ge triple-junction solar cells under concentration

Temperature characteristics of the open-circuit voltage (V_oc) were investigated in the temperature range from 30°C to 240°C for the InGaP/InGaAs/Ge triple-junction cells. Also, single-junction cells that had the similar structure to the subcells in the triple-junction cells were studied. In the high-temperature range (from 170°C to 240°C), the temperature coefficients of V_oc of the InGaP/InGaAs/Ge triple-junction solar cell (dV_oc/dT) were different from those in the low-temperature range (from 30°C to 100°C). This is because photo-voltage from the Ge subcell becomes almost 0 V in the high-temperature range. It was found that the open-circuit voltage of a Ge single-junction cell reduced to almost 0 V temperatures over 120°C under 1 sun condition.     

Stepwise production of CO-rich syngas and hydrogen via solar methane reforming by using a Ni(II)–ferrite redox system

The methane reforming process combined with metal–oxide reduction was examined on iron-based oxides of Ni(II)–, Zn(II)–, and Co(II)–ferrites, for the purpose of converting solar high-temperature heat to chemical fuels of CO-rich syngas and reduced metal oxide as storage and transport of solar energy. It was found that the Ni(II)-doping effectively improves the reactivity of magnetite as an oxidant for methane reforming. A two-step cyclic steam reforming of methane, which produces CO-rich syngas and hydrogen uncontaminated with carbon oxides alternately in the separate steps, was successfully demonstrated by using a ZrO₂-supported Ni(II)–ferrite (Ni_0.39Fe_2.61O₄/ZrO₂) as a working material in the temperature range of 1073–1173 K. The produced CO-rich syngas had the H₂/CO ratio that was more suitable for methanol production than that produced by a conventional single-step steam reforming. This syngas production using the Ni_0.39Fe_2.61O₄/ZrO₂ as an oxidant was also demonstrated under direct irradiation by a solar-simulated, high-flux visible light in laboratory-scale fixed bed system. The directly-irradiated Ni_0.39Fe_2.61O₄/ZrO₂ particles acted simultaneously as good radiant absorbers and reactive chemical reactants to yield more than 90% of methane conversion to a 2:1 molar mixture of CO and H₂ under flux irradiation of 500 kW m⁻² in the residence time less than 1 s.     

High-temperature optical properties and stability of AlxOy–AlNx–Al solar selective absorbing surface prepared by DC magnetron reactive sputtering

Al_xO_y–AlN_x–Al selective absorbing surface was prepared by DC magnetron reactive sputtering with aluminum alloy (LY13)¹ in air and argon. The studies were carried out to access the high-temperature (400°C–600°C) optical properties and stability of the coatings. The coatings were found to withstand heating at 600°C for 30 min in 4.5×10⁻³ Pa vacuum with absorptance 0.94 and emittance 0.07 after annealing. After heating at 450°C for 10 h, the specimen still had good performance whose absorptance and emittance was 0.93 and 0.07, respectively. Auger electron spectroscopy was used to analyse the structure of the solar selective surface before and after annealing.     

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.     

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.     

Field effect surface passivation of SiO2/Si interfaces by heat treatment with high-pressure H2O vapor

We investigated a simple field effect passivation of the silicon surfaces using the high-pressure H₂O vapor heating. Heat treatment with 2.1×10⁶ Pa H₂O vapor at 260°C for 3 h reduced the surface recombination velocity from 405 cm/s (before the heat treatment) to 38 cm/s for the thermally evaporated SiO_x film/Si. Additional deposition of 140 nm-SiO_x films (x<2) with a high density of fixed positive charges on the SiO₂/Si samples further decreased the surface recombination velocity to 22 cm/s. We also demonstrated the field effect passivation for n-type silicon wafer coated with thermally grown SiO₂. Additional deposition of 210 nm SiO_x films on both the front and rear surfaces increased the effective lifetime from 1.4 to 4.6 ms. Combination of thermal evaporation of SiO_x film and the heat treatment with high-pressure H₂O vapor is effective for low-temperature passivation of the silicon surface.     

