US20130252808A1 - Catalysts for thermochemical fuel production and method of producing fuel using thermochemical fuel production - Google Patents

Catalysts for thermochemical fuel production and method of producing fuel using thermochemical fuel production Download PDF

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US20130252808A1
US20130252808A1 US13/600,948 US201213600948A US2013252808A1 US 20130252808 A1 US20130252808 A1 US 20130252808A1 US 201213600948 A US201213600948 A US 201213600948A US 2013252808 A1 US2013252808 A1 US 2013252808A1
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Prior art keywords
thermochemical
fuel
temperature
catalyst
fuel production
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US13/600,948
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Yoshihiro Yamazaki
Sossina M. Haile
Chih-Kai Yang
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Japan Science and Technology Agency
California Institute of Technology CalTech
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Japan Science and Technology Agency
California Institute of Technology CalTech
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Priority to US13/600,948 priority Critical patent/US20130252808A1/en
Priority to TW102110240A priority patent/TWI603779B/zh
Priority to PCT/JP2013/058431 priority patent/WO2013141385A1/fr
Priority to JP2013549447A priority patent/JP5594800B2/ja
Priority to CN201380015007.4A priority patent/CN104203403B/zh
Priority to KR1020147029479A priority patent/KR101790093B1/ko
Priority to EP13764774.9A priority patent/EP2829321A4/fr
Assigned to CALIFORNIA INSTITUTE OF TECHNOLOGY reassignment CALIFORNIA INSTITUTE OF TECHNOLOGY ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: HAILE, SOSSINA M., YANG, CHIH-KAI
Assigned to JAPAN SCIENCE AND TECHNOLOGY AGENCY reassignment JAPAN SCIENCE AND TECHNOLOGY AGENCY ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: YAMAZAKI, YOSHIHIRO
Publication of US20130252808A1 publication Critical patent/US20130252808A1/en
Priority to US14/595,130 priority patent/US9873109B2/en
Assigned to NATIONAL SCIENCE FOUNDATION reassignment NATIONAL SCIENCE FOUNDATION CONFIRMATORY LICENSE (SEE DOCUMENT FOR DETAILS). Assignors: CALIFORNIA INSTITUTE OF TECHNOLOGY
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Definitions

  • the present invention relates to catalysts for thermochemical fuel production, and a method of producing fuel using thermochemical fuel production.
  • thermochemical fuel generating method is a technology of producing a chemical fuel from thermal energy that may be obtained from sunlight and the like, and of storing the thermal energy as a chemical fuel.
  • the fuel is produced by a two-step thermal cycle (thermochemical cycle) which includes a step performed under a high temperature (first temperature) and a step performed under a low temperature (second temperature).
  • thermal cycle thermal cycle
  • first temperature high temperature
  • second temperature low temperature
  • a catalyst oxide absorbs oxygen from a raw material, and thus fuels such as a syngas, methane, hydrocarbon, alcohol, and hydrogen may be produced.
  • oxide-based catalysts mainly, ZnO—Zn, Fe 2 O 3 —FeO, CeO 2 —Ce 2 O 3 , CeO 2 having a nonstoichiometric composition, mixtures thereof, a partially substituted oxide, and the like have been reported.
  • Water vapor modification of methane (CH 4 +H 2 O ⁇ 6H 2 +CO) using LaSrMnO 3 -based perovskite oxide has been reported, but this is completely different from thermochemical fuel generation (H 2 O ⁇ H 2 +1 ⁇ 2O 2 , or CO 2 ⁇ CO+1 ⁇ 2O 2 ) using water or carbon dioxide, and thermochemical fuel production using a perovskite oxide AXO 3 has not been reported until now.
  • hydrogen is a clean energy source that generates only water after combustion, and thus hydrogen is expected as renewable energy.
  • thermochemical cycle which includes a step performed under a high temperature (first temperature) and a step performed under a low temperature (second temperature), with respect to the high temperature heating
  • a technology using solar energy for example, Japanese Unexamined Patent Application, First Publication No. 2009-263165.
  • thermodynamic efficiency is calculated to be 15 to 75% depending on the oxide systems including ZnO—Zn, Fe 2 O 3 —FeO, CeO 2 —Ce 2 O 3 , nonstoichiometric CeO 2 systems, and some combinations between them. Other systems have been largely unexplored.
  • a record solar-fuel conversion efficiency is 0.8% in a solar-thermochemical cycle of 800 to 1,630° C. using undoped ceria, with 1.3 to 1.5 liters of carbon monoxide and hydrogen production.
  • cerium oxide As catalyst oxides that are used in the thermochemical fuel generation method, cerium oxide (ceria) is known as indicated in the specification of US Patent Application Publication No. 2009/0107044.
  • the solar reactor lost energy of 50% or less as heat, specifically above 1,250° C., and energy of 40% or less as solar re-reflection from the aperture.
  • a mechanical engineering approach and a materials science approach are possible.
  • a heat recovery system might also be integrated. The challenge in this route is how to choose an appropriate oxide structure as well as materials chemistry process from millions of candidate oxides that might show the desired properties. Combinatorial synthesis might be very useful to make candidate oxides, but a rapid way to check fuel productivity at high temperatures is required.
