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All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Materials Design Directions for Solar Thermochemical Water Splitting

The sustainable, economical production of molecular hydrogen is a crucial component of a net zero-greenhouse-gas-emissions future. Solar thermochemical water splitting (STWS) offers a renewable route to hydrogen with the potential to help decarbonize several industries, including transportation, manufacturing, mining, metals processing, and electricity generation, as well as provide sustainable hydrogen as a chemical feedstock. STWS uses high temperatures generated from concentrated sunlight or other sustainable means for high-temperature heat to produce hydrogen and oxygen from steam. For example, in its simplest form of a two-step thermochemical cycle, a redox-active metal oxide is heated to ≈1700-2000 K, driving off molecular oxygen while producing oxygen vacancies in the material. The reduced metal oxide then cools (ideally with the extracted heat recuperated for re-use) and, in a separate step, comes into contact with steam, which reacts with oxygen vacancies to produce molecular hydrogen while recovering the original state of the metal oxide. Despite its promising use of the entire solar spectrum to split water thermochemically, the current estimated cost of hydrogen produced via STWS is ≈4-6× the U.S. Department of Energy (DOE) Hydrogen Shot target value of $1/kg. One contributing approach to bridging this cost gap is the design of new materials with improved thermodynamic properties to enable higher efficiencies. The state-of-the-art (SOA) redox-active metal oxide for STWS is ceria (CeO 2 ), due to its close to optimal, although too high, oxygen vacancy formation enthalpy and large configurational and electronic entropy of reduction. However, ceria requires high operating temperatures and its efficiency is insufficient. Therefore, efforts to increase the efficiency of STWS cycles have focused on further optimizing oxygen vacancy formation enthalpies and augmenting the reduction entropy via substitution or doping and materials discovery schemes. Examples of the latter include the perovskites BaCe 0.25 Mn 0.75 O 3 and (Ca,Ce)(Ti,Mn)O 3 . These efforts and others have revealed intuitive chemical principles for the efficient and systematic design of more effective materials, such as the strong correlation between the enthalpies of crystal bond dissociation and solid-state cation reduction with the enthalpy of oxygen vacancy formation, as well as configurational entropy augmentation via the coexistence of two or more redox-active cation sublattices. The purpose of this chapter is to prepare the reader with an up-to-date account of STWS redox-active materials, both the SOA and promising newcomers, as well as to provide chemically intuitive strategies for improving their cycle efficiencies through materials design – in conjunction with ongoing efforts in reactor engineering and gas separations – to reach the cost points for commercial viability. First, we will introduce the thermodynamics of STWS using a two-step, metal-oxide, thermochemical cycle with economics in mind. We also will compare the pros and cons of processes that do or do not involve phase changes. Second, we will describe the qualities that make ceria the SOA STWS redox-active material, as well as its limitations. Third, we will survey some of the most promising candidates to date in the search for materials to supplant ceria, emphasizing the post-ternary, metal-oxide-perovskite alloys. Lastly, we will enumerate and discuss the following materials design directions for STWS redox-active materials: crystal reduction potentials as a proxy for oxygen vacancy formation enthalpies, engineering the electronic and configurational entropy of reduction via f-shells and simultaneous redox, and vetting materials stability via temperature-dependent phase diagrams and melting-point prediction.

08 HYDROGEN↗
DOE OSTI2022

Synthesis and structure of high-purity BaCe 0.25 Mn 0.75 O 3 : 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 CeO 2 as a benchmark active material, but more recently, the 12R phase of BaCe 0.25 Mn 0.75 O 3 (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. Our 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.

08 HYDROGEN↗
DOE OSTI2025

Metal oxide candidates for thermochemical water splitting obtained with a generative diffusion model

Generative diffusion models (DMs) for inorganic crystalline materials are being actively investigated for their potential to expand the chemical and structural design spaces for known functional materials. Generative candidates are particularly useful for applications where few functional, let alone commercially viable, materials currently exist, such as metal oxides for thermochemical water-splitting, which have strict requirements for defect thermodynamics and host stability. Here, we critically examine generated metal oxides from the M ATTER G EN DM conditioned on select chemical systems for thermochemical water splitting applications. Perhaps most notably, we find that M ATTER G EN predicts a novel, thermodynamically stable, quinary metal oxide, Ba 2 SrInFeO 6 , although this compound represents an ordered and layered substitution within the same A 3 B 2 O 6 structural prototype as its two ternary end members. Detailed density functional theory calculations and spin configuration sampling for this material and its possible decomposition products—beyond what existed in M ATTER G EN training data—are required to quantitatively validate hull energy predictions and conclusions of stability. Furthermore, the material exhibits oxygen defect formation energies appropriate for thermochemical water splitting, warranting targeted investigation in an experimental validation campaign, along with other future M ATTER G EN candidates in this application space.