Iron precipitated onto ceria-zirconia nanoparticle mixtures for the production of hydrogen via two-step thermochemical water splitting

Several novel materials were synthesized by precipitating iron oxide (using the previously optimized 10% Fe loading by weight) onto mixtures of nanoparticle zirconia and ceria to investigate the effects of adding CeO₂ to FeO_x/ZrO₂ materials in the thermochemical water splitting reaction. At water splitting temperatures of 1000 °C (after thermal reduction at 1450 °C), the stability of the CeO₂-containing materials was lower than for the FeO_x/ZrO₂ material, and there was no advantage to adding CeO₂ to the FeO_x/ZrO₂ material. However, when operating at a water splitting (WS) temperature of 1200 °C, the stability increased and the hydrogen production was significantly higher over most materials compared with a water splitting temperature of 1000 °C. At a WS temperature of 1200 °C the FeO_x/Zr₇₅Ce₂₅O₂ (75% Zr₇₅O₂ and 25% CeO₂ by weight) and FeO_x/Zr₅₀Ce₅₀O₂ materials performed slightly better than the FeO_x/ZrO₂ material, and X-ray photoelectron spectroscopy data revealed that the surface concertation of iron is less important compared with water splitting at 1000 °C. The temperature programmed reduction data indicated that the FeO_x-CeO₂ interactions were weaker compared with FeO_x-ZrO₂ interactions, since the FeO_x reduction occurred at lower temperatures for the CeO₂-containing materials. The weaker interactions can explain why the stability was lower for the materials containing CeO₂ (sintering of FeO_x was likely more pronounced) The X-ray diffraction data revealed that ZrO₂-CeO₂ solid solutions formed after activation at 1450 °C and lattice volume calculations indicated that iron did incorporate into the ZrO₂-CeO₂ matrices. More incorporation was observed after water-splitting at 1200 °C compared with a lower temperature (1000 °C), and likely explains why the materials were more stable during water-splitting at 1200 °C.     

Oxygen-releasing step of nickel ferrite based on Rietveld analysis for thermochemical two-step water-splitting

We investigated the thermal reduction (T-R) of NiFe₂O₄, either supported by m-ZrO₂ or unsupported, as the oxygen-releasing step of a solar thermochemical water splitting cycle based on a ferrite/wustite redox system, by performing the Rietveld analysis using powder X-ray diffraction. The solid materials obtained after the T-R step at 1300–1400 °C were subjected to Rietveld analysis. The amounts and chemical compositions of the wustite phase produced by the T-R step and the remaining ferrite phase were identified quantitatively. Chemical reaction formulas for the different T-R temperatures were determined from the results. Consistency for the chemical reactions of the thermal reduction was discussed and evaluated comparing the O₂ amounts predicted by the chemical reaction formulas and measured experimentally by mass spectrometry.     

Reduction reactivity of CeO2-ZrO2 oxide under high O2 partial pressure in two-step water splitting process

The O₂-releasing reaction under the air with the reactive ceramics of CeO₂-ZrO₂ oxides which can be applied to solar hydrogen production via a two-step water splitting cycle using concentrated solar thermal energy was investigated. CeO₂-ZrO₂ oxides were synthesized by polymerized complex method at different Ce:Zr molar ratio. The solid solubility of ZrO₂ in fluorite structure of CeO₂ was in good agreement with the initial content of Zr ions at the preparation in CeO₂-ZrO₂ oxide. The O₂-releasing reaction in air with CeO₂-ZrO₂ oxides was studied. Different solid solubility (0%, 10%, 20%, 30%) of ZrO₂ in CeO₂ were examined. The amount of O₂ gas evolved in the reaction with Ce_1−xZr_xO₂ (0 ? x ? 0.3) solid solutions was more than that with CeO₂, and the largest yield of 2.9 cm³/g was exhibited at x = 0.2 (Ce_0.8Zr_0.2O₂) for an O₂ release at 1500 °C in air. The reduced cerium ion in Ce_0.8Zr_0.2O₂ was about 11%, which is seven times higher than that with CeO₂. The optical absorption and luminescence spectra of the CeO₂-ZrO₂ oxide obtained before and after the O₂-releasing reaction suggest that the reduction of Ce⁴⁺ with formation of oxygen defect in the air. The enhancement of the O₂-releasing reaction with CeO₂-ZrO₂ oxide is found to be caused by an introduction of Zr⁴⁺, which has smaller ionic radius than Ce³⁺ or Ce⁴⁺, in the fluorite structure.     

