Thermochemical Water Splitting Research Articles

Thermochemical activation of CO2 into syngas over ceria-supported niobium oxide catalyst: An integrated experimental-DFT study

Thermochemical splitting of a mixture of CO2 and water into syngas (and methane) remains a viable approach toward an industrial-scale treatment of CO2 emission. However, most deployed catalysts encompass expensive metallic ingredients such as Pd or Pt. In an integrated experimental-modelling approach, this work reports a high conversion of CO2 over alternative and cost-effective configurations. Ceria-based catalysts are proven to be effective in numerous catalytic processes owing to the facile switch in the Ce redox cycle. Evolution of H2 and CO from thermochemical splitting of water and carbon dioxide is an important process in the production of syngas and in fuel cell applications. In this study, NbOx ceria catalysts are prepared, characterized, and applied for production of syngas via the thermochemical splitting of CO2 and gaseous water. It was observed that presence of Nb in the ceria matrix up to 12 wt%, increases the reaction yield at higher temperature (up to 79% CO2 conversion with 80% selectivity to syngas at 600 ºC). Moreover, the catalytic reaction was found to display a higher selectivity towards syngas over the ceria supported catalysts. The attained conversion is higher than other ceria-supported catalysts such as Rh-CeO2, CeO2-ZrO2, and V2O5-CeO2. Mapped-out reaction pathways by DFT calculations portray accessible routes into syngas. Results provided herein should be useful to optimize a continuous process for the valorization of CO2 into syngas over relatively affordable a catalytic formulation.

Synthesis and structure of high-purity BaCe0.25Mn0.75O3: an improved material for thermochemical water splitting

Solar thermochemical hydrogen production (STCH) via redox-active metal oxides is an approach for direct solar-driven hydrogen generation typically using a high-temperature redox cycle involving refractory oxides and steam. Typical cycles involve high-temperature reduction of oxides to form oxygen vacancies, followed by lower temperature reaction between oxygen vacancies and steam where the oxide is re-oxidized and the steam is reduced to hydrogen. Only a few materials have demonstrated reversible cycling under the typically harsh STCH conditions (e.g. 1500°C reduction, 900°C re-oxidation) and critical questions remain on the true reversibility of non-stoichiometric multi-cation oxide systems, significantly hampered by the lack of single-phase samples for these material systems. To date, most STCH processes have relied on CeO2 as a benchmark active material, but more recently, the 12R phase of BaCe0.25Mn0.75O3 (BCM) has demonstrated greater hydrogen-generation potential at lower peak temperatures. However, previous reports of 12R-BCM have included large fractions, > 10 wt%, of secondary phases, which complicate analysis of the stability and performance. A comprehensive understanding of the redox mechanism and reversibility of the process in BCM can only be achieved with nearly single-phase samples which, to date, have been difficult to produce. Here two approaches to BCM synthesis are reported: solid state and sol–gel-based routes. It is demonstrated that both routes can be tuned to produce the 12R structure with > 97 wt% yield when annealed ≥1450°C. Herein synchrotron-based diffraction measurements of rhombohedral 12R-BCM enabled characterization of the anisotropy between thermal expansion along the c-axis and within the ab plane. The impact of high-temperature redox cycling on the stability and phase fraction of the 12R-BCM polytype was also investigated. These results offer two viable routes for synthesis of high-purity 12R-BCM critically needed for evaluating the efficacy of BCM as a STCH material and validate its ability to split water at lower temperatures over extended numbers of redox cycles.