  • An object of the invention is to provide a catalyst, which is formed from a perovskite oxide, for thermochemical fuel production, and a method of producing fuel using thermochemical fuel production that is capable of allowing a fuel to be produced in a thermochemical manner.
  • the invention proposes catalysts for thermochemical fuel production, particularly, bio-inspired catalytic perovskite for solar thermochemical water splitting.
  • Natural photosynthesis specifically, water oxidation is catalyzed in the Mn 4 CaO 5 cluster that possesses the cubic-like frame with a projection. It is anticipated that the artificial water splitting might occur in a similar cubic-like structure containing manganese elements. This hypothesis led to the thermochemical water splitting experiment using manganese-based perovskite (a cubic-like structure, a structure shown on the right of graph in FIG. 3 ).
  • the perovskite splits water and produces hydrogen with the amount exceeding the amount of hydrogen the ceria produces.
  • thermochemical water splitting using nonstoichiometric perovskite oxides.
  • the Sr-doped LaMnO 3 perovskites were utilized in the steam reforming of methane, but no thermochemical water splitting has been demonstrated in perovskite oxides.
  • the black color of the perovskite, compared with the white color of ceria, would be beneficial in efficient solar absorbance, thus making possible efficient solar-fuel conversion.
  • the two-step thermochemical cycle reaction which uses the perovskite oxide as catalyst for hydrogen production as an example of the catalyst for the thermochemical fuel production, includes the following two steps of an oxygen releasing reaction and a hydrogen generating reaction.
  • thermochemical cycle reaction which uses the perovskite oxide as a catalyst for thermochemical methane production as an example of the catalyst for the thermochemical fuel production, includes the following two steps of an oxygen releasing reaction and a methane generating reaction.
  • thermochemical cycle reaction which uses the perovskite oxide as a catalyst for thermochemical methanol production as an example of the catalyst for the thermochemical fuel production, includes the following two steps of an oxygen releasing reaction and a methane generating reaction.
  • the invention provides the following means.
  • a catalyst for thermochemical fuel production which is used for producing the fuel from thermal energy by using a two-step thermochemical cycle of a first temperature and a second temperature that is equal to or lower than the first temperature, wherein the catalyst is formed from a perovskite oxide having a compositional formula of AXO 3 ⁇ (provided that, 0 ⁇ 1).
  • A represents one or more of a rare-earth element (excluding Ce), an alkaline earth metal element, and an alkali metal element
  • X represents one or more of a transition metal element and a metalloid element
  • O represents oxygen.
  • thermochemical fuel production wherein the element A is one or more selected from a group consisting of La, Mg, Ca, Sr, and Ba, and the element X is one or more selected from a group consisting of Mn, Fe, Ti, Zr, V, Cr, Co, Ni, Cu, Zn, Mg, Al, Ga, In, C, Si, Ge, and Sn.
  • thermochemical fuel production wherein the element A is La, and the element X is Mn.
  • thermochemical fuel production A method of producing fuel using thermochemical fuel production, wherein the catalyst for thermochemical fuel production according to any one of (1) to (11) is used.
  • thermochemical fuel production which produces the fuel from thermal energy by using the catalyst for thermochemical fuel production according to any one of (1) to (11) and by using a two-step thermochemical cycle of a first temperature and a second temperature that is equal to or lower than the first temperature, wherein the first temperature is 600 to 1,600° C., and the second temperature is 400 to 1,600° C.
  • thermochemical fuel production according to (13) wherein the first temperature is attained by irradiation of condensed sunlight energy and heating, or by heating using waste heat.
  • thermochemical fuel production which produces the fuel from thermal energy by using a two-step thermochemical cycle of a first temperature and a second temperature that is equal to or lower than the first temperature, the method including: a process of heating a perovskite oxide having a compositional formula of AXO 3 ⁇ (provided that, 0 ⁇ 1) to the first temperature to reduce the perovskite oxide; and a process of bringing a raw material gas into contact with the reduced perovskite oxide and oxidizing the perovskite oxide to produce the fuel.
  • thermochemical fuel production according to (15), wherein the fuel is any one of hydrogen, methane, and methanol.
  • thermochemical fuel production is a concept broadly extending to a concept of “thermochemical hydrogen production” in which water is decomposed into oxygen and hydrogen in relatively mild thermal conditions by combination of a plurality of chemical reactions to fuels including hydrogen.
  • the case of “partially substituted with” is that in which the concentration (x) of the substituted element is in the range of more than 0 to less than 1 when the amount of the element to be substituted before substitution is set to 1.
  • thermochemical fuel production is possible by changing an atmosphere, but in a case where the atmosphere is the same in each case, the “second temperature” represents a temperature lower than the “first temperature”.
  • thermochemical fuel production it is possible to provide a catalyst, which is formed from a perovskite oxide, for thermochemical fuel production, and a method of producing fuel using thermochemical fuel production that is capable of allowing a fuel to be produced in a thermochemical manner.
  • the present invention provides a new catalyst for thermochemical fuel production by using perovskite oxide AXO 3 .