36 MATERIALS SCIENCE↗
DOE OSTI2023

LaMnO 3 Dopants for Efficient Thermochemical Water Splitting Identified by Density Functional Theory Calculations

While ceria is the standard material for two-step water splitting, perovskites are emerging as viable alternatives. In this work, based on the orthorhombic LaMnO 3 supercell, we substitute Li Na K Rb Mg Ca Sr Ba on the A-sites (La sites) and Al Ga In Mg Zn on the B-sites (Mn sites) at a concentration of 37.5%. The range of temperature and oxygen partial pressure at which each composition is stable is predicted. For compositions that are stable in relevant temperature and pressure ranges, the oxygen vacancy formation energies are determined for all of the oxygen vacancy site positions available in the computational supercell. Mg, Ca, Sr, and Ba A-site-substituted LaMnO 3 and Al and In B-site-substituted LaMnO 3 meet these two criteria for candidates in solar-thermal water splitting applications. Finally, oxygen vacancy formation energy can also be controlled by adjusting the doping strategy.

08 HYDROGEN↗
NASA NTRS2014

Solar Metal Sulfate-Ammonia Based Thermochemical Water Splitting Cycle for Hydrogen Production

Two classes of hybrid/thermochemical water splitting processes for the production of hydrogen and oxygen have been proposed based on (1) metal sulfate-ammonia cycles (2) metal pyrosulfate-ammonia cycles. Methods and systems for a metal sulfate MSO.sub.4--NH3 cycle for producing H2 and O2 from a closed system including feeding an aqueous (NH3)(4)SO3 solution into a photoctalytic reactor to oxidize the aqueous (NH3)(4)SO3 into aqueous (NH3)(2)SO4 and reduce water to hydrogen, mixing the resulting aqueous (NH3)(2)SO4 with metal oxide (e.g. ZnO) to form a slurry, heating the slurry of aqueous (NH4)(2)SO4 and ZnO(s) in the low temperature reactor to produce a gaseous mixture of NH3 and H2O and solid ZnSO4(s), heating solid ZnSO4 at a high temperature reactor to produce a gaseous mixture of SO2 and O2 and solid product ZnO, mixing the gaseous mixture of SO2 and O2 with an NH3 and H2O stream in an absorber to form aqueous (NH4)(2)SO3 solution and separate O2 for aqueous solution, recycling the resultant solution back to the photoreactor and sending ZnO to mix with aqueous (NH4)(2)SO4 solution to close the water splitting cycle wherein gaseous H2 and O2 are the only products output from the closed ZnSO4--NH3 cycle.

Huang, Cunping↗
DOE OSTI2025

Large-scale experimental validation of thermochemical water-splitting oxides discovered by defect graph neural networks

Thermochemical water-splitting (TCH) based on 2-step thermal redox cycles in metal oxides is a promising approach to generating H 2 , but state-of-the-art (SOTA) CeO 2 has several practical limitations, which has motivated continued materials discovery efforts in this field. Here, in this study, we improve upon a SOTA defect graph neural network (dGNN) surrogate model's oxygen vacancy predictions and combine them with materials project phase diagrams to down-select and discover structurally diverse, experimentally known metal oxides whose TCH performance was previously unknown. Amongst twelve candidates selected based on our high-throughput screening and down-selection criteria, we achieved ∼80% accuracy in identifying materials with stable redox cycling and hydrogen production in stagnation flow reactor water-splitting experiments. Closer to 100% accuracy can be achieved if higher-accuracy, hybrid DFT-predicted vacancy formation energies were computed and used in lieu of the most uncertain dGNN-based screening predictions, as they correct false positives to true negatives. Notably, two discovered candidates, Sr 3 PrMn 2 O 8 and Ba 2 Fe 2 O 5 , display hydrogen yields greater than CeO 2 under specific redox conditions. In conclusion, these results demonstrate our ability to computationally predict and experimentally validate promising candidate TCH materials that have the potential to compete with CeO 2 .

08 HYDROGEN↗
NASA NTRS1975

Ispra Mark-10 water splitting process

A thermochemical water splitting process, the Ispra Mark-10 chemical reaction cycle, was chosen for examining the possibility of using water to produce hydrogen on a large scale for fuel and major industrial chemical uses. The assumed energy source for the process is an HTGR (helium cooled). A process flow diagram, a material balance, and an energy balance were developed for the thermochemical reaction cycle. Principal reactions which constitute the cycle are included.

