WO2018070381A1 - Catalyseur d'oxyde composite à base de fer pour la purifification des gaz d'échappement, et procédé de production de celui-ci - Google Patents

Catalyseur d'oxyde composite à base de fer pour la purifification des gaz d'échappement, et procédé de production de celui-ci Download PDF

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WO2018070381A1
WO2018070381A1 PCT/JP2017/036679 JP2017036679W WO2018070381A1 WO 2018070381 A1 WO2018070381 A1 WO 2018070381A1 JP 2017036679 W JP2017036679 W JP 2017036679W WO 2018070381 A1 WO2018070381 A1 WO 2018070381A1
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fenbo
mass
catalyst
exhaust gas
iron
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PCT/JP2017/036679
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English (en)
Japanese (ja)
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庸裕 田中
三郎 細川
謙太郎 寺村
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国立大学法人京都大学
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8906—Iron and noble metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
    • B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/847—Vanadium, niobium or tantalum or polonium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0207—Pretreatment of the support
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/04—Mixing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust

Definitions

  • the present invention relates to an iron-based composite oxide catalyst for exhaust gas purification and a method for producing the same, and more particularly, the development of a novel iron-based composite oxide catalyst for purifying automobile exhaust gas in a high oxygen concentration region (lean atmosphere) and It relates to the manufacturing method.
  • Automobile exhaust gas purification requires a main catalyst containing Pt, Rh, and Pd as noble metals and a co-catalyst of a CeO 2 -based composite oxide as an oxygen storage material (Non-patent Documents 1 and 2).
  • the role of the main catalyst is to purify harmful substances such as CO and NO contained in the exhaust gas and hydrocarbon (HC) as fuel residue into CO 2 , H 2 O, and N 2 . That is, in exhaust gas purification, it is necessary to proceed simultaneously with an oxidation reaction resulting from combustion of HC and CO and a reduction reaction for converting NO into N 2 . For this reason, the purification efficiency of harmful substances varies greatly depending on the oxygen concentration in the exhaust gas.
  • Non-Patent Document 3 This is because, under conditions where the air-fuel ratio is small (A / F ⁇ 14.6), the exhaust gas atmosphere is under reducing conditions, and HC and CO cannot be completely purified. On the other hand, under conditions where the air-fuel ratio is large (A / F> 14.6), it becomes an oxidizing atmosphere and it becomes difficult to purify NO. Based on this background, the development of a catalyst exhibiting high NO reduction activity under an oxygen-excess atmosphere (under a lean atmosphere) is regarded as an extremely important issue from the viewpoint of improving fuel efficiency.
  • An object of the present invention is to provide a catalyst having improved conversion of nitrogen oxides to nitrogen in exhaust gas in an oxidized state generated by lean burn.
  • the present invention provides the following iron-based composite oxide catalyst for exhaust gas purification and a method for producing the same.
  • Item 1 Formula (I) M / M 1 x O y / FeNbO 4 (I) (In the formula, M represents at least one noble metal selected from the group consisting of Pd, Rh and Pt. M 1 represents Mn or Fe. X represents an integer of 1 to 3, and y represents 2 to 4. When x is 1, y is 2, when x is 2, y is 3, and when x is 3, y is 4. The mass of M 1 x O y is FeNbO. 0 to 50% of the mass of 4.
  • M is supported on M 1 x O y / FeNbO 4