  • elements such as iron and manganese, which are, at present, abundantly found in the Earth's crust, are used, and thus the used amount of rare-earth elements may be reduced. Therefore, it is possible to provide a catalyst for thermochemical fuel production and a method of producing fuel using thermochemical fuel production, in which significant cost reduction may be anticipated, and this will enable the conversion of solar energy into chemical fuel in high efficiency and the storage thereof.
  • FIG. 2 is secondary electron microscope photographs of La 0.8 Sr 0.2 Mn 1-x Fe x O 3 ⁇ .
  • FIG. 3 is a graph illustrating a hydrogen production amount in the case of using La 0.8 Sr 0.2 Mn 1-x Fe x O 3 ⁇ as a catalyst for thermochemical fuel (hydrogen) production.
  • FIG. 4 is a graph illustrating dependency of a hydrogen production (generation) amount on an iron concentration (x) in the case of using La 0.8 Sr 0.2 Mn 1-x Fe x O 3 ⁇ as a catalyst for thermochemical fuel (hydrogen) production.
  • FIG. 5 is a graph illustrating a cycle characteristic of the hydrogen production amount in the case of using La 0.8 Sr 0.2 Mn 1-x Fe x O 3 ⁇ .
  • FIG. 6A is a graph illustrating a cycle characteristic of the hydrogen production amount and an oxygen production amount in the case of using La 0.8 Sr 0.2 Mn 1-x Fe x O 3 ⁇
  • FIG. 6B is a graph illustrating a cycle characteristic of the hydrogen production amount and the oxygen production amount.
  • FIG. 7 is a graph illustrating a hydrogen production amount in the case of using (La 0.8 Sr 0.2 )MnO 3 ⁇ , (La 0.8 Sr 0.2 )(Mn 0.85 Ti 0.15 )O 3 ⁇ , (La 0.8 Sr 0.2 )(Mn 0.85 Fe 0.15 )O 3 ⁇ , (La 0.8 Sr 0.2 )(Mn 0.85 Ni 0.15 )O 3 ⁇ , (La 0.8 Sr 0.2 )(Mn 0.85 Mg 0.15 )O 3 ⁇ , and La(Mn 0.5 Mg 0.5 )O 3 ⁇ as a catalyst for thermochemical hydrogen production, respectively.
  • FIG. 8 is a graph illustrating a cycle characteristic of the hydrogen production amount in the case of using (La 0.8 Sr 0.2 )MnO 3 ⁇ , (La 0.8 Sr 0.2 )(Mn 0.85 Ti 0.15 )O 3 ⁇ , (La 0.8 Sr 0.2 )(Mn 0.85 Fe 0.15 )O 3 ⁇ , (La 0.8 Sr 0.2 )(Mn 0.85 Ni 0.15 )O 3 ⁇ , and (La 0.8 Sr 0.2 )(Mn 0.85 Mg 0.15 )O 3 ⁇ as a catalyst for producing thermochemical hydrogen, respectively.
  • FIG. 9 is a graph illustrating a hydrogen production amount and an oxygen production amount in a case where (La 0.8 Sr 0.2 )CrO 3 ⁇ as a catalyst for producing thermochemical hydrogen is used, a first temperature is set to 1,300° C., and a second temperature is set to 800° C.
  • FIG. 10 is a graph illustrating a hydrogen production amount and an oxygen production amount in a case where (La 0.8 Sr 0.2 )CrO 3 ⁇ as a catalyst for producing thermochemical hydrogen is used, a first temperature is set to 1,500° C., and a second temperature is set to 800° C.
  • FIG. 11 is a graph illustrating a hydrogen production amount in the case of using Ba(Ti 0.6 Mn 0.4 )O 3 ⁇ as a catalyst for thermochemical hydrogen production.
  • FIG. 13 is a graph illustrating a hydrogen production amount in the case of using (La 0.8 Sr 0.2 )MnO 3 ⁇ and (La 0.8 Ba 0.2 )MnO 3 ⁇ as a catalyst for thermochemical hydrogen production.
  • FIG. 14 is a graph illustrating a hydrogen production amount in the case of using (La 0.8 Ba 0.2 )(Mn 0.25 Fe 0.75 )O 3 ⁇ as a catalyst for thermochemical hydrogen production.
  • the catalyst for thermochemical fuel production according to the invention is a catalyst for thermochemical fuel production, which is used for producing the fuel from thermal energy by using a two-step thermochemical cycle of a first temperature and a second temperature that is equal to or lower than the first temperature.
  • the catalyst is formed from a perovskite oxide having a compositional formula of AXO 3 ⁇ (provided that, 0 ⁇ 1).
  • A represents one or more of a rare-earth element (excluding Ce), an alkaline earth metal element, and an alkali metal element
  • X represents one or more of a transition metal element and a metalloid (semi-metallic) element
  • O represents oxygen.
  • a value of ⁇ may be determined in a range not deteriorating an effect of the invention.
  • rare-earth element examples include Sc (scandium), Y (yttrium), La (lanthanum), Pr (praseodymium), Nd (neodymium), Pm (promethium), Sm (samarium), Eu (europium), Gd (gadolinium), Tb (terbium), Dy (dysprosium), Ho (holmium), Er (erbium), Tm (thulium), Yb (ytterbium), Lu (lutetium), and the like.
