Search Results (40)

Solar fuels production requires developing redox active materials with porous structures able to withstand thermochemical cycles with enhanced thermal stability under concentrated solar irradiation conditions. The mechanical performance of 3D-printed, macroporous black zirconia gyroid structures, coated with redox-active ceria, was assessed for their suitability in solar thermochemical cycles for CO₂ and H₂O splitting. Experiments were conducted using a 1.5 kW solar furnace to supply the high-temperature concentrated heat to a windowed reaction chamber to carry out thermal redox cycling under realistic on-sun conditions. The ceria coating on ceramic structures improved the thermal stability and redox efficiency while minimizing the quantity of the redox material involved. Crushing strength measurements showed that samples not directly exposed to the concentrated solar flux retained their mechanical performance after thermal cycling (~10 MPa), while those near the concentrated solar beam focus exhibited significant degradation due to thermal stresses and the formation of Ce_xZr_1−xO₂ solid solutions (~1.5 MPa). A Weibull modulus of 8.5 was estimated, marking the first report of such a parameter for fused filament fabrication (FFF)-manufactured black zirconia with gyroid architecture. Failure occurred via a damage accumulation mechanism at both micro- and macro-scales. These findings support the viability of ceria-coated cellular ceramics for scalable solar fuel production and highlight the need for optimized reactor designs. Full article

Superdeep diamonds and their syngenetic inclusions are crucial for understanding Earth’s deep carbon cycle and slab–mantle redox dynamics. The origins of these diamonds, especially their links to iron (Fe) carbides and ferropericlase with varying Mg# [=Mg/(Mg+Fe)_at], however, remain elusive. In this study, we performed high pressure–temperature (P-T) experiments (10–16 GPa and 1200–1700 K) across cold-to-warm subduction zones using a multi-anvil press. The results reveal a stepwise Fe-mediated carbonate reduction process for the formation of superdeep diamonds: MgCO₃ → Fe-carbides (Fe₃C/Fe₇C₃) → graphite/diamond. This mechanism explains two phenomena regarding superdeep diamonds: (1) anomalous ¹³C depletion results from kinetic isotope fractionation during ¹²C enrichment into the intermediate Fe-carbides; (2) nitrogen scarcity is due to Fe-carbides acting as nitrogen sinks. Ferropericlase [(Mg,Fe)O] formed during the reactions in our experiments shows Mg# variations (0.2–0.9), similar to those found in natural samples. High Mg# (>0.7) variants from lower temperature experiments indicate diamond crystallization from carbonatitic melts in the shallow lower mantle, while the broad Mg# range (0.2–0.9) from experiments at higher temperatures suggests multi-depth formation processes as found in Brazilian diamonds. These findings suggest that slab–mantle interactions produce superdeep diamonds with distinctive Fe-carbides and ferropericlase assemblages as inclusions, coupled with their ¹³C- and nitrogen-depleted signatures, which underscore thermochemical carbon cycling as a key factor in deep carbon storage and mantle mineralogy. Full article

Solar power generation systems, recognized for their high energy quality and environmental benefits, require efficient energy storage to ensure stable grid integration and reduce reliance on fossil fuels. Thermochemical energy storage (TCS) using metal oxides, such as the Mn₂O₃/Mn₃O₄ redox system, offers advantages like high energy density, wide temperature range, and stability, making it ideal for solar power applications. This study investigates Mn₃O₄ and Mn₂O₃ as initial reactants, analyzing reaction temperature range, rate, conversion efficiency, and cyclic performance via synchronous thermal analysis. Microstructural characterization was performed using XRD, SEM, BET, XPS, nanoparticle size, and zeta potential measurements. The results show that Mn₃O₄ reversibly converts to Mn₂O₃ with over 100% conversion efficiency over five cycles with 3.3% weight loss, indicating stable performance. Mn₃O₄ oxidation follows Arrhenius’ Law below 700 °C but deviates at higher temperatures. The oxidation mechanism function is G(α) = α and f(α) = 1, with an activation energy of 20.47 kJ/mol and a pre-exponential factor of 0.268/s. Mn₂O₃ synthesized via ammonia precipitation exhibits reversible redox behavior with 3.3% weight loss but samples from low-concentration precursors show poor cyclic performance. The reduction reaction of Mn₂O₃ has an activation energy of 249.87 kJ/mol. By investigating the Mn₂O₃/Mn₃O₄ redox system for TCS, this study advances its practical integration into solar thermal power systems and offers critical guidance for developing scalable, low-carbon energy storage technologies. These findings can support Sustainable Development Goals (SDGs) by advancing renewable energy storage technologies, reducing carbon emissions, and promoting the integration of solar power into sustainable energy grids. Full article

