Thermochemical two-step water splitting cycle using perovskite oxides based on LaSrMnO3 redox system for solar H2 production

Gokon, Nobuyuki; Hara, Kazuma; Sugiyama, Yoshinobu; Bellan, Selvan; Kodama, Tetsuya; Cho, Hyunseok

doi:10.1016/j.tca.2019.178374

Cited by 31 publications

(12 citation statements)

References 29 publications

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“…The Sr 2+ cation in A-site leads to an increase of the Mn oxidation state for electronic neutrality that allows increasing the reduction extent. The optimum Sr stoichiometry in the lanthanum manganite perovskites is assumed to be in the range 0.3-0.5 [15,[17][18][19][20][21][22][23][24]. Another A-site dopant for lanthanum manganite perovskites is Ca 2+ .…”

Section: Introductionmentioning

confidence: 99%

Two-step CO2 and H2O splitting using perovskite-coated ceria foam for enhanced green fuel production in a porous volumetric solar reactor

Haeussler

Abanades

Julbe

et al. 2020

Journal of CO2 Utilization

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Solar thermochemical cycles offer a viable option for the production of green synthetic fuels from CO 2 and H 2 O. Two-step cycles using redox materials consist of a high-temperature reduction creating oxygen vacancies, followed by a re-oxidation step with an oxidant gas (CO 2 and/or H 2 O), resulting in CO and/or H 2 production. This study focuses on the thermochemical performance in a solar reactor of a new kind of composite reactive material: reticulated ceria foam with uniform perovskite coating, forming a dual-phase layered heterostructure. La 0.5 Sr 0.5 Mn 0.9 Mg 0.1 O 3 (LSMMg) was selected as perovskite coating due to its high fuel productivity and thermochemical stability upon cycling. The perovskite coating improves the reduction step by increasing the reduction extent reached by the reactive material. The results revealed significant enhancement of oxygen exchange in the dual-phase composite material during reduction compared to individual components. The enhanced reduction extent had a beneficial effect on the oxygen release rate and the total amount of fuel produced by CO 2 and H 2 O splitting, whereas an adverse impact on the peak rate during H 2 /CO evolution was noticed. Decreasing the reduction pressure allowed enhancing the non-stoichiometric oxygen extent, while the re-oxidation extent increased with the inlet oxidant molar fraction. With suitable operating conditions (reduction at 0.100 bar and oxidation in 100% CO 2 ), the LSMMg-coated ceria foam produced a higher amount of fuel but with lower fuel production rate in comparison with pure ceria foam. This study points out the beneficial effects of composite redox materials consisting of LSMMg-coated ceria foam in enhancing the oxygen exchange capacity of ceria for solar fuel production.

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Section: Introductionmentioning

confidence: 99%

Two-step CO2 and H2O splitting using perovskite-coated ceria foam for enhanced green fuel production in a porous volumetric solar reactor

Haeussler

Abanades

Julbe

et al. 2020

Journal of CO2 Utilization

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“…Perovskites have recently emerged as promising alternatives for thermochemical CO 2 splitting due to a lower operation temperature and a higher CO yield. ,− The general formula for perovskite is ABO 3 , wherein cation A is in 12-fold coordination with oxygen and cation B is in 6-fold coordination with oxygen, as shown in Figure a. The A/B sites of perovskite materials can be partially replaced by one or more elements, resulting in a highly flexible elemental composition and a tunable two-step thermochemical CO 2 -splitting performance. ,,− Among them, Mn-based perovskite materials are widely studied. McDaniel et al first found that Sr- and Al-doped LaMnO 3 exhibited a remarkable improvement of CO production compared with that of CeO 2 in the temperature range of 1000–1350 °C, and the material was not deactivated after 80 cycles.…”

Section: Introductionmentioning

confidence: 99%

Ca- and Ga-Doped LaMnO₃ for Solar Thermochemical CO₂ Splitting with High Fuel Yield and Cycle Stability

Liu

Wang

Gao

et al. 2021

ACS Appl. Energy Mater.