  • alkaline earth metal element examples include Be (beryllium), Mg (magnesium), Ca (calcium), Sr (strontium), Ba (barium), and Ra (radium).
  • alkali metal examples include Li (lithium), Na (sodium), K (potassium), Rb (rubidium), Cs (cesium), and Fr (francium).
  • transition metal element examples include first transition elements (3d transition elements) such as Sc (scandium), Ti (titanium), V(vanadium), Cr (chromium), Mn (manganese), Fe (iron), Co (cobalt), Ni (nickel), Cu (copper), and Zn (zinc), second transition elements (4d transition elements) such as Y (yttrium), Zr (zirconium), Nb (niobium), Mo (molybdenum), Tc (technetium), Ru (ruthenium), Rh (rhodium), Pd (palladium), Ag (silver), and Cd (cadmium), and third transition elements (4f transition elements) such as La (lanthanum), Pr (praseodymium), Nd (neodymium), Pm (promethium), Sm (samarium), Eu (europium), Gd (gadolinium), Tb (terbium), Dy (dysprosium), Ho (holmium), Er (erbium), T
  • metalloid element examples include B (boron), Si (silicon), Ge (germanium), As (arsenic), Sb (antimony), Te (tellurium), Se (selenium), Po (polonium), and At (astatine).
  • a method of producing fuel using thermochemical fuel production according to an embodiment of the invention is a method of producing fuel using thermochemical fuel production, which produces the fuel from thermal energy by using the catalyst for thermochemical fuel production of the invention and by using a two-step thermochemical cycle of a first temperature and a second temperature that is equal to or lower than the first temperature.
  • the first temperature is 600 to 1,600° C.
  • the second temperature is 400 to 1,600° C.
  • the first temperature and/or the second temperature are attained, for example, by irradiation of condensed sunlight energy and heating, or by heating using waste heat.
  • waste heat for example, waste heat of a power generator, a blast furnace, and the like may be used.
  • the first temperature may be set to 600 to 1,600° C. (for example, 1,400° C.), and the second temperature may be set to 400 to 1,600° C. (for example, 800° C.).
  • the first temperature may be set to 600 to 1,600° C. (for example, 1,400° C.), and the second temperature may be set to 300 to 1,600° C. (for example, 450° C.).
  • the first temperature may be set to 600 to 1,600° C. (for example, 1,400° C.), and the second temperature may be set to 200 to 1,600° C. (for example, 350° C.).
  • a method of producing fuel using thermochemical fuel production is a method of producing fuel using thermochemical fuel production, which produces the fuel from thermal energy by using a two-step thermochemical cycle of a first temperature and a second temperature that is equal to or lower than the first temperature.
  • the method includes a process of heating a perovskite oxide having a compositional formula of AXO 3 ⁇ (provided that, 0 ⁇ 1) to the first temperature to reduce the perovskite oxide, and a process of bringing a raw material gas into contact with the reduced perovskite oxide and oxidizing the perovskite oxide to produce the fuel.
  • a value of ⁇ may be determined in a range not deteriorating an effect of the invention.
  • Examples of the fuel which may be produced by the method of producing fuel using thermochemical fuel production of the invention, include hydrogen, methane, and methanol, but are not limited thereto.
  • water vapor may be exemplified, but it is not limited thereto.
  • Hydrogen may be produced by using the water vapor.
  • carbon dioxide and water vapor may be exemplified.
  • Methane or methanol may be produced by using carbon dioxide and water vapor.
  • perovskite oxide In the production of the catalyst for thermochemical hydrogen, a known method of producing perovskite oxide may be used. For example, powders of raw materials (oxide, hydroxide, oxide-hydroxide, and the like) including elements of a desired perovskite oxide are weighed to obtain a target compositional ratio, and are mixed and crushed. Then, the resultant mixture is calcined, and then the resultant calcined material is fired to produce the catalyst for producing thermochemical hydrogen.
  • Porous pellet of La 0.8 Sr 0.2 Mn 1-x Fe x O 3 ⁇ were synthesized via solid-state reaction.
  • raw material oxides La 2 O 3 , SrCO 2 , MnCO 3 , and Fe 2 O 3
  • These powders, that were obtained, were put into a die with isopropanol and were sintered at 1,500° C. for 10 hours to obtain the porous pellets.
  • the pellet of La 0.8 Sr 0.2 Mn 1-x Fe x O 3 ⁇ had a perovskite structure by X-ray diffraction (refer to FIG. 1 ).
  • the resultant porosity of the pellet was approximately 60%.
  • the resultant pellets had various sizes of pores, ranging from a few to over 100 ⁇ m from a secondary electron microscopy image (refer to FIG. 2 ).
  • the production of hydrogen may be carried out as described below by using the catalyst for thermochemical hydrogen production.