A Comparative Assessment of Thermodynamic and Exergoeconomic Performances of Three Thermochemical Water-Splitting Cycles of Chlorine Family for Hydrogen Production

Hydrogen production processes utilizing hydrocarbon-based sources as feedstocks have severe environmental implications (when not incorporating carbon capturing and storage technology) in addition to resulting in depletion of non-sustainable naturally occurring fuel sources. In this regard, thermochemical water-splitting is an extremely environmentally benign pathway for obtaining sustainable hydrogen. Thus, this paper studies and comparatively evaluates three different thermochemical cycles of the chlorine family for hydrogen production which include iron-chlorine, copper-chlorine, and magnesium-chlorine cycles. Each cycle is first modeled and simulated in Aspen-plus and then analyzed from thermodynamic and exergoeconomic viewpoints. A thermodynamic and exergoeconomic performance comparison of the three thermochemical cycles is further performed in terms of their overall efficiencies, net heat input and rejection rates, exergy destruction rates, unit costs of hydrogen, hourly levelized cost rates, and cost rates of exergy destruction. All cycles are modeled and simulated by considering the incorporation of waste heat recovery from a steel plant and internal heat recovery within each cycle to improve the process efficiencies by reducing the overall thermal energy consumption. According to the performed analyses, the copper-chlorine cycle has the highest energy (79.7%) and exergy (81.1%) efficiencies followed by the iron-chlorine cycle (energy and exergy efficiencies of 48.8% and 49.6%, respectively) with the magnesium-chlorine cycle exhibiting the lowest overall energy (19.8%) and exergy (20.2%) efficiencies. Moreover, the iron-chlorine cycle demonstrates the lowest unit cost of hydrogen (0.7 $/kg) followed by the copper-chlorine cycle (4 $/kg) with the magnesium-chlorine cycle exhibiting an extremely high unit hydrogen cost (8.9 $/kg). This study also identifies certain key factors that largely impact the cost of hydrogen and comprehensively discusses the influence and extent of each factor on the cost of hydrogen.

Dynamic behavior of solar thermochemical reactors for fuel generation: Modeling and control strategies

Solar thermochemical water splitting provides an efficient route for converting solar energy into renewable fuels. The operation of solar thermochemical reactor under real on-sun condition requires in-depth understanding of its dynamic behaivor under fluctuating direct normal irradiation (DNI). In this work, we developed a 2D axial-symmetric multi-physical model to assess the reactor’s dynamic behavior with three oxygen removing technologies electrochemical oxygen pump (EOP), sweep gas (SG), and vacuum pump (VP), under varying solar irradiations. To alleviate the negative effect of decreased DNI, two control strategies (CS) including varying operational conditions for oxygen removing technologies (CS1) and replacing the reduction step with the oxidation step (CS2) were conducted. We found that CS1 was only effective when DNI reduction was larger than 75 % over the whole reduction step (case 2). In general, CS2 can be implemented to alleviate the efficiency decrease for all DNI variations expect for the case 2 in this study. Especially, CS2 significantly increased the solar-to-fuel efficiency compared to the case without control strategy for the reduced DNI from 1000 W/m2 to 500 W/m2 during the whole reduction step. The reactor dynamic behavior in response to the daily DNI variations is also reported which shows that the efficiency profiles are highly in line with the DNI profile. This modeling work as well as proposed control strategies can be used to guide the design and control of solar thermochemical reactors under realistic conditions and hence for better assessing the performance of the reactor in practice.

Techno economic feasibility study on hydrogen production using concentrating solar thermal technology in India

The techno-economic analysis of hydrogen (H2) production using concentrating solar thermal (CST) technologies is performed in this study. Two distinct hydrogen production methods, namely: a) thermochemical water splitting [model 1] and b) solid oxide electrolysers [model 2], are modeled by considering the total heat requirement and supplied from a central tower system located in Jaisalmer, India. The hourly simulated thermal energy obtained from the 10 MWth central tower system is fed as an input to both these hydrogen production systems for estimating the hourly hydrogen production rate. The results revealed that these models yield hydrogen at a rate of 31.46 kg/h and 25.2 kg/h respectively for model 1 and model 2. Further, the Levelized cost of hydrogen (LCoH) for model 1 and model 2 is estimated as ranging from $ 8.23 and $ 14.25/kg of H2 and $ 9.04 and $ 19.24/kg, respectively, for different scenarios. Overall, the present work displays a different outlook on real-time hydrogen production possibilities and necessary inclusions to be followed for future hydrogen plants in India. The details of the improvisation and possibilities to improve the LCoH are also discussed in this study.