The chemical looping reforming of methane using an SrFeO₃ oxygen carrier to produce synthesis gas from solar energy was experimentally investigated and validated. High-temperature solar heat was used to provide the reaction enthalpy, and therefore the methane feedstock was entirely dedicated to producing syngas. The two-step isothermal process encompassed partial perovskite reduction with methane (partial oxidation of CH₄) and exothermic oxidation of SrFeO_3-δ with CO₂ or H₂O splitting under the same operating temperature. The oxygen carrier material was shaped in the form of a reticulated porous foam structure for enhancing heat and mass transfer, and it was cycled in a solar-heated tubular reactor under different operating parameters (temperature: 950–1050 °C, methane mole fraction: 5–30%, and type of oxidant gas: H₂O vs. CO₂). This study aimed to assess the fuel production capacity of the two-step process and to demonstrate the potential of using strontium ferrite perovskite during solar cycling for the first time. The maximum H₂ and CO production rates during CH₄-induced reduction were 70 and 25 mL/min at 1000 °C and 15% CH₄ mole fraction. The increase in both the cycle temperature and the methane mole fraction promoted the reduction step, thereby enhancing syngas yields up to 569 mL/g during reduction at 1000 °C under 30% CH₄ (778 mL/g including both cycle steps), and thus outperforming the performance of the benchmark ceria material. In contrast, the oxidation step was not significantly affected by the experimental conditions and the material’s redox performance was weakly dependent on the nature of the oxidizing gas. The syngas yield remained above 200 mL/g during the oxidation step either with H₂O or CO₂. Twelve successive redox cycles with stable patterns in the syngas production yields validated material stability. Combining concentrated solar energy and chemical looping reforming was shown to be a promising and sustainable pathway toward carbon-neutral solar fuels. Full article

Apparent kinetics is often used to describe a variety of reactions in the field of chemical looping and solar thermochemical processes, yet a rigorous analytical methodology for utilizing such kinetics has been lacking. The implementation of a novel approach was exemplified in the ceria thermochemical cycle for producing solar thermochemical hydrogen, specifically in the H₂O-driven oxidation step. The H₂ production rate equation was derived, rearranging apparent kinetics from experimental data in the literature into a more suitable analytical form. The 1D model integrates heat transfer, fluid dynamics, and redox chemistry, providing the description of a directly irradiated solar receiver–reactor. Model robustness is ensured through the oxygen mass balance across the cycle, and the comparison against experimental data shows high agreement. The methodology can be useful for simulating chemical looping cycles using any nonstoichiometric oxide, such as ceria-based oxides and, most importantly, oxidation-limited perovskites, for which optimizing the oxidation step in terms of fluid flow, kinetics, and reaction times is crucial. The proposed analytical model can be applied to arbitrarily complex reactor geometries. The inherently local nature of the model also allows the spatial distributions of the redox material’s conversion and utilization to be obtained, paving the way for optimization strategies of the reactor’s design and operation. Full article

Perovskite materials are promising for thermochemical energy storage due to their ability to undergo redox cycling over a wide temperature range. Although BaCoO₃ exhibits excellent air cycling properties, its heat storage capacity in air remains suboptimal. This study introduces Na into the lattice structure to enhance oxygen vacancy formation and mobility. DFT+U simulations of the surface structure of Na-doped BaCoO_3−δ indicate that incorporating Na improves surface stability and facilitates the formation of surface oxygen vacancies. Na_xBa_1−xCoO_3−δ compounds were synthesized using a modified sol–gel method, and their properties were investigated. The experimental results demonstrate that Na doping significantly enhances the redox activity of the material. The heat storage capacity increased by above 50%, with the Na_0.0625Ba_0.9375CoO_3−δ solid solution achieving a heat storage density of up to 341.7 kJ/kg. XPS analysis reveals that Na doping increases the concentration of surface defect oxygen, leading to more active oxygen release sites at high temperatures. This enhancement in redox activity aligns with DFT predictions. During high-temperature cycling, the distribution of Na within the material becomes more uniform, and no performance degradation is observed after 300 cycles. Even after 450 cycles, Na_0.0625Ba_0.9375CoO_3−δ retains over 96% of its initial redox activity, significantly outperforming fresh BaCoO_3−δ. These findings elucidate the mechanism by which Na doping enhances the thermochemical heat storage performance of BaCoO_3−δ and provide new insights for the design of perovskite-based materials. Full article