Source record↗
DOE OSTI2023

Accuracy of DFT computed oxygen-vacancy formation energies and high-throughput search of solar thermochemical water-splitting compounds

The enthalpy change involved in metal oxide reduction is a key quantity in various processes related to energy conversion and storage, and is of particular interest for computational prediction. Often this prediction involves the simulation of a high temperature reduction process with a 0K methodology like density functional theory (DFT), and it is not infrequent for the high temperature and 0K stable crystal structures to differ. This introduces a conundrum with regards to the choice of crystal structure to utilize in the computation, with approaches in the literature varying and experimental validation remaining scarce. In this work we address both the crystal structure conundrum and the experimental validation, and then apply the insights we gain to guide a high-throughput search for new materials for solar thermochemical water-splitting applications. By computing the DFT+U oxygen vacancy formation energy (ΔE vf ) of a selection of ABO 3 compounds and comparing different crystal structures for each composition, we highlight the issues that arise when the structure utilized in the computation is dynamically unstable at 0K, namely the presence of an artificial lowering of ΔE vf , and the lack of convergence of ΔE vf with cell size. We solve these limitations by identifying and employing a suitable surrogate dynamically stable structure. We then validate the predictive power of our calculations against appositely generated experimental measurements of reduction enthalpy for a series of Hubbard U values, finding an accuracy ranging between 0.2-0.6 eV/O. In light of such conclusions, we revise and expand a previous a high-throughput DFT study on ABO 3 perovskite oxides. As a result, we provide a list of candidate STCH materials, highlight trends with redox-active cation and structural distortion, and identify Mn 4+ , Mn 3+ and Co 3+ as the most promising redox-active cations.

08 HYDROGEN↗
NASA NTRS1980

Studies of thermochemical water-splitting cycles

Higher temperatures and more isothermal heat profiles of solar heat sources are developed. The metal oxide metal sulfate class of cycles were suited for solar heat sources. Electrochemical oxidation of SO2 and thermochemical reactions are presented. Electrolytic oxidation of sulfur dioxide in dilute sulfuric acid solutions were appropriate for metal oxide metal sulfate cycles. The cell voltage at workable current densities required for the oxidation of SO2 was critical to the efficient operation of any metal oxide metal sulfate cycle. A sulfur dioxide depolarized electrolysis cell for the splitting of water via optimization of the anode reaction is discussed. Sulfuric acid concentrations of 30 to 35 weight percent are preferred. Platinized platinum or smooth platinum gave the best anode kinetics at a given potential of the five materials examined.

Remick, R. J.↗
DOE OSTI2026

Scalable Solar Fuels Production in A Reactor Train System by Thermochemical Redox Cycling of Novel Nonstoichiometric Perovskites

Hydrogen production via two-step thermochemical water splitting redox cycles using nonstoichiometric redox-active metal oxides has the potential to dramatically increase fuel production rates. At moderate-to-low water splitting temperatures, surface reaction kinetics co-limit the process. In such cases, stable and high surface area microstructures that allow exploitation of the full thermodynamic potential of the materials are essential as is tight thermal integration of the reactor module. This project’s goals were the development of novel nonstoichiometric perovskite oxides with high stability and favorable thermodynamic and kinetic properties, to optimize their microstructure for maximizing the fuel productivity, and to build a prototype reactor train system (RTS) comprising at least one reactor to meet specific performance targets: (1) capable of an in-house solar thermochemical hydrogen (STCH) productivity ≥ 12 mL g -1 for stable continuous operation ≥ 20 cycles; and (2) demonstration of scalable solar fuels production at practical solar reactor level in an industrial-scale concentrated solar tower (CST) using developed perovskites to achieve a hydrogen production rate ≥ 1 g h -1 .

08 HYDROGEN↗
DOE OSTI2023

Mixed Ionic Electronic Conducting Quaternary Perovskites: Materials by Design for Solar Thermochemical Hydrogen