  • the porous pallet was placed inside an infrared furnace and was heated up to 1,400° C. (corresponding to the “first temperature” of the two-step thermochemical cycle) in dry nitrogen containing 10 ppm of oxygen. At this time, it was observed that oxygen was released from the pellet by using mass spectroscopy. Then, the pellet was cooled down to 800° C. (corresponding to the “second temperature” of the two-step thermochemical cycle), followed by flowing 10% water vapor containing argon gas. Hydrogen evolution was observed at 800° C. with an amount of 3 ml/g (corresponding to 60% or less of a hydrogen evolution amount in the case of using undoped ceria). The hydrogen evolution reaction was completed within 10 minutes as shown in FIG. 3 .
  • La 0.8 Sr 0.2 Mn 1-x Fe x O 3 ⁇ in which manganese is partially replaced with iron that has a higher electronegativity in the valence bond theory was synthesized. Analysis results of La 0.8 Sr 0.2 Mn 1-x Fe x O 3 ⁇ are shown below.
  • FIG. 1 shows a graph illustrating X-ray diffraction results of La 0.8 Sr 0.2 Mn 1-x Fe x O 3 ⁇ .
  • the perovskite structure is maintained at the entire iron concentrations (x) of La 0.8 Sr 0.2 Mn 1-x Fe x O 3 ⁇ . Differential scanning calorimetry also showed no evidence in phase transformation up to 1,400° C.
  • FIG. 2 shows secondary electron microscope photographs of La 0.8 Sr 0.2 Mn 1-x Fe x O 3 ⁇ .
  • (a), (c), (e), (g), and (i) represent the secondary electron microscope photographs before the thermal cycle
  • (b), (d), (f), (h), and (j) represent the secondary electron microscope photographs after the thermal cycle of 800 to 1400° C.
  • the iron concentration x is 0, in (c) and (d)
  • the iron concentration x is 0.3
  • the iron concentration x is 0.5
  • the iron concentration x is 0.75
  • in (i) and (j) the iron concentration x is 1.
  • porous structure is maintained after the thermal cycle in any specimen.
  • FIG. 3 shows a graph illustrating a hydrogen production amount in the case of using La 0.8 Sr 0.2 Mn 1-x Fe x O 3 ⁇ as a catalyst for thermochemical hydrogen production.
  • the first temperature and the second temperature of the thermal (thermochemical) cycle were 1,400° C. and 800° C., respectively.
  • FIG. 4 shows a graph illustrating dependency of a hydrogen production (generation) amount on an iron concentration (x) in the case of using La 0.8 Sr 0.2 Mn 1-x Fe x O 3 ⁇ as a catalyst for thermochemical hydrogen production.
  • the first temperature and the second temperature of the thermal cycle were 1,400° C. and 800° C., respectively.
  • Results indicated by a white circle represent first cycle results, and results indicated by a black circle represent ninth cycle results.
  • FIG. 5 shows a graph illustrating a cycle characteristic of the hydrogen production amount in the case of using La 0.8 Sr 0.2 Mn 1-x Fe x O 3 ⁇ as the catalyst for thermochemical hydrogen production.
  • the first temperature and the second temperature of the thermal cycle were 1,400° C. and 800° C., respectively.
  • the hydrogen production amount gradually increased with the cycle.
  • the hydrogen production amount became constant at fifteen cycles.
  • FIG. 6A shows a graph illustrating a cycle characteristic of the hydrogen production amount and the oxygen production amount in the case of using La 0.8 Sr 0.2 Mn 1-x Fe x O 3 ⁇
  • FIG. 6B shows a graph illustrating a cycle characteristic of the hydrogen production amount and the oxygen production amount.
  • the first temperature and the second temperature of the thermal cycle were 1,400° C. and 800° C., respectively.
  • a ratio (H 2 amount/O 2 amount) of the hydrogen production amount and the oxygen production amount is approximately two, and FIG. 6B shows results of water splitting.
  • FIG. 7 shows a graph illustrating a hydrogen production amount in the case of using (La 0.8 Sr 0.2 )MnO 3 ⁇ , (La 0.8 Sr 0.2 )(Mn 0.85 Ti 0.15 )O 3 ⁇ , (La 0.8 Sr 0.2 )(Mn 0.85 Fe 0.15 )O 3 ⁇ , (La 0.8 Sr 0.2 )(Mn 0.85 Ni 0.15 )O 3 ⁇ , (La 0.8 Sr 0.2 )(Mn 0.85 Mg 0.15 )O 3 ⁇ , and La(Mn 0.5 Mg 0.5 )O 3 ⁇ as a catalyst for thermochemical hydrogen production.
  • the hydrogen production amount is indicated by a flow rate (ml/min/g) per unit gram.
  • the first temperature and the second temperature of the thermal (thermochemical) cycle were 1,400° C. and 800° C.
  • hydrogen may be produced in a thermochemical manner.
  • FIG. 8 shows a graph illustrating a cycle characteristic of the hydrogen production amount in the case of using (La 0.8 Sr 0.2 )MnO 3 ⁇ , (La 0.8 Sr 0.2 )(Mn 0.85 Ti 0.15 )O 3 ⁇ , (La 0.8 Sr 0.2 )(Mn 0.85 Fe 0.15 )O 3 ⁇ , (La 0.8 Sr 0.2 )(Mn 0.85 Ni 0.15 )O 3 ⁇ , and (La 0.8 Sr 0.2 )(Mn 0.85 Mg 0.15 )O 3 ⁇ as a catalyst for thermochemical hydrogen production.
