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.     

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.     

One-pot sulfurized synthesis of ZnIn2S4/S,N-codoped carbon composites for solar light driven water splitting

To enhance the intrinsic active sites and to suppress the recombination of charge carriers, ZnIn₂S₄ modified with S,N-codoped carbon (ZIS/SN-C) composites were prepared for solar light driven water splitting via the one-pot sulfurized route. Compared with g-C₃N₄ and S-doped g-C₃N₄, the combined effect between S,N-codoped carbon and ZnIn₂S₄ can greatly enhance the photocatalytic activity of ZIS/SN-C. The optimal 4-ZIS/SN-C with the Zn(II) content of 13.78% and the calculated In/Zn molar ratio of 2.03:1 presents the H₂ evolution rate of 2937.1 μmol g^?1 h^?1, which is 2.98 and 23.42 times higher than that of one-pot sulfurized ZnIn₂S₄ and S-doped g-C₃N₄, respectively. However, long-term photo-corrosion induces to the declined durability of 4-ZIS/SN/C for water splitting after three cycles. S vacancies of ZnIn₂S₄ serve as the efficient active sites of H₂ evolution reaction, and S, N-codoped carbon acts as the photo-induced electrons trapper. The one-pot sulfurized approach is thus a potential strategy to fabricate metal sulfide-based photocatalysts.     

Hydrogen production by water splitting on manganese ferrite-sodium carbonate mixture: Feasibility tests in a packed bed solar reactor-receiver

The sodium manganese mixed ferrite thermochemical cycle Na(Mn_1/3Fe_2/3)O₂/(MnFe₂O₄ + Na₂CO₃) for sustainable hydrogen production has been implemented in a solar reactor-receiver, packed with indirectly heated MnFe₂O₄/Na₂CO₃ mixture pellets, with the aim of verifying its feasibility and of determining the critical aspects of the process. The reactor operates at nearly constant temperature in the range 750–800 °C; the shift between the hydrogen-producing and regeneration steps is obtained by switching the reactive gas from water to carbon dioxide. Hydrogen produced during 1-h operation of the reactor is in the range of 130–460 μmol/g of mixture, depending on experimental conditions. Compared to other existing prototypes, the implemented process obtains comparable production efficiencies while operating at lower temperature both in the hydrogen production and regeneration phases.     

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.     

Light-assisted synthesis of Au/TiO2 nanoparticles for H2 production by photocatalytic water splitting

A series of Au/TiO₂ photocatalysts was synthesized via the light assistance through the photo-deposition for H₂ production by photocatalytic water splitting using ethanol as the hole scavenger. Effect of solution pH in the range of 3.2–10.0 on the morphology and photocatalytic activity for H₂ production of the obtained Au/TiO₂ photocatalysts was explored. It was found that all Au/TiO₂ photocatalysts prepared in different solution pH exhibited comparable anatase fraction (～0.84–0.85) and crystallite size of TiO₂ (21–22 nm), but showed different quantity of deposited Au nanoparticles (NPs) and other properties, particularly the particle size of the Au NPs. Among all prepared Au/TiO₂ photocatalysts, the Au/TiO₂ (10.0) photocatalyst exhibited the highest photocatalytic activity for H₂ production, owning to its high metallic state and small size of Au NPs. Via this photocatalyst, the maximum H₂ production of 296 μmol (～360 μmol/g?h) was gained at 240 min using the 30 vol% ethanol as the hole scavenger at the photocatalyst loading of 1.33 g/L under the UV light intensity of 0.24 mW/cm² with the quantum efficiency of 61.2% at 254 nm. The loss of the photocatalytic activity of around 20% was observed after the 5th use.     

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

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

Monolithically-integrated BiVO4/p+-n GaAs1-xPx tandem photoanodes capable of unassisted solar water splitting

Monolithically-integrated tandem photoanodes were fabricated on substrates consisting of epitaxial n-GaAs_1-xP_x (x ? 0.32) grown on n⁺-GaAs wafers. A p⁺-n junction photovoltaic (PV) cell was first formed by zinc diffusion into the n-GaAs_0.68P_0.32 from a deposited ZnO coating. After diffusion the ZnO serves as a transparent electrical contact to the resulting p⁺-GaAs_0.68P_0.32 surface layer. Transparent, conducting SnO₂:F provides chemical and mechanical protection for the ZnO and the underlying PV cell, and it electrically connects this cell to a top BiVO₄ photocatalyst layer. In some photoanodes, a WO₃ thin film was interposed between the SnO₂:F and BiVO₄. All oxide coatings were produced by ultrasonic spray pyrolysis except WO₃, which was spin coated. Unassisted (unbiased) solar water splitting was achieved, with a solar-to-hydrogen efficiency approaching 2%, without addition of any co-catalyst to the BiVO₄ surface. This work can provide insights to other researchers regarding scalable, low cost approaches for the planar monolithic integration of oxide photoanode materials with PV cells to create new tandem devices.     

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%).     

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.     

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.