Thermochemical multistep water- and CO₂-splitting processes are promising options to face future energy problems. Particularly, the possible incorporation of solar power makes these processes sustainable and environmentally attractive since only water, CO₂ and solar power are used; the concentrated solar energy is converted into storable and transportable fuels. One of the major barriers to technological success is the identification of suitable active materials like catalysts and redox materials exhibiting satisfactory durability, reactivity and efficiencies. Moreover, materials play an important role in the construction of key components and for the implementation in commercial solar plants. The most promising thermochemical water- and CO₂-splitting processes are being described and discussed with respect to further development and future potential. The main materials-related challenges of those processes are being analyzed. Technical approaches and development progress in terms of solving them are addressed and assessed in this review.

Global trade of green hydrogen will probably become a vital factor in reaching climate neutrality. The sunbelt of the Earth has a great potential for large-scale hydrogen production. One promising pathway to solar hydrogen is to use economically priced electricity from photovoltaics (PV) for electrochemical water splitting. However, storing electricity with batteries is still expensive and without storage only a small operating capacity of electrolyser systems can be reached. Combining PV with concentrated solar power (CSP) and thermal energy storage (TES) seems a good pathway to reach more electrolyser full load hours and thereby lower levelized costs of hydrogen (LCOH). This work introduces an energy system model for finding cost-optimal designs of such PV/CSP hybrid hydrogen production plants based on a global optimization algorithm. The model includes an operational strategy which improves the interplay between PV and CSP part, allowing also to store PV surplus electricity as heat. An exemplary study for stand-alone hydrogen production with an alkaline electrolyser (AEL) system is carried out. Three different locations with different solar resources are considered, regarding the total installed costs (TIC) to obtain realistic LCOH values. The study shows that a combination of PV and CSP is an auspicious concept for large-scale solar hydrogen production, leading to lower costs than using one of the technologies on its own. For today’s PV and CSP costs, minimum levelized costs of hydrogen of 4.04 USD/kg were determined for a plant located in Ouarzazate (Morocco). Considering the foreseen decrease in PV and CSP costs until 2030, cuts the LCOH to 3.09 USD/kg while still a combination of PV and CSP is the most economic system.

The Future Fuels project combines research in several institutes of the German Aerospace Center (DLR) on the production and use of synthetic fuels for space, energy, transportation, and aviation. This article gives an overview of the research questions considered and results achieved so far and also provides insight into the multidimensional and interdisciplinary project approach. Various methods and models were used which are embedded in the research context and based on established approaches. The prospects for large-scale fuel production using renewable electricity and solar radiation played a key role in the project. Empirical and model-based investigations of the technological and cost-related aspects were supplemented by modelling of the integration into a future electricity system. The composition, properties, and the related performance and emissions of synthetic fuels play an important role both for potential oxygenated drop-in fuels in road transport and for the design and certification of alternative aviation fuels. In addition, possible green synthetic fuels as an alternative to highly toxic hydrazine were investigated with different tools and experiments using combustion chambers. The results provide new answers to many research questions. The experiences with the interdisciplinary approach of Future Fuels are relevant for the further development of research topics and co-operations in this field.

Non-abatable emissions are one of the decarbonization challenges that could be addressed with carbon-neutral fuels. One promising production pathway is the direct air capture (DAC) of carbon dioxide, followed by a solar thermochemical cycle and liquid fuel synthesis. In this study, we explore different combinations of these technologies to produce methanol from an economic perspective in order to determine the most efficient one. For this purpose, a model is built and simulated in Aspen Plus^®, and a solar field is designed and sized with HFLCAL^®. The inherent dynamics of solar irradiation were considered with the meteorological data from Meteonorm^® at the chosen location (Riyadh, Saudi Arabia). Four different integration strategies are assessed by determining the minimum selling price of methanol for each technology combination. These values were compared against a baseline with no synergies between the DAC and the solar fuels production. The results show that the most economical methanol is produced with a central low-temperature DAC unit that consumes the low-quality waste heat of the downstream process. Additionally, it is determined with a sensitivity analysis that the optimal annual production of methanol is 11.8 kt/y for a solar field with a design thermal output of 280 MW.

Methanol is an example of a valuable chemical that can be produced from water and carbon dioxide through a chemical process that is fully powered by concentrated solar thermal energy and involves three steps: direct air capture (DAC), thermochemical splitting and methanol synthesis. In the present work, we consider the whole value chain from the harvesting of raw materials to the final product. We also identify synergies between the aforementioned steps and collect them in five possible scenarios aimed to reduce the specific energy consumption. To assess the scenarios, we combined data from low and high temperature DAC with an Aspen Plus^® model of a plant that includes water and carbon dioxide splitting units via thermochemical cycles (TCC), CO/CO₂ separation, storage and methanol synthesis. We paid special attention to the energy required for the generation of low oxygen partial pressures in the reduction step of the TCC, as well as the overall water consumption. Results show that suggested synergies, in particular, co-generation, are effective and can lead to solar-to-fuel efficiencies up to 10.2% (compared to the 8.8% baseline). In addition, we appoint vacuum as the most adequate strategy for obtaining low oxygen partial pressures.

Concentrated solar power is capable of providing high-temperature process streams to different applications. One promising application is the high-temperature electrolysis process demanding steam and air above 800 °C. To overcome the intermittence of solar energy, energy storage is required. Currently, thermal energy at such temperatures can be stored predominately as sensible heat in packed beds. However, such storage suffers from a loss of usable storage capacity after several cycles. To improve such storage, a one-dimensional packed bed thermal energy storage model using air as a heat transfer medium is set up and used to investigate and quantify the benefit of the incorporation of different thermochemical materials from the class of perovskites. Perovskites undergo a non-stoichiometric reaction extension which offers the utilization of thermochemical heat over a larger temperature range. Three different perovskites were considered: SrFeO₃, CaMnO₃ and Ca_0.8Sr_0.2MnO₃. In total, 15 vol% of sensible energy storage has been replaced by one perovskite and different positions of the reactive material are analyzed. The effect of reactive heat on storage performance and thermal degradation over 15 consecutive charging and discharging cycles is studied. Based on the selected variation and reactive material, storage capacity and useful energy capacity are increased. The partial replacement close to the cold inlet/outlet of the storage system can increase the overall storage capacity by 10.42%. To fully utilize the advantages of thermochemical material, suitable operation conditions and a fitting placement of the material are vital.