  • the first temperature and the second temperature of the thermal cycle were 1,400° C. and 800° C., respectively.
  • FIG. 9 shows a graph illustrating a hydrogen production amount and an oxygen production amount in a case of using (La 0.8 Sr 0.2 )CrO 3 ⁇ as the catalyst for thermochemical hydrogen production.
  • the production amount is indicated by a flow rate (ml/min/g) per unit gram.
  • the first temperature and the second temperature of the thermal (thermochemical) cycle were 1,400° C. and 800° C., respectively.
  • FIG. 10 shows a graph illustrating a hydrogen production amount and an oxygen production amount in the case of using (La 0.8 Sr 0.2 )CrO 3 ⁇ as the catalyst for producing thermochemical hydrogen similarly to FIG. 9 .
  • the first temperature and the second temperature of the thermal (thermochemical) cycle were 1,500° C. and 800° C., respectively.
  • FIG. 11 shows a graph illustrating the hydrogen production amount in the case of using Ba(Ti 0.6 Mn 0.4 )O 3 ⁇ as the catalyst for thermochemical hydrogen production.
  • the first temperature and the second temperature of the thermal (thermochemical) cycle were 1,400° C. and 800° C., respectively.
  • the production amount is indicated by a flow rate (sccm/g) per unit gram.
  • the first temperature and the second temperature of the thermal (thermochemical) cycle were 1,500° C. and 800° C., respectively.
  • FIG. 13 shows a graph illustrating a hydrogen production amount in the case of using (La 0.8 Sr 0.2 )MnO 3 ⁇ and (La 0.8 Ba 0.2 )MnO 3 ⁇ as a catalyst for thermochemical hydrogen production.
  • the production amount is indicated by a flow rate (ml/min/g) per unit gram.
  • the first temperature and the second temperature of the thermal (thermochemical) cycle were 1,400° C. and 800° C., respectively.
  • FIG. 14 is a graph illustrating the hydrogen production amount in the case of using (La 0.8 Ba 0.2 )(Mn 0.25 Fe 0.75 )O 3 ⁇ as the catalyst for thermochemical hydrogen production.
  • the production amount is indicated by a flow rate (ml/min/g) per unit gram.
  • the first temperature of the thermal (thermochemical) cycle was 1,400° C., but the second temperatures thereof were 700° C., 800° C., and 1,000° C., respectively.
  • the hydrogen production amount did not vary largely. However, conversely, in the case where the second temperature was 1,000° C., the hydrogen production amount decreased compared to the case in which the second temperatures were 700° C. and 800° C. by approximately 10%.
  • the concentrated solar energy needs to be absorbed by the perovskite oxide.
  • the solar spectrum ranges from ultraviolet to visible and infrared region (250 nm to over 2700 nm).
  • the absorbed photon excites electrons from the lower-state to the excited state, which will eventually be converted to heat via phonon.
  • the solar absorbance measurement shows that the La 0.8 Sr 0.2 Mn 0.25 Fe 0.75 O 3 ⁇ perovskite absorbs solar energy quite efficiently, at 4 times of ceria.
  • the elements composed in the perovskite are quite earth abundant.
  • the earth abundance of iron and manganese are 35 and 0.6 times the earth abundance of carbon, respectively.
  • Strontium (Sr) exists in the earth crust 5 times more than copper (Cu), and the lanthanum (La) is a half of copper.
  • the present inventors developed catalytic La 0.8 Sr 0.2 Mn 1-x Fe x O 3 ⁇ perovskites for thermochemical hydrogen production by mimicking the catalytic center of Mn 4 CaO 5 cluster in photosystem II.
  • La 0.8 Sr 0.2 Mn 0.25 Fe 0.75 O 3 ⁇ produces 5.3 ml/g of hydrogen in the thermochemical cycle between 800 and 1400° C.
  • the advantages of utilizing nonstoichiometric perovskite over undoped ceria are more efficient solar absorbance by 4 times or less, the earth abundant element utilization for scalable solar fuel production, and lower temperature operation at 1200 to 1400° C.
  • the strontium which is abundant in the Earth in this system is completely soluble in lanthanum, and it is possible to mimic the rare-earth utilization in the catalytic perovskite.
  • the invention will allow the conversion of solar energy into chemical fuel in high efficiency and the storage thereof, and the obtained chemical fuel will be used as clean energy in the field of each industry and as clean industrial raw materials in chemical industry.