Techno-economic evaluation of solar-driven ceria thermochemical water-splitting for hydrogen production in a fluidized bed reactor

Thermochemical water splitting (TCWS) is an attractive and promising approach for hydrogen fuel production to replace fossil fuels and address climate change. The novel approach used in this study is the indirect irradiation of the ceria particle with solar-heated nitrogen in a fluidized bed reactor which improved the ceria thermo-reduction and increased hydrogen yield. The TCWS plant featured additional units for oxygen co-production, and excess heat recovery to generate electricity and reduce the saleable hydrogen price. Two fluidized bed reactors for ceria thermo-reduction and oxidation using steam were modelled in Aspen Plus for hydrogen production at a 70% capacity factor. A photovoltaic (PV)-battery module in addition to the solar parabolic dish collector (PDC) was then used to deliver operation-round electricity supply and drive mechanical and control systems, reducing overall plant energy cost. Three minimum selling prices of hydrogen were considered based on the achievable products of the TCWS plant: (i) pricing based on no co-products, (ii) pricing including oxygen revenue, and (iii) pricing including oxygen and electricity revenue. The TCWS plant achieved a minimum selling price (MSP) of 3.92 USD/kg H2 (including oxygen and electricity revenue) at a 10% discount rate which is the lowest for solar-driven TCWS hydrogen compared with other similar studies. Sensitivity analyses showed that discount rate, steam Rankine cycle, power block, cost of ceria and hydrogen storage, and price of oxygen, respectively, had the highest impact on the MSP of the TCWS hydrogen plant. The switch value analysis (SVA) was used to determine the potential of achieving the global target hydrogen price of 2 USD/kg based on a single parameter assessment. The TCWS plant proposed in this work provides a promising approach toward achieving future hydrogen prices below 2 USD/kg when a lower discount rate of 5% is utilised. It was established that the choice and size of concentrated solar power (CSP) technology integration, co-generation, and heat recovery are critical to the system efficiency and economic viability of a solar-driven TCWS hydrogen production. This work demonstrated the use of ceria as a metal oxide feed suitable for solar TCWS hydrogen production with a promising economic potential for a global target price of less than 2 USD/kg H2 based on the choice of process-CSP configuration.

Wettability of Nanostructured Transition-Metal Oxide (Al2O3, CeO2, and AlCeO3) Powder Surfaces.

Wettability has been the focal point of many studies in metal oxide materials due to their applications in water–gas shift reactions, organic reactions, thermochemical water splitting, and photocatalysis. This paper presents the results of systematic experimental studies on the wettability of surfaces of nanostructured transition-metal oxides (TMOs) (Al2O3, CeO2, and AlCeO3). The wettability of nanoparticles was investigated by measuring contact angles of different concentrations of water-based nanofluids (0.05–0.1 wt%) on the glass slide. The morphology, the heterostructure, and the nature of incorporated nanoparticles were confirmed by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Characteristic diffraction patterns of the nanomaterials were evaluated using energy-dispersive X-ray spectroscopy (EDS) and X-ray diffraction (XRD) techniques. The contact angles of water–Al2O3, water–CeO2, and water–AlCeO3 were measured as 77.5 ± 5°, 89.8 ± 4°, and 69.2 ± 1°, respectively. This study suggests that AlCeO3 is strongly water-wet (hydrophilic), while CeO2 is weakly water-wet (hydrophobic). It further demonstrated that the sizes and compositions of the nanoparticles are key parameters that influence their wetting behaviors.

