Comparing the solar-to-fuel energy conversion efficiency of ceria and perovskite based thermochemical redox cycles for splitting H2O and CO2

A thermodynamic analysis was conducted on a solar thermochemical plant for syngas generation via H₂O/CO₂-splitting redox cycles in order to determine the performance of six candidate redox materials under an array of operation conditions. The values obtained for the solar-to-fuel energy conversion efficiency are higher in relative order Zr-doped CeO₂ > undoped CeO₂ > La_0.6Ca_0.4MnO₃ > La_0.6Ca_0.4Mn_0.6Al_0.4O₃ > La_0.6Sr_0.4MnO₃ > La_0.6Sr_0.4Mn_0.6Al_0.4O₃. This ordering is attributed to their relative reducibility and re-oxidizability, where the doped and undoped ceria, that favor oxidation, outperform perovskites, that favor reduction and therefore require high flowrates of excess H₂O and CO₂ during re-oxidation. Solids-solid heat recuperation during the temperature swing between the redox steps is crucial, particularly for ceria because of its low specific oxygen exchange capacity per mole and cycle. Conversely, the efficiencies of the perovskites are more dependent on gas-gas heat recuperation due to the massive excess of H₂O/CO₂. Redox material thermodynamics and plant/reactor performance are closely coupled, and must be considered together to maximize efficiency. Overall, we find that Zr-CeO₂ is the most promising redox material, while perovskites which seem promising due to high H₂/CO production capacities under large H₂O/CO₂ flow rates, perform poorly from an efficiency perspective due to the high heating duties, especially for steam.     

Thermodynamic analysis of solar thermochemical energy absorption

Thermochemical energy conversion is analysed on a thermodynamic basis with particular interest in obtaining guidance as to solar thermochemical absorber design at an early stage of development when technical and cost information is often unreliable. An earlier-used thermodynamic equivalence technique which is equally applicable to both the endothermic and exothermic reactions has been developed to the point where it gives a clear insight into all sources of heat and work. The method is applied in particular to separating endothermic reactions of which ammonia dissociation is a prime example. A reversibility ratio is defined as the ratio of irreversible to reversible work and it is shown that in a practical solar thermochemical absorber design the reversibility ratio should be minimized, corresponding to reaction temperature minimization and therefore to tower energy losses and to potential for use of lower cost reactor materials and more active catalysts. Values of reversibility ratio are calculated for the ammonia system and are discussed in relation to solar thermochemical absorber design. In a final analysis employing the thermodynamic equivalence technique, it is shown that the apparent paradox between liquid and alternative gas pump work requirements in a liquid/gas thermochemical system is thermodynamically consistent with the internal generation of effective work from the heat source used to drive the endothermic reaction system.     

Comparison of thermochemical,electrolytic, photoelectrolytic and photochemical solar-to-hydrogen production technologies

Hydrogen produced from solar energy is one of the most promising solar energy technologies that can significantly contribute to a sustainable energy supply in the future. This paper discusses the unique advantages of using solar energy over other forms of energy to produce hydrogen. Then it examines the latest research and development progress of various solar-to-hydrogen production technologies based on thermal, electrical, and photon energy. Comparisons are made to include water splitting methods, solar energy forms, energy efficiency, basic components needed by the processes, and engineering systems, among others. The definitions of overall solar-to-hydrogen production efficiencies and the categorization criteria for various methods are examined and discussed. The examined methods include thermochemical water splitting, water electrolysis, photoelectrochemical, and photochemical methods, among others. It is concluded that large production scales are more suitable for thermochemical cycles in order to minimize the energy losses caused by high temperature requirements or multiple chemical reactions and auxiliary processes. Water electrolysis powered by solar generated electricity is currently more mature than other technologies. The solar-to-electricity conversion efficiency is the main limitation in the improvement of the overall hydrogen production efficiency. By comparison, solar powered electrolysis, photoelectrochemical and photochemical technologies can be more advantageous for hydrogen fueling stations because fewer processes are needed, external power sources can be avoided, and extra hydrogen distribution systems can be avoided as well. The narrow wavelength ranges of photosensitive materials limit the efficiencies of solar photovoltaic panels, photoelectrodes, and photocatalysts, hence limit the solar-to-hydrogen efficiencies of solar based water electrolysis, photoelectrochemical and photochemical technologies. Extension of the working wavelength of the materials is an important future research direction to improve the solar-to-hydrogen efficiency.     