Thermochemical methane reforming using WO3 as an oxidant below 1173 K by a solar furnace simulator

Thermochemical methane reforming by a reactive redox system of WO₃ was demonstrated under direct irradiation of the metal oxide by a concentrated, solar-simulated Xe-lamp beam below 1173 K, for the purpose of converting solar high-temperature heat to chemical fuels. In the proposed cycling redox process, the metal oxide is expected to react with methane as an oxidant to produce syngas with a H₂/CO ratio of two, which is suitable for the production of methanol, and the reduced metal oxide which is oxidized back with steam in a separate step to generate hydrogen uncontaminated with carbon oxide. The ZrO₂-supported WO₃ gave about 45% of CO yield and 55% of H₂ yield with a H₂/CO ratio of about 2.4 in a temperature range of 1080–1160 K at a W/F ratio of 0.167 g min Ncm⁻³ (W is the weight of WO₃ phase and F is the flow rate of CH₄). The activity data under the solar simulation were compared to those for the WO₃/ZrO₂ heated by irradiation of an infrared light. This comparison indicated that the CO selectivity was much improved to 76–85% in the solar-simulated methane reforming, probably by photochemical effect due to WO₃ phase. The main solid product of WO₂ in the reduced WO₃/ZrO₂ was reoxidized to WO₃ with steam to generate hydrogen below 1173 K.     

Photocatalytic water splitting ability of Fe/MgO-rGO nanocomposites towards hydrogen evolution

Photocatalytic water splitting has greatly stimulated as an ideal technique for producing hydrogen (H₂) fuel by employing two renewable sources, i.e., water and solar energy. Here, we have adopted a facile hydrothermal approach for the successful synthesis of reduced graphene oxide (rGO) incorporated Fe/MgO nanocomposites followed by thermal treatment at inert atmosphere to investigate their ability for photodegradation and photocatalytic hydrogen evolution via water splitting. Transmission Electron Microscopy images of Fe/MgO-rGO nanocomposite ensured the distribution of Fe/MgO nanoparticles throughout rGO sheets. Notably, all rGO supported nanocomposites, especially the one, thermally treated at 500 °C at Argon (Ar) atmosphere has demonstrated significantly higher photocatalytic efficiency towards the photodegradation of a toxic textile dye, rhodamine B, than pristine MgO and commercially available Degussa P25 titania nanoparticles as well as other composites. Under solar irradiation, Fe/MgO-rGO (500) nanocomposite exhibited 86% degradation of rhodamine B dye and generated almost four times higher H₂ via photocatalytic water splitting compared to commercially available P25 titania nanoparticles. This promising photocatalytic ability of the Fe/MgO-rGO(500) nanocomposite can be attributed to the improved morphological and surface features due to heat treatment at inert atmosphere as well as escalated charge carrier separation with increased light absorption capacity imputed to rGO incorporation.     

A hybrid solar-assisted adsorption cooling unit for vaccine storage

A concept of a hybrid adsorption cooling unit for vaccine storage utilizing solar energy as a main power supply and a gas burner as an alternative power supply has been developed. The components of the cooling unit have been designed to work under the weathering conditions of Burkina Faso, West coast of Africa according to the requirements of the World Health Organization. For the first adsorber, which is driven by a gas burner, zeolite-13X has been selected. For the second adsorber to be driven by solar energy selective water sorbent SWS-2L has been applied. Water is selected as a refrigerant for both adsorbents. Theoretical investigations of the expected performance of the designed cooling unit have shown a coefficient of performance (COP) of 0.28 for the solar-operated system based on the heat input to the adsorption unit, at the design conditions of T_evap=−5 °C, T_con=55 °C, T_ads=38 °C, T_des(max)=122 °C. For the gas-heated system, also a COP of 0.28 has been estimated at the design conditions of T_evap=−5 °C, T_con=55 °C, T_ads=38 °C, T_des(max)=280 °C. The variations of COP, cooling capacity and the heating power required to operate both systems have been estimated for a broad range of desorption temperatures. It turns out that the SWS-2L/water system is much more sensitive to the operating conditions than the zeolite-13X/water system. The obtained results should serve in designing both control and heating components of the cooling unit.     

Experimental studies on bubble pump operated diffusion absorption machine based on light hydrocarbons for solar cooling

An experimental investigation of an air-cooled diffusion absorption machine operating with a binary light hydrocarbon mixture (C₄H₁₀/C₉H₂₀) as working fluids and helium as pressure equalizing inert gas is presented in this paper. The machine, made of copper an available and very good heat conducting metal, is intended to be solar powered heat from flat plate or common evacuated tube collectors. The cooling capacity is 40–47 W respectively for 9 and 11°C chilled water temperature. Cold is produced at temperatures between −10 and +10 °C for a driving temperature in the range of 120–150 °C.     