Screening Ruddlesden-Popper (n=1) Oxide Materials for Thermochemical Water Splitting By Density Functional Theory

Thermochemical redox reactors store concentrated solar power by thermally inducing an oxygen deficiency within a metal oxide structure. The metal oxide’s affinity for reoxidation allows it to facilitate the splitting of H2O or CO2 to produce H2 or CO for syngas formation.[1] Typically, high temperatures (>1400 °C) are used to drive the reduction of the benchmark material, CeO2, [2] however there is motivation to lower this temperature and investigate new metal oxides capable of larger fuel productions. Perovskite materials have been thoroughly investigated due to their crystallographic stability and ability to accommodate relatively large oxygen deficiencies. Emery et al. [3] conducted a wide computational screening of this family of materials based on a few simple thermodynamic parameters originally proposed by Meredig and Wolverton. [4]Herein, we extend these previous studies and investigate the A2BO4 Ruddlesden-Popper (RP) oxides family [5], layered perovskites, that have previously demonstrated fast redox kinetics and large oxygen storage as solid oxide fuel cell cathodes.[6] A combination of screening parameters based on charge neutrality, Goldschmidt tolerance and computed defect formation energy, identified 38 possible RP candidate materials. One of which - Ca2MnO4-δ – was taken forward to experimental testing due to its Earth abundant elements. The powder was synthesized via a modified Pechini method and thermal analysis experiments demonstrated thermally driven oxygen evolution from 800 to 1200 °C equating to a non-stoichiometry of δ=0.18. High-temperature X-ray diffraction alluded to the formation of a CaMn2O4 secondary phase above 1075 °C, therefore consequent thermochemical water splitting cycles were carried out at a maximum of 1000 °C. Oxidation under steam at 800 °C demonstrated good hydrogen production volumes, although gas production on further cycles was limited by particle sintering observed by scanning electron microscopy. Further investigations aim to understand and improve the cyclability and kinetics under different reaction temperatures and humidity. This study outlines, with experimental validation, how computational screening can be used to find future suitable RP candidates for thermochemical water splitting whose performance can be further improved with doping strategies and morphological adaptation.

Review of Thermochemical Technologies for Water and Energy Integration Systems: Energy Storage and Recovery

Thermochemical technologies (TCT) enable the promotion of the sustainability and the operation of energy systems, as well as in industrial sites. The thermochemical operations can be applied for energy storage and energy recovery (alternative fuel production from water/wastewater, in particular green hydrogen). TCTs are proven to have a higher energy density and long-term storage compared to standard thermal storage technologies (sensible and latent). Nonetheless, these require further research on their development for the increasing of the technology readiness level (TRL). Since TCTs operate with the same input/outputs streams as other thermal storages (for instance, wastewater and waste heat streams), these may be conceptually analyzed in terms of the integration in Water and Energy Integration System (WEIS). This work is set to review the techno-economic and environmental aspects related to thermochemical energy storage (sorption and reaction-based) and wastewater-to-energy (particular focus on thermochemical water splitting technology), aiming also to assess their potential into WEIS. The exploited technologies are, in general, proved to be suitable to be installed within the conceptualization of WEIS. In the case of TCES technologies, these are proven to be significantly more potential analogues to standard TES technologies on the scope of the conceptualization of WEIS. In the case of energy recovery technologies, although a conceptualization of a pathway to produce usable heat with an input of wastewater, further study has to be performed to fully understand the use of additional fuel in combustion-based processes.

A Comprehensive Review on Two-Step Thermochemical Water Splitting for Hydrogen Production in a Redox Cycle

The interest in and need for carbon-free fuels that do not rely on fossil fuels are constantly growing from both environmental and energetic perspectives. Green hydrogen production is at the core of the transition away from conventional fuels. Along with popularly investigated pathways for hydrogen production, thermochemical water splitting using redox materials is an interesting option for utilizing thermal energy, as this approach makes use of temperature looping over the material to produce hydrogen from water. Herein, two-step thermochemical water splitting processes are discussed and the key aspects are analyzed using the most relevant information present in the literature. Redox materials and their compositions, which have been proven to be efficient for this reaction, are reported. Attention is focused on non-volatile redox oxides, as the quenching step required for volatile redox materials is unnecessary. Reactors that could be used to conduct the reduction and oxidation reaction are discussed. The most promising materials are compared to each other using a multi-criteria analysis, providing a direction for future research. As evident, ferrite supported on yttrium-stabilized zirconia, ceria doped with zirconia or samarium and ferrite doped with nickel as the core and an yttrium (III) oxide shell are promising choices. Isothermal cycling and lowering of the reduction temperature are outlined as future directions towards increasing hydrogen yields and improving the cyclability.