In this investigation, an effort was made to introduce Ag into the CeO₂ fluorite crystal lattice to form Ce_0.99Ag_0.01O_2-δ (ACRM) using an ammonium hydroxide-assisted co-precipitation method. The resulting powder obtained after the co-precipitation reaction, filtration, and drying was annealed at 800 °C in a muffle furnace to obtain crystalline ACRM. The phase composition and microstructure of the synthesized ACRM were analyzed using a powder X-ray diffractometer (PXRD) and a scanning electron microscope (SEM). The characterized ACRM powder was then subjected to multiple thermochemical thermal reduction (TR) and CO₂ splitting (CDS) cycles using a high-temperature thermogravimetric analyzer (TGA). The TR step was conducted using Ar gas as an inert atmosphere, maintaining the temperature at 1400 °C for 60 min. Subsequently, the same powder was subjected to the CDS step by treating it with a gaseous mixture of 50% CO₂ and Ar gas at 1000 °C for 30 min. ACRM displayed stable redox reactivity towards thermochemical CDS cycles by generating an average of 50.9 μmol of O₂/g·cycle and 101.6 μmol of CO/g·cycle, respectively, over 10 thermochemical cycles. Full article

The solar thermochemical process of splitting CO₂, known as CDS, is studied here using a redox cycle involving GeO₂/GeO. The required thermodynamic data for a second-law-efficiency analysis is obtained from the HSC Chemistry software. The goal of this study is to investigate how different parameters, such as the operating temperatures and molar flow rate of the inert sweep gas, as well as the inclusion of separation units, heat exchangers, heaters, and coolers, can affect the solar-to-fuel energy conversion efficiency of the GeO₂/GeO cycle. All calculations assume a constant gas-to-gas heat recovery effectiveness of 0.5. The analysis shows that the solar-to-fuel energy conversion efficiency is lower at a thermal reduction temperature of 1600 K (11.9%) compared to 2000 K. This is because high energy duties are required for heater-2, heater-3, and separator-1 due to the need for a higher inert gas flow rate. After conducting a comparative analysis of the three CDS cycles, it can be inferred that the GeO₂/GeO cycle exhibits a significantly higher solar-to-fuel energy conversion efficiency in comparison to the ZnO/Zn and SnO₂/SnO cycles across all thermal reduction temperatures. According to the comparison, it is confirmed that the GeO₂/GeO CDS cycle can achieve a reasonably high solar-to-fuel energy conversion efficiency of 10% at less than 1600 K. On the other hand, ZnO/Zn and SnO₂/SnO CDS cycles require a thermal reduction temperature of more than 1850 K to achieve a solar-to-fuel energy conversion efficiency of 10%. Full article

The effects of substitution at the A- and B sites on the redox performance of a series of lanthanum–strontium–manganese (LSM)-based perovskite oxides (Z = Ni, Co, and Mg) were studied for application in a two-step thermochemical CO₂ splitting cycle to produce liquid fuel from synthesis gas using concentrated solar radiation as the proposed energy source and CO₂ recovered from the atmosphere as the prospective chemical source. The redox reactivity, stoichiometry of oxygen/CO production, and optimum chemical composition of Ni-, Co-, and Mg-substituted LSM perovskites were investigated to enhance oxygen/CO productivity. Furthermore, the long-term thermal stabilities and thermochemical repeatabilities of the oxides were evaluated and compared with previous data. The valence changes in the constituent ionic species of the perovskite oxides were studied and evaluated by X-ray photoelectron spectroscopy (XPS) for each step of the thermochemical cycle. From the perspectives of high redox reactivity, stoichiometric oxygen/CO production, and thermally stable repeatability in long-term thermochemical cycling, Ni_0.20-, Co_0.35-, and Mg_0.125-substituted La_0.7Sr_0.3Mn perovskite oxides are the most promising materials among the LSM perovskite oxides for two-step thermochemical CO₂ splitting, showing CO productivities of 387–533 μmol/g and time-averaged CO productivities of 12.9–18.0 μmol/(min·g) compared with those of LSM perovskites reported in the literature. Full article