  • An iron-based composite oxide catalyst for exhaust gas purification represented by Item 2.
  • Item 6. The iron-based composite oxide catalyst for exhaust gas purification according to Item 1, wherein M is Rh.
  • Item 3. Item 3.
  • Item 6. The iron-based composite oxide catalyst for purifying exhaust gas according to Item 3, wherein the mass of Fe 2 O 3 is 15 to 25% of the mass of FeNbO 4 .
  • Item 5. M 1 x O y / FeNbO 4 (M 1 represents Mn or Fe.
  • X represents an integer of 1 to 3
  • y represents an integer of 2 to 4.
  • x is 1, y is 2.
  • x is 2, y is 3, and when x is 3, y is 4.
  • the mass of M 1 x O y is 0 to 50% of the mass of FeNbO 4 ).
  • the step of bringing the oxide carrier into contact with a solution containing at least one of a Pd compound, a Pt compound and an Rh compound, followed by firing, is carried out by the following formula (I) M / M 1 x O y / FeNbO 4 (I) (Wherein M represents at least one noble metal selected from the group consisting of Pd, Rh and Pt.
  • M 1 x O y is as defined above.
  • the mass of M 1 x O y is FeNbO 4. (M is supported on Fe 2 O 3 / FeNbO 4. )
  • the manufacturing method of the iron type complex oxide catalyst for exhaust gas purification represented by these.
  • a carrier supporting a noble metal (M) selected from the group consisting of Pd (palladium), Rh (rhodium) and Pt (platinum) is M 1 x O y / FeNbO 4 (M 1 , x, y As defined above, the mass of M 1 x O y is 0 to 50% of the mass of FeNbO 4 ).
  • M 1 x O y is 0 to 50% of the mass of FeNbO 4 ).
  • the iron-based composite oxide catalyst for exhaust gas purification of the present invention is useful as a three-way catalyst.
  • a schematic diagram of the three-way catalyst is shown in FIG.
  • the three-way catalyst includes hydrocarbons (HC), carbon monoxide (CO), nitrogen oxides (NOx), which are harmful components of exhaust gas, water (H 2 O), carbon dioxide (CO 2 ), which are harmless gases, It is a catalyst that converts to nitrogen (N 2 ).
  • the three-way catalyst of the present invention has a structure in which at least one kind of noble metal (Pt, Pd, Ph) is supported on a carrier represented by M 1 x O y / FeNbO 4 .
  • the supported amount of the noble metal M is preferably about 0.1 to 2%, more preferably 0.2 to 1.5, based on the mass of the composite oxide support represented by M 1 x O y / FeNbO 4. %, More preferably about 0.5 to 1.5%, particularly preferably about 0.8 to 1.2%.
  • a smaller amount of noble metal supported is preferable because the cost is reduced. However, if the amount is too small, there is a risk that the NO reduction activity is reduced.
  • the noble metal M supported on the composite oxide support includes at least one selected from the group consisting of Pd, Rh and Pt, preferably Pd, Rh or Pt, more preferably Pd or Rh, most preferably Is Rh.
  • M 1 x O y includes five types of iron oxide or manganese oxide of MnO 2 , Mn 2 O 3 , Fe 2 O 3 , Mn 3 O 4 , Fe 3 O 4 , preferably MnO 2 , Mn 2 O 3 and Fe 2 O 3 , particularly preferably Fe 2 O 3 .
  • the carrier of the present invention is composed of FeNbO 4 and M 1 x O y (M 1 , x, and y are as defined above).
  • the mass of M 1 x O y is 0 to 50% of the mass of FeNbO 4 .
  • the lower limit of the mass of M 1 x O y is 0%, 1%, 2%, 3%, 5%, 7%, 10%, 12% or 15% of the mass of FeNbO 4
  • the upper limit is 50% 45%, 40%, 35%, 30% or 25%.
  • the mass of M 1 x O y is preferably 0 to 40%, more preferably 10 to 30%, and further preferably 15 to 25% of the mass of FeNbO 4 .
  • the iron-based composite oxide catalyst for exhaust gas purification of the present invention becomes M / FeNbO 4 .
  • M 1 x O when y mass is less than 50% greater than 0% of the mass of FeNbO 4 of, FeNbO 4 and M 1 x O y may be generated simultaneously by firing but, Fe compound FeNbO 4 or Mn