The innovative research conducted by Arizona State University and Princeton University in the project "Mixed Ionic-Electronic Conducting Quaternary Perovskites: Materials by Design for Solar Thermochemical Hydrogen" marks a significant stride forward in thermochemical water splitting. Through an intricate blend of computational design and experimental validation, the project delved into the promising potential of Mixed Ionic Electronic Conducting (MIEC) perovskites. These complex materials, characterized by their unique redox-active nature and adaptability in stoichiometry, present a promising frontier for efficient solar thermochemical hydrogen production. Firstly, the research enhanced the science by utilizing state-of-the-art computational methodologies to unravel the nuanced chemical potentials of MIEC perovskites. By simulating various off-stoichiometric scenarios and redox conditions, the team was able to predict material behaviors under diverse environmental conditions, a feat unachievable through conventional experimental methodologies alone. This approach not only fast-tracks the material screening process, significantly reducing the time from laboratory re-search to practical application, but also uncovers trends and correlations that are pivotal for future materials innovation. Regarding technical effectiveness, the project stands out in its economic feasibility. Traditional methods of materials discovery are often marred by high costs and extensive timeframes, owing to the iterative nature of experimental processes. However, by employing theoretical computations and validating these findings with targeted experiments, the project introduced a cost-effective paradigm for materials discovery and the first ever prediction, synthesis, and preliminary validation of a material solely from computational and theoretical considerations. This synergy between computation and experimentation expedites the discovery of optimal materials conducive to high-efficiency solar-to-hydrogen conversion processes. Furthermore, the public stands to benefit substantially from this research. The success of MIEC perovskites in solar thermochemical applications heralds a shift towards lower cost and lower electricity input for clean hydrogen production, hence potentially impacting climate and energy resilience. By improving the efficiency of solar-to-hydrogen conversions, the research paves the way for reduced dependency on fossil fuels, addressing the urgent global need for accessible and renewable energy sources. Moreover, the project's advancements contribute to scientific literacy in renewable energy technologies, empowering society through knowledge and spurring future innovations. In essence, this research project demonstrates significant progress in the realm of advanced water splitting through solar thermochemistry. Through its groundbreaking approaches in computational materials science and its implications for real-world applications, it holds the promise of a cleaner, more energy-resilient future.

08 HYDROGEN↗
NASA NTRS1975

Thermochemical production of hydrogen via multistage water splitting processes

This paper presents and reviews the fundamental thermodynamic principles underlying thermochemical water splitting processes. The overall system is considered first and the temperature limitation in process thermal efficiency is developed. The relationship to an ideal water electrolysis cell is described and the nature of efficient multistage reaction processes is discussed. The importance of the reaction entropy change and the relation of the reaction free energy change to the work of separation is described. A procedure for analyzing thermochemical water splitting processes is presented and its use to calculate individual stage efficiency is demonstrated. A number of processes are used to illustrate the concepts and procedures.

Funk, J. E.↗
DOE OSTI2022

Reticulated porous lanthanum strontium manganite structures for solar thermochemical hydrogen production

Porous ceramic foams are utilized in various fields and applications due to their advantageous properties such as high porosity, high specific surface area, and controlled permeability. Non-stoichiometric oxide foams are of particular interest for the solar thermochemical production of hydrogen in directly irradiated solar receivers due to their enhanced heat transfer capabilities and structural integrity. Here we report the fabrication of lanthanum strontium manganite replica foams and their solar thermochemical water splitting performance. Highly porous (>80%) foams were produced with controlled structure and tested in a high temperature water splitting furnace to demonstrate stability and overall performance. The temperature profile of the burnout and sintering of the foam structure were altered based on simultaneous differential scanning calorimetry and thermal gravimetry analysis. Two-step sintering was used both to retain micron-sized pores (D50 = 0.4 μm) on the foam's struts and to limit grain growth to a grain size of ~1 μm. The structural characteristics were confirmed by porosimetry and scanning electron microscopy. The foams were repeatedly cycled, producing approximately 200 μmol/g of H 2 per cycle. Water splitting performance was tested for 50 cycles and approximately 35 h at 1400 °C. No statistical difference in the effective hydrogen production per cycle was observed, which is promising for long-term redox cycle stability.

08 HYDROGEN↗
DOE OSTI2024

Predicting Thermochemical Equilibria with Interacting Defects: Sr 1 − x Ce x Mn O 3 − δ Alloys for Water Splitting

Solar thermochemical hydrogen is one of the few potential routes towards direct fuel production from renewable energy sources, but the thermodynamic boundary conditions for efficient and economic energy conversion are challenging. Success or failure of a given oxide working material depends on the subtle balance between enthalpy and entropy contributions in the redox processes. Developing a mechanistic understanding of the behavior of materials on the basis of atomistic models and first-principles calculations is an important part of advancing the technology. One challenge is to quantitatively predict thermochemical equilibria at high concentrations when the redox-active defects start to interact with each other, thereby impeding the formation of additional defects. This problem is of more general importance to applications that rely on high levels of off-stoichiometry or doping, including, for example, batteries, thermoelectrics, and ceramic fuel cells. To account for such repulsive defect interactions, we introduce a statistical mechanics approach, defining an expression for the free energy of defect interaction based on limited sampling of defect configurations in density functional theory supercell calculations. The parameterization of this energy contribution as a function of defect concentration and temperature allows on-the-fly simulation of thermochemical equilibria. The approach consistently incorporates finite temperature effects by including the leading contributions to the temperature-dependent free energy for the case at hand, i.e., the ideal gas and configurational enthalpies and entropies. We demonstrate the capability and utility of the approach by simulating the water splitting redox processes for Sr 1 − x Ce x Mn O 3 − δ alloys. Published by the American Physical Society 2024

08 HYDROGEN↗