Metal oxide (MO) based solar thermochemical H₂O (WS) and CO₂ splitting (CDS) is one of the most promising and potential-containing processes that can be used to produce H₂ and syngas (liquid fuel precursor). Several non-volatile and volatile MOs were considered redox materials for the solar-driven WS and CDS operation. Among all the examined redox materials, based on their high O² storage capacity, faster oxidation kinetics, and good stability, ceria and doped ceria materials are deemed to be one of the best alternatives for the operation of the thermochemical redox reactions associated with the WS and CDS. Pure ceria was used for solar fuel production for the first time in 2006. A review paper highlighting the work done on the ceria-based solar thermochemical redox WS and CDS cycle from 2006 until 2016 is already published elsewhere by the author. This review paper presents all the significant findings reported in applying pure ceria and doped ceria materials for the WS and CDS by research teams worldwide. Full article

This study focuses on the generation of solar thermochemical fuel (hydrogen, syngas) from CO₂ and H₂O molecules via two-step thermochemical cycles involving intermediate oxygen-carrier redox materials. Different classes of redox-active compounds based on ferrite, fluorite, and perovskite oxide structures are investigated, including their synthesis and characterization associated with experimental performance assessment in two-step redox cycles. Their redox activity is investigated by focusing on their ability to perform the splitting of CO₂ during thermochemical cycles while quantifying fuel yields, production rates, and performance stability. The shaping of materials as reticulated foam structures is then evaluated to highlight the effect of morphology on reactivity. A series of single-phase materials including spinel ferrite, fluorite, and perovskite formulations are first investigated and compared to state-of-the-art materials. NiFe₂O₄ foam exhibits a CO₂-splitting activity similar to its powder analog after reduction at 1400 °C, surpassing the performance of ceria but with much slower oxidation kinetics. On the other hand, although identified as high-performing materials in other studies, Ce_0.9Fe_0.1O₂, Ca_0.5Ce_0.5MnO₃, Ce_0.2Sr_1.8MnO₄, and Sm_0.6Ca_0.4Mn_0.8Al_0.2O₃ are not found to be attractive candidates in this work (compared with La_0.5Sr_0.5Mn_0.9Mg_0.1O₃). In the second part, characterizations and performance evaluation of dual-phase materials (ceria/ferrite and ceria/perovskite composites) are performed and compared to single-phase materials to assess a potential synergistic effect on fuel production. The ceria/ferrite composite does not provide any enhanced redox activity. In contrast, ceria/perovskite dual-phase compounds in the form of powders and foams are found to enhance the CO₂-splitting performance compared to ceria. Full article

Redox materials have been investigated for various thermochemical processing applications including solar fuel production (hydrogen, syngas), ammonia synthesis, thermochemical energy storage, and air separation/oxygen pumping, while involving concentrated solar energy as the high-temperature process heat source for solid–gas reactions. Accordingly, these materials can be processed in two-step redox cycles for thermochemical fuel production from H₂O and CO₂ splitting. In such cycles, the metal oxide is first thermally reduced when heated under concentrated solar energy. Then, the reduced material is re-oxidized with either H₂O or CO₂ to produce H₂ or CO. The mixture forms syngas that can be used for the synthesis of various hydrocarbon fuels. An alternative process involves redox systems of metal oxides/nitrides for ammonia synthesis from N₂ and H₂O based on chemical looping cycles. A metal nitride reacts with steam to form ammonia and the corresponding metal oxide. The latter is then recycled in a nitridation reaction with N₂ and a reducer. In another process, redox systems can be processed in reversible endothermal/exothermal reactions for solar thermochemical energy storage at high temperature. The reduction corresponds to the heat charge while the reverse oxidation with air leads to the heat discharge for supplying process heat to a downstream process. Similar reversible redox reactions can finally be used for oxygen separation from air, which results in separate flows of O₂ and N₂ that can be both valorized, or thermochemical oxygen pumping to absorb residual oxygen. This review deals with the different redox materials involving stoichiometric or non-stoichiometric materials applied to solar fuel production (H₂, syngas, ammonia), thermochemical energy storage, and thermochemical air separation or gas purification. The most relevant chemical looping reactions and the best performing materials acting as the oxygen carriers are identified and described, as well as the chemical reactors suitable for solar energy absorption, conversion, and storage. Full article