  • a composite oxide carrier of the present invention composed of FeNbO 4 and M 1 x O y (M 1 , x, and y are as defined above) can be produced by supporting and firing a compound. Is possible.
  • Fe compounds include organic acid salts such as nitrates and acetates, carbonates, halides (fluorides, chlorides, bromides, iodides), acetylacetone, alkoxides (methoxide, ethoxide, tert-butoxide, etc.)
  • organic acid salts such as nitrates and acetates
  • carbonates halides (fluorides, chlorides, bromides, iodides), acetylacetone, alkoxides (methoxide, ethoxide, tert-butoxide, etc.)
  • halides fluorides, chlorides, bromides, iodides
  • acetylacetone alkoxides (methoxide, ethoxide, tert-butoxide, etc.)
  • alkoxides methoxide, ethoxide, tert-butoxide, etc.
  • Mn compounds include organic acid salts such as nitrates and acetates, carbonates, halides (fluorides, chlorides, bromides, iodides), acetylacetone, alkoxides (methoxide, ethoxide, tert-butoxide, etc.)
  • a complex compound in which a ligand is coordinated, an organic acid salt such as acetate, and a nitrate can be preferably used.
  • the firing temperature is about 400 ° C. to 1000 ° C., preferably about 500 to 700 ° C.
  • the firing time is about 10 minutes to 24 hours, preferably about 30 minutes to 5 hours. Firing can be performed under air flow.
  • Catalyst represented by the general formula (I) of the present invention the solution containing the noble metal compound M 1 x O y / FeNbO 4 (M 1, x, y are as defined above .M 1 x O
  • the mass of y is 0 to 50% of the mass of FeNbO 4 ).
  • the composite oxide carrier represented by (2) is impregnated or immersed, or a solution containing a noble metal compound is applied to the carrier by spraying or the like. Then, it can manufacture by baking.
  • platinum compounds such as hexachloroplatinic acid, tetrachloroplatinic acid, potassium tetrachloroplatinate, sodium tetrachloroplatinate, platinum chloride, dinitrodiamineplatinum; palladium chloride, palladium nitrate, palladium sulfate, palladium acetate, etc.
  • Palladium compounds; rhodium compounds such as rhodium chloride, rhodium sulfate, rhodium nitrate, rhodium hydroxide and acetylacetonatodium.
  • the firing temperature is about 400 ° C. to 1000 ° C., preferably about 500 to 700 ° C.
  • the firing time is about 10 minutes to 24 hours, preferably about 30 minutes to 5 hours. Firing can be performed under air flow.
  • the catalyst of the present invention can treat CO, hydrocarbon (HC) and NOx under lean burn conditions, it is particularly excellent as a three-way catalyst for automobile exhaust gas purification.
  • Example 1 To FeNbO 4 obtained in Reference Production Example 1, the amount is 10 mass% of Fe 2 O 3 after firing 20 wt%, 30 wt%, the amount of Fe (NO 3) becomes 50 mass% 3 ⁇ 9H 2
  • An aqueous solution containing O is impregnated with FeNbO 4 (1 g), fired at 500 ° C., 10 Fe 2 O 3 / FeNbO 4 , 20 Fe 2 O 3 / FeNbO 4 , 30 Fe 2 O 3 / FeNbO 4 , 50 Fe 2 O
  • a composite oxide carrier represented by 3 / FeNbO 4 was obtained.
  • Rhodium acetylacetonate (III) Rh
  • Rhodium acetylacetonate (III) (Rh) so that Rh is 1.0 wt% as a metal with respect to ⁇ -Al 2 O 3 (reference catalyst ALO-7 (180 m 2 / g), provided by the Catalysis Society of Japan, 0.99 g).
  • (Acac) 3 , 0.0401 g) was impregnated and supported in a 9 ml ethyl acetate solution, dried, and then calcined in air at 500 ° C. for 30 minutes to obtain 1 wt% Rh / Al 2 O 3 .
  • Comparative Examples 2-6 1 wt% Rh / Fe 2 O 3 (Comparative Example 3), 1 wt% Rh / 20Fe 2 O 3 / CeO 2 (Comparative Example 4) in the same manner as in Comparative Example 1 except that the metal oxide catalyst used is changed. 1 wt% Rh / 20Fe 2 O 3 / ZrO 2 (Comparative Example 5) and 1 wt% Rh / 20Fe 2 O 3 / Al 2 O 3 (Comparative Example 6) were prepared.
  • Test example 1 The 1 wt% Rh / Al 2 O 3 and 1 wt% Rh / FeNbO 4 catalysts obtained in Comparative Examples 1 and 2 were reacted using an atmospheric pressure fixed bed flow reactor schematically shown in FIG. .