Life cycle assessment of three types of hydrogen production methods using solar energy

A comprehensive life cycle assessment (LCA) is carried out for three methods of hydrogen production by solar energy: hydrogen production by PEM water electrolysis coupling photothermal power generation, hydrogen production by PEM water electrolysis coupling photovoltaic power generation, and hydrogen production by thermochemical water splitting method using S–I cycle coupling solar photothermal technology. The assessment also contains an evaluation of four environmental factors which are global warming potential, acidification potential, ozone depletion potential, and nutrient enrichment potential. After conducting a quantitative analysis of all three methods with environmental factors being considered, a conclusion has been drawn: The global warming potential and the acidification potential of the thermochemical water splitting by S–I cycle coupling solar photothermal technology are 1.02 kg CO 2 -eq and 6.56E-3 kg SO 2 -eq. And this method has significant advantages in the environmental impact of the whole ecosystem. • Photothermal technology coupling hydrogen production by S–I cycle has the lowest environmental impact. • Optimal heat source for PEM water electrolysis is photovoltaic power generation. • Reducing the pollution in the construction of plant can reduce the pollution of the whole hydrogen production system. • Increasing the lifetime of the system can reduce the environmental impact of hydrogen production.

Towards chemical equilibrium in thermochemical water splitting. Part 1: Thermal reduction

The efficiency of many processes strongly depends on their thermodynamic reversibility, i.e., proximity to equilibrium throughout the process. In thermochemical cycles for water and/or carbon dioxide splitting, thermochemical air separation, and thermochemical energy storage, operating near equilibrium means that the oxygen chemical potential of the solid and gas phases must not differ significantly. We show that approaching this ideal is possible in thermal reduction only if the reaction step occurs at a specific, reaction coordinate- and material-dependent temperature. The resulting thermal reduction temperature profile also depends on the ratio of gas and solid flows. • Method to achieve reversible/equilibrium reduction in water splitting cycles. • Reversible isothermal reduction is not feasible in practice. • Strong technical and physical limitations on the amount of sweep gas. • Limited impact of gas purity on reduction extent at fixed flow/maximum temperature. • High reduction temperatures expand the solution space for high cycle efficiency.

Study of a new receiver-reactor cavity system with multiple mobile redox units for solar thermochemical water splitting

Solar thermochemical redox cycles could be a path to efficient, large-scale renewable hydrogen production. A new receiver-reactor concept is presented that combines characteristics of the most successful receiver-reactor systems to date, with features of concepts showing the highest efficiency potential. The key features of the system are movable reactive structures in combination with linear transportation systems and dedicated oxidation reactors. The application of several of these units allows the continuous operation of the receiver-reactor and permits the implementation of a solid–solid heat recovery system. Both of these characteristics are important to increase the system efficiency beyond the current state of technology. A numerical model is developed to simulate a basic cubic design version of the new concept and to analyse its performance. Parameter variations are studied amongst others for different cavity sizes, solar concentration factors and numbers of movable reactive structures. By avoiding the cyclic heating of the inert reactor vessel, the model predicts high efficiency values above 14% even for non-optimized designs. Furthermore, the basic concept of the heat recovery system is modelled with heat recovery rates of up to 20% in its most simple implementation. The new concept has the features required for highly performant systems and opens up a large parameter space for reactor design and operation optimization.