The heat-discharging kinetics of an iron-substituted Mn₂O₃/Mn₃O₄ redox pair subjected to long-term thermal cycling tests using a temperature swing process at high temperatures was investigated for next-generation concentrated solar power plants equipped with thermochemical energy storage. The heat-discharge mode kinetics for long-term thermal-cycled samples have never been reported. Additionally, comparisons of the heat-discharge mode kinetics for both long-term thermal-cycled and as-prepared samples have never been discussed. In terms of the reproducibility and sustainability of thermochemical energy storage, kinetic evaluations of samples with thermally stable morphologies subjected to long-term thermal cycling at high temperatures are important for next-generation solar thermal power plants. For the long-term thermal-cycled sample, the A2 model based on the Avrami–Erofeev reaction describes the discharging mode behavior in a fractional conversion range of 0–0.24, the contracting area (R2) model best fits in a fractional conversion range of 0.24–0.50, and the third-order (F3) model matches in a fractional conversion range of 0.50–0.70. For the as-prepared sample, the power-law (P2) model describes the behavior of the first part of the discharging mode, whereas the Avrami–Erofeev (A4) model best fits the last half of the discharging mode. The predicted theoretical models for both samples were compared with previous kinetic data. Full article

The implementation of electricity-charged thermochemical energy storage (TCES) using high-temperature solid cycles would benefit the energy system by enabling the absorption of variable renewable energy (VRE) and its conversion into dispatchable heat and power. Using a Swedish case study, this paper presents a process for TCES-integrated district heating (DH) production, assesses its technical suitability, and discusses some practical implications and additional implementation options. The mass and energy flows of a biomass plant retrofitted with an iron-based redox loop are calculated for nine specific scenarios that exemplify its operation under electricity generation mixes that differ with respect to variability and price. In addition, the use of two types of electrolyzers (low-temperature and high-temperature versions) is investigated. The results show that for the Swedish case, the proposed scheme is technically feasible and capable of covering the national DH demand by making use of the existing DH plants, with an estimated process energy efficiency (electricity to heat) of 90%. The results also show that for a retrofit of the entire Swedish DH fleet, the required inventories of iron are approximately 2.8 Mt for the intermediate scenario, which represents 0.3% and 11.0% of the national reserves and annual metallurgical production rates of the national industry, respectively. In addition to the dispatchable heat, the process generates a significant amount of nondispatchable heat, especially for the case that employs low-temperature electrolyzers. This added generation capacity allows the process to cover the heat demand while decreasing the maximum capacity of the charging side computed herein. Full article

Nano zero-valent iron particles (nZVFe) are known as one of the most effective materials for the treatment of contaminated water. However, a strong tendency to agglomerate has been reported as one of their major drawbacks. The present study describes a green approach to synthesizing stabilized nZVFe, using biomass as a porous support material. Therefore, in the first step, biomass-derived activated carbon was prepared by thermochemical procedure from rice straw (RSAC), and then the RSAC-supported nZVFe composite (nZVFe–RSAC) was employed to extract Pb(II) from aqueous solution and was successfully synthesized by the sodium borohydride reduction method. It was confirmed through scanning electron microscopy (SEM) and X-ray diffraction (XRD) characteristics that the nZVFe particles are uniformly dispersed. Results of the batch experiments showed that 6 (g L⁻¹) of this nanocomposite could effectively remove about 97% of Pb(II) ions at pH = 6 from aqueous solution. The maximum adsorption capacities of the RS, RSAC, and nZVFe–RSAC were 23.3, 67.8, and 140.8 (mg g⁻¹), respectively. Based on the results of the adsorption isotherm studies, the adsorption of Pb(II) on nZVFe–RSAC is consistent with the Langmuir–Freundlich isotherm model ${\mathrm{R}}^2=0.996)$. The thermodynamic outcomes exhibited the endothermic, possible, and spontaneous nature of adsorption. Adsorption enthalpy and entropy values were determined as 32.2 kJ mol⁻¹ and 216.9 J mol⁻¹ K⁻¹, respectively. Adsorption kinetics data showed that Pb(II) adsorption onto nZVFe–RSAC was fitted well according to a pseudo-second-order model. Most importantly, the investigation of the adsorption mechanism showed that nZVFe particles are involved in the removal of Pb(II) ions through two main processes, namely Pb adsorption on the surface of nZVFe particles and direct role in the redox reaction. Subsequently, all intermediates produced through the redox reaction between nZVFe and Pb(II) were adsorbed on the nZVFe–RSAC surface. According to the results of the NZVFe–RSAC recyclability experiments, even after five cycles of recovery, this nanocomposite can retain more than 60% of its initial removal efficiency. So, the nZVFe–RSAC nanocomposite could be a promising material for permeable reactive barriers given its potential for removing Pb(II) ions. Due to low-cost and wide availability of iron salts as well as rice biowaste, combined with the high adsorption capacity, make nZVFe–RSAC an appropriate choice for use in the field of Pb(II) removal from contaminated water. Full article