Improved photon management in a photoelectrochemical cell with Nd-modified TiO2 thin film photoanode

Photon management involving particularly an up-conversion process is proposed as a relatively novel strategy for improving the efficiency of hydrogen generation in photoelectrochemical cells (PEC) with wide-band gap photoanodes. Optically active photoanode has been constructed by electrodeposition of titanium dioxide nanopowders containing Nd³⁺ ions, synthesized via a sol-gel method, onto ITO/TiO₂(thin film) substrates. Thin films of TiO₂ have been deposited by means of RF magnetron sputtering in an ultra-high-vacuum system. X-ray diffraction, scanning electron microscopy, UV-VIS-NIR spectrophotometry, and photoluminescence have been applied to assess the properties of photoanodes. In experiments involving photon-assisted water splitting, an external up-converter containing Yb³⁺/Er³⁺ rare-earth ions has been used. Photocurrent as a function of voltage (V_B) under illumination with white light is relatively high (280 μA at V_B = 0 V) for pure TiO₂ thin films and it is not affected by the electrodeposition of TiO₂:Nd³⁺ powders. NIR-driven up-conversion with laser excitation at λ = 980 nm has been found responsible for a 13-fold increase in photocurrent at V_B = 0 V in the modified PEC configuration.     

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.     

Likely near-term solar-thermal water splitting technologies

Thermodynamic and materials considerations were made for some two- and three-step thermochemical cycles to split water using solar-thermal processing. The direct thermolysis of water to produce H₂ using solar-thermal processing is unlikely in the near term due to ultra-high-temperature requirements exceeding 3000 K and the need to separate H₂ from O₂ at these temperatures. However, several lower temperature (<2500 K) thermochemical cycles including ZnO/Zn, Mn₂O₃/MnO, substituted iron oxide, and the sulfur–iodine route (S–I) provide an opportunity for high-temperature solar-thermal development. Although zirconia-based materials are well suited for metal oxide routes in terms of chemical compatibility at these temperatures, thermal shock issues are a major concern for solar-thermal applications. Hence, efforts need to be directed towards methods for designing reactors to eliminate thermal shock (ZrO₂ based) or that use graphite (very compatible in terms of temperature and thermal shock) with designs that prevent contact of chemical species with graphite materials at high temperatures. Fluid-wall reactor configurations where inert gases provide a blanket to protect the graphite wall appear promising in this regard, but their use will impact process efficiency. For the case of S–I up to 1800 K, silicon carbide appears to be a suitable material for the high-temperature H₂SO₄ dissociation. There is a need for a significant amount of work to be done in the area of high-temperature solar-thermal reactor engineering to develop thermochemical water splitting processes.     

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

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

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.     

Modeling of a two-step solar hydrogen production plant

The promising advances in research in two-step solar hydrogen production from water have increased interest in producing hydrogen with this technology. In this framework, the Hydrosol II Project pilot plant for producing continuous solar hydrogen from water using a ferrite-based redox technology was erected at the CIEMAT-Plataforma Solar de Almería. Two reactors allow the oxidation and reduction steps to be performed in parallel, which, sequentially switched, make hydrogen production quasi-continuous.     

A spinel ferrite/hercynite water-splitting redox cycle

Cobalt ferrites are deposited on Al₂O₃ substrates via atomic layer deposition, and the efficacy of using these in a ferrite water splitting redox cycle to produce H₂ is studied. Experimental results are coupled with thermodynamic modeling, and results indicate that CoFe₂O₄ deposited on Al₂O₃ is capable of being reduced at lower temperatures than CoFe₂O₄ (200–300 °C) due to a reaction between the ferrite and substrate to form FeAl₂O₄. Although the reaction of FeAl₂O₄ and H₂O is not as thermodynamically favorable as that of FeO and H₂O, it is shown to be capable of splitting H₂O to produce H₂ if non-equilibrium conditions are maintained. Significant quantities of H₂ are produced at reduction temperatures of only 1200 °C, whereas, CoFe₂O₄ produced little or no H₂ until reduction temperatures of 1400 °C. CoFe₂O₄/Al₂O₃ was capable of being cycled at 1200 °C reduction/ 1000 °C oxidation with no obvious deactivation.