Permeability and stability enhancement of dual-phase membrane by nickel-based porous layer for water splitting

The high oxygen permeability and stability of oxygen transport membrane (OTM) materials remain critical issues in the implementation of hydrogen production via thermochemical water splitting. In this study, a novel design of a fluorite phase Ce0.85Pr0.15O2-δ (CP) porous layer coupled with a nickel-based catalyst anchored to a dual-phase Ce0.85Pr0.15O2-δ-Pr0.6Sr0.4Fe0.9Al0.1O3-δ (CP-PSFA) ceramic membrane is developed owing to its excellent tolerance in the reductive atmosphere during static experiments. The oxygen permeability and hydrogen production performance of the modified CP-PSFA OTM were improved significantly with the coating of the CP porous layer; that is, a high O2 permeation flux of 3.7 mL cm-2 min-1 at 925 °C under a reductive atmosphere was achieved, which was approximately 43% higher than that of its counterpart. Meanwhile, after the nickel-based catalyst was loaded, the hydrogen production rate reached 1.79 mL cm-2 min-1 at 925 °C with the condition of optimal catalyst loading (30 wt% NiO), which shows a 64% increase compared to its counterpart. In addition, the long-term stability of the modified membranes remained intact. The results prove that the CP porous layer loaded with a nickel-based catalyst improves the permeability of the CP-PSFA ceramic membrane as well as the stability, providing an effective strategy for the design of high-performance OTMs for thermochemical water splitting for hydrogen production.

Sorbent-based oxygen separation with YBC114 for energy storage systems

In this work, we aimed to design, build, and evaluate an oxygen separation system to provide an inert sweep gas with low oxygen partial pressure (pO2) to redox-active thermochemical energy conversion reactors for a range of applications, including two-step redox cycles for thermochemical energy storage, water splitting, and carbon-dioxide splitting. The separation is based on an oxygen-selective sorbent, YBaCo4O7+δ (YBC114), which has excellent oxygen sorption and desorption properties demonstrated in our previous work. The oxygen separation performance of YBC114 was comprehensively studied by thermogravimetric analysis, sorption breakthrough experiments, and temperature swing sorption - desorption cycles. The results reveal that YBC114 can produce inert sweep gas with an oxygen concentration of less than 100 ppmv for at least 20 min during the thermal swing adsorption (TSA) cycle with the current sorption bed configuration, and the performance is consistent from cycle to cycle. The optimal sorption and desorption temperatures for the TSA process with YBC114 are determined to be 300 °C and 500 °C, respectively. Although challenges remain for the current separation system (e.g., high sorption temperature and slow kinetics), this study demonstrates the potential to use the oxygen-selective sorbent to produce an inert sweep gas, the feasibility of the oxygen separation concept, and guides new sorbent material development to make this application economically practical. A simple procedure is described for designing the YBC114 oxygen separation process.

Hydrogen production by thermochemical water splitting cycle using low‐grade solar heat and phase change material energy storage system

Hydrogen production by thermochemical water splitting cycle using low‐grade solar heat and phase change material energy storage system

Thermodynamic Guiding Principles for Designing Nonstoichiometric Redox Materials for Solar Thermochemical Fuel Production: Ceria, Perovskites, and Beyond

Two-step solar thermochemical water splitting is a promising pathway for renewable fuel production. Among the state-of-the-art materials, ceria tends to favor the oxidation step while perovskites favor the reduction step and developing a champion material with well-balanced redox thermodynamics remains a key challenge. A generic thermodynamic framework is thus presented to guide material design. More details can be found in article number 2000925, Wojciech Lipiński and co-workers.