  • a catalyst 200 mg was filled in a quartz reaction tube, and as a pretreatment, He was allowed to flow at 30 mL min ⁇ 1 at 500 ° C. for 1 h.
  • reaction gases NO: 1000 ppm, CO: 1000 ppm, C 3 H 6 : 250 ppm, O 2 : (1462 ppm ⁇ 1125 ppm ⁇ 675 ppm ⁇ 1125 ppm ⁇ 1462 ppm), He: balance mixed gas is circulated to the catalyst layer at 100 mL min ⁇ 1 I let you.
  • the stoichiometric amount of oxygen was 1125 ppm, and in the experiment for varying the oxygen concentration, the concentrations of NO, CO, and C 3 H 6 were fixed.
  • the outlet gas analysis was performed after changing from a high oxygen concentration to a low oxygen concentration and holding for 30 minutes at each oxygen concentration condition when the oxygen concentration was changed again to a high oxygen concentration.
  • Test example 2 The 1 wt% Rh / FeNbO 4 obtained in Example 1 and the 1 wt% Rh / Al 2 O 3 catalyst obtained in Comparative Example 1 were tested using the catalyst shown in FIG.
  • a catalyst 200 mg was filled in a quartz reaction tube, and as a pretreatment, He was allowed to flow at 30 mL min ⁇ 1 at 500 ° C. for 1 h.
  • a catalyst 200 mg was filled in a quartz reaction tube, and as a pretreatment, He was allowed to flow at 30 mL min ⁇ 1 at 500 ° C. for 1 h.
  • the analysis of the reaction gas was performed by two TCD-GC8A (MS-5A and Porapak Q manufactured by Shimadzu). C 3 H 6 , CO, CO 2 , N 2 and N 2 O were measured by two TCD-GC8A (MS-5A and Porapak Q), and the conversion efficiency from NO to N 2 was determined. The results are shown in FIG. 4 and FIG. Was examined supporting amount effect of Fe 2 O 3, it revealed that carrying 20 wt% Fe 2 O 3 1wt% Rh / Fe 2 O 3 / FeNbO 4 is longest maintaining high activity. Further, when the carrier was changed from FeNbO 4 to various carriers, the retention time of all the carriers was lower than that of FeNbO 4 .
  • the XRD pattern was measured for each 2 O 3 catalyst. The results are shown in FIG. In 1 wt% Rh / Fe 2 O 3 / FeNbO 4 supporting 20 mass% or more of Fe 2 O 3 , a peak of ⁇ -Fe 2 O 3 was observed in addition to FeNbO 4 having an ⁇ -PbO 2 type structure.
  • Test Example 5 Obtained in Example 1 was 1wt% Rh / 20 Fe 2 O 3 / FeNbO 4, Comparative Example 3 1 wt% was obtained at a Rh / Fe 2 O 3, FeNbO 4 and ⁇ -Fe 2 O 3 obtained in Reference Production Example 1
  • a catalyst (200 mg) was filled in a quartz reaction tube, and as a pretreatment, He was allowed to flow at 30 mL min ⁇ 1 at 500 ° C. for 1 h.
  • Example 1 In 1wt% Rh / 20 Fe 2 O 3 / FeNbO 4 obtained in Comparative Example 3 1 wt% was obtained at a Rh / Fe 2 O 3, and FeNbO 4 obtained in Reference Production Example 1 ⁇ ⁇ -Fe 2 O An XRD pattern was measured for a catalyst in which 1 wt% Rh was supported on a support obtained by physically mixing 3 in a weight ratio of 80:20. The results are shown in FIG. Compared to the physical mixture catalyst, the peak intensity of the person carrying the Fe 2 O 3 in FeNbO 4 impregnated carrier is Fe 2 O 3 is small, the high activity of carrying a Fe 2 O 3 nano-sized FeNbO 4 It was suggested that this is one of the factors to maintain.
  • Test Example 7 The oxygen storage capacity of the 1 wt% Rh / FeNbO 4 and 1 wt% Rh / 20 Fe 2 O 3 / FeNbO 4 obtained in Example 1 and the 1 wt% Rh / Fe 2 O 3 catalyst obtained in Comparative Example 3 was measured. .
  • the catalyst 100 mg was set in an alumina cell for thermogravimetric analysis (TG-820, manufactured by Rigaku). 5% O 2 / Ar as a reaction gas was passed through the catalyst layer at 100 mL min ⁇ 1 and the temperature was raised to 500 ° C. After holding in a 5% O 2 / Ar atmosphere for 30 minutes, 5% H 2 / Ar was switched to a gas of 100 mL min ⁇ 1 and the change in weight was measured for 20 minutes.
  • TG-820 thermogravimetric analysis