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US20130266504A1 (en) * 2012-04-06 2013-10-10 California Institute Of Technology Methods and Materials for the Thermochemical Production of Hydrogen From Water
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US11370724B2 (en) 2012-05-24 2022-06-28 Lummus Technology Llc Catalytic forms and formulations
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101856726B1 (ko) * 2014-12-08 2018-05-10 주식회사 엘지화학 유무기 하이브리드 페로브스카이트 화합물, 이의 제조방법 및 이를 포함하는 태양전지
GB201511855D0 (en) * 2015-07-07 2015-08-19 Univ Newcastle Chemical looping
US10343904B2 (en) * 2015-12-14 2019-07-09 Kyocera Corporation Member for hydrogen production and hydrogen production apparatus
CN108698938B (zh) * 2016-02-25 2021-08-27 京瓷株式会社 光吸收构件、制氢用构件以及制氢装置
US10946362B1 (en) * 2017-02-24 2021-03-16 University Of South Florida Perovskite oxides for thermochemical conversion of carbon dioxide
JP6787826B2 (ja) * 2017-03-28 2020-11-18 京セラ株式会社 水素生成用セル、集光型水素生成用セルおよび水素製造装置
CN111954642B (zh) * 2018-04-12 2023-01-03 国立研究开发法人物质·材料研究机构 六方6h型钡锗氧化物、其制备方法、烧结体和靶
CN110152678B (zh) * 2019-06-05 2021-12-14 内蒙古元瓷新材料科技有限公司 一种电催化还原CO2为能源的纳米Cu-Yb合金催化剂
FR3102764B1 (fr) * 2019-11-06 2022-05-13 Psa Automobiles Sa Dispositif de production d’hydrogene par boucle chimique avec un materiau porteur d’oxygene de type perovskite
JP7417224B2 (ja) * 2020-01-31 2024-01-18 Ｅｎｅｏｓ株式会社 水素の製造方法、一酸化炭素の製造方法および反応媒体
CN111285327B (zh) * 2020-02-18 2021-10-19 西北大学 一种甲烷化学链部分氧化制合成气的方法
CN112076755B (zh) * 2020-10-19 2023-02-28 宁夏大学 一种co2加氢催化剂的制备方法及应用
CN113582240B (zh) * 2020-12-11 2022-09-23 浙江大学 热化学储热材料、热化学储热模块及制备方法
JPWO2022163819A1 (fr) * 2021-01-28 2022-08-04
WO2022181619A1 (fr) * 2021-02-26 2022-09-01 京セラ株式会社 Dispositif de production d'hydrogène et procédé de production d'hydrogène
EP4299509A1 (fr) 2021-02-26 2024-01-03 Kyocera Corporation Dispositif de production d'hydrogène
EP4309786A1 (fr) * 2021-03-17 2024-01-24 Sekisui Chemical Co., Ltd. Agent réducteur, et procédé de production de gaz
WO2023119956A1 (fr) * 2021-12-24 2023-06-29 Ｅｎｅｏｓ株式会社 Méthode de production d'hydrogène et/ou de monoxyde de carbone, méthode de production de gaz de synthèse et milieu réactionnel

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5380692A (en) * 1991-09-12 1995-01-10 Sakai Chemical Industry Co., Ltd. Catalyst for catalytic reduction of nitrogen oxide
US6033632A (en) * 1993-12-08 2000-03-07 Eltron Research, Inc. Solid state oxygen anion and electron mediating membrane and catalytic membrane reactors containing them
US20050245391A1 (en) * 2002-07-09 2005-11-03 Hirohisa Tanaka Catalyst for exhaust gas purification
US20070105715A1 (en) * 2004-12-24 2007-05-10 Hisashi Suda Particulate matter oxidation catalyst and filter
US20100278709A1 (en) * 2007-10-24 2010-11-04 David Waller Catalyst for production of nitric oxide
US20110082030A1 (en) * 2009-10-01 2011-04-07 Gm Global Technology Operations, Inc. Washcoating technique for perovskite catalysts
US20110297666A1 (en) * 2008-07-10 2011-12-08 Epcos Ag Heating Apparatus and Method for Producing the Heating Apparatus

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1095455C (zh) * 2000-01-03 2002-12-04 中国科学院物理研究所 掺锰钛酸钡薄膜材料及其制备方法
JP2004269296A (ja) 2003-03-06 2004-09-30 Kurosaki Harima Corp 水の分解による水素製造法とそれに使用する反応媒体
WO2009055037A1 (fr) 2007-10-26 2009-04-30 California Institute Of Technology Synthèse thermochimique de combustibles pour le stockage d'énergie thermique
JP2009263165A (ja) 2008-04-25 2009-11-12 Tokyo Institute Of Technology 反応性セラミックスおよびその製造方法、ならびに水素製造方法および水素製造装置
RU2509828C2 (ru) * 2008-07-29 2014-03-20 Йеда Рисёч Энд Девелопмент Компани Лтд. Система и способ производства химической потенциальной энергии
CN102030311A (zh) * 2009-09-28 2011-04-27 琳德股份公司 氢气和合成气的生产方法
US8435486B2 (en) * 2010-05-24 2013-05-07 Toyota Jidosha Kabushiki Kaisha Redox material for thermochemical water splitting, and method for producing hydrogen

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5380692A (en) * 1991-09-12 1995-01-10 Sakai Chemical Industry Co., Ltd. Catalyst for catalytic reduction of nitrogen oxide
US6033632A (en) * 1993-12-08 2000-03-07 Eltron Research, Inc. Solid state oxygen anion and electron mediating membrane and catalytic membrane reactors containing them
US6214757B1 (en) * 1993-12-08 2001-04-10 Eltron Research, Inc. Solid state oxygen anion and electron mediating membrane and catalytic membrane reactors containing them