Thermochemical two-step water-splitting for hydrogen production using Fe-YSZ particles and a ceramic foam device

Fe₃O₄ supported on cubic yttria-stabilized zirconia (Fe₃O₄/c-YSZ) is proposed as a promising redox material for the production of hydrogen from water via a thermochemical two-step water-splitting cycle. In this study, the evolution of oxygen and hydrogen during the cyclic reaction was examined using Fe₃O₄/c-YSZ particles in order to demonstrate reproducible and stoichometric oxygen/hydrogen production through a repeatable two-step reaction. Subsequently, a ceramic foam device coated with Fe₃O₄ and c-YSZ particles was prepared and examined as a thermochemical water-splitting device in a directly irradiated receiver/reactor hydrogen production system. The Fe₃O₄/c-YSZ system formed a Fe-containing YSZ (Fe-YSZ) by high-temperature reaction between Fe₃O₄ and the c-YSZ support at 1400 °C in an inert atmosphere. The reaction mechanism of the two-step water-splitting cycle is associated with the redox transition of Fe²⁺–Fe³⁺ ions in the c-YSZ lattice. The Fe-YSZ particles exhibit good reproducibility for reaction with a hydrogen/oxygen ratio of approximately 2.0 throughout repeated cycles. The foam device coated with Fe-YSZ particles was also successful for continual hydrogen production through 32 repeated cycles. A 20–27% ferrite conversion was obtained using 10.5 wt% Fe₃O₄ loading over an irradiation period of 60 min.     

Annealing effects on Zn1−xMgxO/CIGS interfaces characterized by ultraviolet light excited time-resolved photoluminescence

Annealed Zn_1−xMg_xO/Cu(In,Ga)Se₂ (CIGS) interfaces have been characterized by ultraviolet light excited time-resolved photoluminescence (TRPL). The TRPL lifetime of the Zn_1−xMg_xO/CIGS film increased on increasing the annealing temperature to 250 °C, whereas the TRPL lifetime of the CdS/CIGS film had little change by annealing at temperatures lower than 200 °C. This is attributed to the recovery of physical damages by annealing, induced by sputtering of the Zn_1−xMg_xO film. The TRPL lifetime abruptly decreased with annealing at 300 °C. The diffusion of excess Zn from the Zn_1−xMg_xO film into the CIGS interface is clearly observed in secondary ion mass spectroscopy (SIMS) depth profiles. These results indicate that excess Zn at the vicinity of the CIGS surface acts as non-radiative centers at the interface. The TRPL lifetime of the Zn_1−xMg_xO/CIGS film annealed at 250 °C reached values to be comparable to that of the as-deposited CdS/CIGS film. Performance of the Zn_1−xMg_xO/CIGS cells varied with the annealing temperature in the same manner as the TRPL lifetime. The highest efficiency of the Zn_1−xMg_xO/CIGS solar cells was achieved for annealing at 250 °C. The results of the TRPL lifetime on annealing show that the cell efficiency is strongly influenced by the Zn_1−xMg_xO/CIGS interface states related to the damages and diffusion of Zn.     

Electrochromism in NiOx and WOx obtained by spray pyrolysis

Electrochromic films of NiO_x and WO_x were produced by the spray pyrolysis technique. The nickel-oxide-based coatings were obtained from an aqueous solution of nickel nitrate. Those obtained below 300° C did not show any diffraction peak when subjected to X-ray diffraction analysis, and those obtained above 400° C showed a diffraction pattern corresponding to cubic NiO. Films obtained below 300° C showed an electrochromic effect with an electrochromic efficiency of 30 cm²/C.Tungsten-oxide-based coatings were obtained from a solution of H₂WO₄ in aqueous ammonia. The films were grown at 150° C, and they showed a diffraction pattern corresponding to monoclinic WO₃ when subjected to a post-heat treatment at 400° C during ten minutes. The WO_x films showed a noticeable electrochromism under cation insertion, and presented an electrochromic efficiency of 42 cm²/C. Both as-deposited and heat-treated samples showed good electrochromism.