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Solar thermochemical CO 2 splitting to produce fuels is an effective route to reduce carbon emission. However, it is still a daunting challenge to achieve a high CO yield and good cycle stability simultaneously at a low reaction temperature. Here, Caand Ga-doped LaMnO 3 is introduced for solar thermochemical CO 2 splitting with an ultrahigh CO yield and excellent cycle stability at a moderate operation temperature. The average CO production reaches 513 μmol/g for La 0.6 Ca 0.4 Mn 0.8 Ga 0.2 O 3 when operating between 1350 and 1050 °C. Such a high value sets a record among directly measured thermochemical CO production in the literature with the temperature swing limited within 300 °C. No obvious performance deterioration over eight cycles is observed due to stable structures. The high CO production of La 0.6 Ca 0.4 Mn 0.8 Ga 0.2 O 3 can be attributed to the transition of the surface reaction to internal bulk diffusion induced by Ca doping and enhanced non-stoichiometry due to Ga doping. This work provides a promising alternative for solar thermochemical CO 2 splitting with high fuel yield and cycle stability.

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“…[20] Researchers then sought new materials that can achieve high fuel yield at appreciably lower reduction temperatures; examples include doped ceria [21][22][23][24][25][26] and perovskites. [27][28][29][30][31][32][33][34][35][36] Although these materials could be reduced at more easily achieved conditions, they were more difficult to oxidize, necessitating a lower temperature and/or larger supply of oxidizer. [27,28] Consequently, the energy burden only shifted from the reduction to the oxidation step, resulting in little or no improvement in process efficiency.…”

Section: Introductionmentioning

confidence: 99%

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

Wheeler

Kumar

et al. 2021

Energy Tech

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Two‐step solar thermochemical water splitting is a promising pathway for renewable fuel production due to its potential for high thermal efficiency via full‐spectrum sunlight utilization. Such a promise critically relies on simultaneous innovation in the redox materials and the reactor systems. Most prior efforts on material design are focused on improving the fuel yield at lower reduction temperatures. However, developing materials with both high fuel output and efficiency remains a key challenge, requiring a rigorous understanding of the effects of material thermodynamic properties. Herein, a generic thermodynamic framework is described to decipher the material effects by studying both the state‐of‐the‐art and hypothetical materials within a counterflow reactor system. A global efficiency map is presented for redox materials, revealing inevitable tradeoffs among competing factors such as thermal losses, sweep gas and oxidizer demand, solid preheating, and reduction enthalpy. The choice of the most efficient material is closely linked to the system conditions. Ceria‐based materials outperform perovskites under most scenarios, and the optimal hypothetical materials tend to favor higher reduction enthalpies and entropies than existing materials. This work offers a valuable material design roadmap to identify solutions toward efficient solar fuel production.

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Thermochemical two-step water splitting cycle using perovskite oxides based on LaSrMnO3 redox system for solar H2 production

Cited by 31 publications

References 29 publications

Two-step CO2 and H2O splitting using perovskite-coated ceria foam for enhanced green fuel production in a porous volumetric solar reactor

Two-step CO2 and H2O splitting using perovskite-coated ceria foam for enhanced green fuel production in a porous volumetric solar reactor

Ca- and Ga-Doped LaMnO₃ for Solar Thermochemical CO₂ Splitting with High Fuel Yield and Cycle Stability

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

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Thermochemical two-step water splitting cycle using perovskite oxides based on LaSrMnO3 redox system for solar H2 production

Cited by 31 publications

References 29 publications

Two-step CO2 and H2O splitting using perovskite-coated ceria foam for enhanced green fuel production in a porous volumetric solar reactor

Two-step CO2 and H2O splitting using perovskite-coated ceria foam for enhanced green fuel production in a porous volumetric solar reactor

Ca- and Ga-Doped LaMnO3 for Solar Thermochemical CO2 Splitting with High Fuel Yield and Cycle Stability

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

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Ca- and Ga-Doped LaMnO₃ for Solar Thermochemical CO₂ Splitting with High Fuel Yield and Cycle Stability