US20050245391A1 (en) * 2002-07-09 2005-11-03 Hirohisa Tanaka Catalyst for exhaust gas purification
US20070105715A1 (en) * 2004-12-24 2007-05-10 Hisashi Suda Particulate matter oxidation catalyst and filter
US20100278709A1 (en) * 2007-10-24 2010-11-04 David Waller Catalyst for production of nitric oxide
US20110297666A1 (en) * 2008-07-10 2011-12-08 Epcos Ag Heating Apparatus and Method for Producing the Heating Apparatus
US20110082030A1 (en) * 2009-10-01 2011-04-07 Gm Global Technology Operations, Inc. Washcoating technique for perovskite catalysts

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
Keith et al., "Synthesis, Crystal Structure, and Characterization of Ba(Ti1/2Mn1/2)O3: A High Permittivity 12R-Type Hexagonal Perovskite," Chem. Mater. 2004, 16, 2007-2015. *
Kindermann et al., "Chemical Interactions between La-Sr-Mn-Fe-O Based Perovskites and Yttria-Stabilized Zirconia," J. Am. Chem. Soc., 80 [4] 909-14 (1997). *
Langhammer et al., "Crystal Structure and Related Properties of Manganese-Doped Barium Titanate Ceramics," J. Am. Chem. Soc., 83 [3] 605-11 (2000). *

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US10195603B2 (en) 2010-05-24 2019-02-05 Siluria Technologies, Inc. Production of ethylene with nanowire catalysts
US9718054B2 (en) 2010-05-24 2017-08-01 Siluria Technologies, Inc. Production of ethylene with nanowire catalysts
US9963402B2 (en) 2011-05-24 2018-05-08 Siluria Technologies, Inc. Catalysts for petrochemical catalysis
US11795123B2 (en) 2011-05-24 2023-10-24 Lummus Technology Llc Catalysts for petrochemical catalysis
US10654769B2 (en) 2011-05-24 2020-05-19 Siluria Technologies, Inc. Catalysts for petrochemical catalysis
US9751818B2 (en) 2011-11-29 2017-09-05 Siluria Technologies, Inc. Nanowire catalysts and methods for their use and preparation
US11078132B2 (en) 2011-11-29 2021-08-03 Lummus Technology Llc Nanowire catalysts and methods for their use and preparation
US8940269B2 (en) * 2012-04-06 2015-01-27 California Institute Of Technology Methods and materials for the thermochemical production of hydrogen from water
US20130266504A1 (en) * 2012-04-06 2013-10-10 California Institute Of Technology Methods and Materials for the Thermochemical Production of Hydrogen From Water
US9206042B2 (en) 2012-04-06 2015-12-08 California Institute Of Technology Methods and materials for the catayltic reduction of carbon dioxide
US11370724B2 (en) 2012-05-24 2022-06-28 Lummus Technology Llc Catalytic forms and formulations
US9868636B1 (en) * 2012-12-06 2018-01-16 National Technology & Engineering Solutions Of Sandia, Llc Thermochemically active iron titanium oxide materials
US9738571B2 (en) * 2013-03-15 2017-08-22 Siluria Technologies, Inc. Catalysts for petrochemical catalysis
US20160122261A1 (en) * 2013-03-15 2016-05-05 Siluria Technologies, Inc. Catalysts for petrochemical catalysis
US10865166B2 (en) 2013-03-15 2020-12-15 Siluria Technologies, Inc. Catalysts for petrochemical catalysis
US10308565B2 (en) 2013-03-15 2019-06-04 Silura Technologies, Inc. Catalysts for petrochemical catalysis
US10780420B2 (en) 2014-05-02 2020-09-22 Lummus Technology Llc Heterogeneous catalysts
US9956544B2 (en) 2014-05-02 2018-05-01 Siluria Technologies, Inc. Heterogeneous catalysts
US10604854B2 (en) 2014-07-17 2020-03-31 The Board Of Trustees Of The Leland Stanford Junior University Heterostructures for ultra-active hydrogen evolution electrocatalysis
US10300465B2 (en) 2014-09-17 2019-05-28 Siluria Technologies, Inc. Catalysts for natural gas processes
US11000835B2 (en) 2014-09-17 2021-05-11 Lummus Technology Llc Catalysts for natural gas processes
US9751079B2 (en) 2014-09-17 2017-09-05 Silura Technologies, Inc. Catalysts for natural gas processes
US10189708B2 (en) * 2016-08-18 2019-01-29 The United States Of America As Represented By The U.S. Environmental Protection Agency Ruthenium on chitosan (ChRu): concerted catalysis for water splitting and reduction
CN109745991A (zh) * 2018-12-13 2019-05-14 大连海事大学 用于煤气化的复合金属氧化物催化剂的制备方法及应用
US11634322B2 (en) 2019-04-03 2023-04-25 California Institute Of Technology Integration of thermochemical water splitting with CO2 direct air capture
CN114904511A (zh) * 2022-03-24 2022-08-16 南京航空航天大学 一种基于SmMnO3钙钛矿的CO2热化学转化材料制备方法和应用

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