Effects of coexisting oxoanions on SO<sub>3</sub> decomposition activity of molten-phase potassium metavanadate catalysts

Molten-state potassium metavanadate (KVO3) supported on mesoporous SiO2 materials have emerged as active catalysts for SO3 decomposition over a moderate temperature range (≤650 °C), which is a potential O2 evolution reaction useful for solar thermochemical water splitting. The molten phase formed at ≥520 °C contained tetrahedral VO42−, which plays a vital role in accelerating the SO3 uptake and conversion to SO2/O2. The present study aimed to reveal how the SO3 decomposition activity is affected by adding other oxoanions such as borate (BO33−), carbonate (CO32−), and phosphate (PO43−) into the melt. Although borate showed a deteriorating effect, phosphate tended to improve the catalytic activity when the P/V molar ratio was equal to or less than 0.5. The addition of phosphate produced a mixed phosphate vanadate with a composition of KV2PO8, which consists of infinite tetrahedral PO4 and pyramidal VO5 linked by vertex sharing. Because of the congruent melting at temperature as low as ∼530 °C, KV2PO8 may be expected as another candidate of active molten phase catalyst for SO3 decomposition.

Hydrogen production by thermochemical water splitting with La0.8Al0.2MeO3-δ (Me= Fe, Co, Ni and Cu) perovskites prepared under controlled pH

Aluminum based perovskites, La0.8Al0.2MeO3-δ (Me = Co, Ni, Fe, Cu), were synthesized following the Pechini method at different pHs and evaluated for hydrogen production by water splitting in a two-step thermochemical cycle. The pH of the synthesis medium showed a critical influence in the redox properties of the aluminum-based perovskites during the thermochemical cycle. Both the thermal reduction and the hydrolysis step produce irreversible changes in the crystalline structure of La0.8Al0.2MeO3-δ perovskites prepared at acid pH, avoiding the cyclability of the material and a stable production of hydrogen during consecutive cycles. However, these changes are not observed when the perovskites were synthesized at basic pH and operated at isothermal conditions at 800 ºC. In this case, the materials keep the crystalline structure leading to stable hydrogen production during consecutive cycles. Among all the studied materials, the nickel-based La0.8Al0.2NiO3-δ perovskites exhibited the best hydrogen productivity per cycle, 4.4 cm3 STP /gmaterial·cycle (Standard Temperature and Pressure conditions), which is a remarkable result considering that the thermochemical water splitting is conducted under isothermal conditions at just 800 ºC. Moreover, this result is accompanied with a good performance of the perovskite in terms of solar to fuel efficiency (being 0.46 the ratio between the potential energy recovery from the produced hydrogen and the solar heat required for its production), comparable or even higher than values reported in the literature for other metal oxides. These results confirm the La0.8Al0.2NiO3-δ perovskite as an auspicious material for a full-scale H2 production from water splitting by solar-driven thermochemical cycles at low temperatures.

The role of entropy in the success of nonstoichiometric oxides for two-step thermochemical water and CO2 splitting

Owing to their high theoretical efficiency, two-step solar thermochemical water and CO2 splitting cycles, using a metal oxide intermediate, provide a promising pathway to store solar energy in a stable chemical bond. To date, the most successful demonstrations have utilized nonstoichiometric oxides, a class of materials capable of continuously transitioning from an oxidized to reduced state via formation of oxygen vacancies. The success of nonstoichiometric oxides is typically attributed to their ability to maintain their crystallographic phase, allowing them to be cycled many times without destabilizing–a tremendous practical advantage. In this work, we utilize a combined empirical and statistical thermodynamics approach to present an alternative explanation of the success of nonstoichiometric oxides from an entropy perspective. We first illuminate the importance of the entropy change of the reduction reaction as a key material parameter. We then develop a methodology for plotting nonstoichiometric oxides on the Ellingham diagram, enabling a direct comparison to stoichiometric materials. This analysis reveals the unique ability of nonstoichiometric oxides to achieve a significant solid-state entropy contribution, which results from the disorder generated via oxygen vacancy formation. To quantify the solid-state entropy, we develop a simple configurational entropy model applicable to any oxygen-deficient nonstoichiometric oxide. We compare model predictions to existing data for two important nonstoichiometric oxides, CeO2−δ and La0.6Ca0.4Mn0.6Al0.4O3−δ, to reveal the main trends in entropy vs δ and material composition and discuss the causes and implications of deviations from the theory.