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Abstract

La présente invention concerne un catalyseur d'oxyde composite à base de fer pour la purification des gaz d'échappement, qui est représenté par la formule (I). M/M1 xOy/FeNbO4 (I) (dans la formule, M, M1, x et y sont tels que définis dans la description.)
PCT/JP2017/036679 2016-10-14 2017-10-10 Catalyseur d'oxyde composite à base de fer pour la purifification des gaz d'échappement, et procédé de production de celui-ci WO2018070381A1 (fr)

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JP2016202201A JP2018061943A (ja) 2016-10-14 2016-10-14 排ガス浄化用鉄系複合酸化物触媒及びその製造方法
JP2016-202201 2016-10-14

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003520126A (ja) * 2000-01-24 2003-07-02 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー ゲル触媒およびこれを接触脱水素工程で用いる方法
JP2010046604A (ja) * 2008-08-21 2010-03-04 Utsunomiya Univ 光触媒、水素製造方法、及び有機物分解方法
JP2011136278A (ja) * 2009-12-28 2011-07-14 Mitsubishi Heavy Ind Ltd 排ガス処理触媒およびそれを用いた排ガス浄化方法ならびに排ガス浄化装置
JP2015231593A (ja) * 2014-06-09 2015-12-24 国立研究開発法人物質・材料研究機構 光触媒複合体材料及びその製造方法

Patent Citations (4)

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Publication number Priority date Publication date Assignee Title
JP2003520126A (ja) * 2000-01-24 2003-07-02 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー ゲル触媒およびこれを接触脱水素工程で用いる方法
JP2010046604A (ja) * 2008-08-21 2010-03-04 Utsunomiya Univ 光触媒、水素製造方法、及び有機物分解方法
JP2011136278A (ja) * 2009-12-28 2011-07-14 Mitsubishi Heavy Ind Ltd 排ガス処理触媒およびそれを用いた排ガス浄化方法ならびに排ガス浄化装置
JP2015231593A (ja) * 2014-06-09 2015-12-24 国立研究開発法人物質・材料研究機構 光触媒複合体材料及びその製造方法

Non-Patent Citations (3)

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Title
MAEDA, RAIZO ET AL., OXIDATION/REDUCTION CHARACTERISTICS OF FE-BASED COMPOSITE SYNTHESIZED BY COMPLEX POLYMERIZATION METHOD, vol. 95, no. 2, 11 March 2015 (2015-03-11), pages 412, ISSN: 0285-7626 *
MAEDA, RAIZO ET AL., OXYGEN STORAGE CAPACITY OF FENBO4, CATALYST FORUM, PRE-NOTE FOR FORUM A, vol. 118, 14 September 2016 (2016-09-14), pages 446, ISSN: 1343-9936 *
MAEDA, RAIZO, ET AL., OXYGEN STORAGE CAPACITY OF FENBO4 SYNTHESIZED BY COMPLEX POLYMERIZATION METHOD, CATALYST FORUM, PRE-NOTE FOR FORUM A, vol. 116, 9 September 2015 (2015-09-09), pages 388, ISSN: 1343-9936 *

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