JPH11139826A - Production of laminar compound having interlaminar crosslinked structure - Google Patents
Production of laminar compound having interlaminar crosslinked structureInfo
- Publication number
- JPH11139826A JPH11139826A JP9325495A JP32549597A JPH11139826A JP H11139826 A JPH11139826 A JP H11139826A JP 9325495 A JP9325495 A JP 9325495A JP 32549597 A JP32549597 A JP 32549597A JP H11139826 A JPH11139826 A JP H11139826A
- Authority
- JP
- Japan
- Prior art keywords
- powder
- compound
- interlaminar
- compd
- kca
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 150000001875 compounds Chemical class 0.000 title claims description 39
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 238000000034 method Methods 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 6
- 239000002184 metal Substances 0.000 claims abstract description 6
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 4
- 229910052802 copper Inorganic materials 0.000 claims abstract description 4
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 4
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 4
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 4
- 239000011229 interlayer Substances 0.000 claims description 26
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- 239000010410 layer Substances 0.000 claims description 12
- 239000000377 silicon dioxide Substances 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 5
- 238000004132 cross linking Methods 0.000 claims description 2
- 239000011941 photocatalyst Substances 0.000 abstract description 12
- 150000003973 alkyl amines Chemical class 0.000 abstract description 7
- 230000004048 modification Effects 0.000 abstract description 2
- 238000012986 modification Methods 0.000 abstract description 2
- 239000000843 powder Substances 0.000 description 42
- 239000010955 niobium Substances 0.000 description 34
- 239000000126 substance Substances 0.000 description 23
- 239000003153 chemical reaction reagent Substances 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 14
- 239000011575 calcium Substances 0.000 description 13
- 239000004065 semiconductor Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000011734 sodium Substances 0.000 description 11
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 10
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 10
- 239000011651 chromium Substances 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 8
- 238000009830 intercalation Methods 0.000 description 7
- 230000002687 intercalation Effects 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- 150000002736 metal compounds Chemical class 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 5
- 238000010304 firing Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 229910017604 nitric acid Inorganic materials 0.000 description 5
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- QHMGFQBUOCYLDT-RNFRBKRXSA-N n-(diaminomethylidene)-2-[(2r,5r)-2,5-dimethyl-2,5-dihydropyrrol-1-yl]acetamide Chemical compound C[C@@H]1C=C[C@@H](C)N1CC(=O)N=C(N)N QHMGFQBUOCYLDT-RNFRBKRXSA-N 0.000 description 4
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000013032 photocatalytic reaction Methods 0.000 description 2
- 238000006303 photolysis reaction Methods 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- GVHCUJZTWMCYJM-UHFFFAOYSA-N chromium(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GVHCUJZTWMCYJM-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000003574 free electron Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000003506 n-propoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 229910000484 niobium oxide Inorganic materials 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、光触媒などとして
有用な層間架橋構造を有する層状化合物を、層状ペロブ
スカイト型化合物を用い、インターカレーション反応を
利用して効率よく製造する方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for efficiently producing a layered compound having an interlayer crosslinked structure useful as a photocatalyst or the like by using a layered perovskite type compound and utilizing an intercalation reaction.
【０００２】[0002]
【従来の技術】酸化チタンに代表される光応答性半導体
特性を有する金属化合物を利用した半導体光触媒反応
は、半導体電極での水の光分解の発見［「工業化学雑
誌」，第７２巻，第１０８〜１１３ページ（１９６９
年）］以来、光エネルギーから化学エネルギーへの交換
の有力な手段として、多くの研究がなされてきており、
様々な分野における潜在的有用性が明らかになりつつあ
る。2. Description of the Related Art A semiconductor photocatalytic reaction utilizing a metal compound having photoresponsive semiconductor characteristics represented by titanium oxide is disclosed by the discovery of photodecomposition of water at a semiconductor electrode [Industrial Chemistry Magazine, Vol. Pages 108 to 113 (1969
Years)], many studies have been conducted as a promising means of converting light energy into chemical energy.
The potential utility in various fields is emerging.
【０００３】この光応答性半導体特性を有する金属化合
物、いわゆる光触媒は、その結晶分子における価電子帯
と伝導帯との間のエネルギーギャップである「禁止帯」
の値以上のエネルギーを有する光を吸収すると、価電子
帯の電子が伝導帯に光励起されて、伝導帯には自由電子
が、価電子帯には正孔が生成し、これらがそれぞれ還元
反応と酸化反応を起こすことによって光触媒反応が進行
する。A metal compound having photoresponsive semiconductor properties, a so-called photocatalyst, has a "forbidden band" which is an energy gap between a valence band and a conduction band in a crystal molecule.
When light having energy equal to or greater than is absorbed, electrons in the valence band are photoexcited into the conduction band, free electrons are generated in the conduction band, and holes are generated in the valence band. The photocatalytic reaction proceeds by causing the oxidation reaction.
【０００４】しかしながら、半導体光触媒によって水の
光分解が起こるためには、半導体のバンド幅が水の電解
圧（理論値１．２３Ｖ＋過電圧０．４Ｖ＝１．６３Ｖ）
より大きくなければならず、さらに伝導体の電子が水を
還元でき、かつ価電子帯の正孔が水を酸化できる能力が
なければならない。すなわち、伝導帯の下端が水からの
水素発生電位よりマイナス側に、価電子帯の上端が酸素
発生電位よりプラス側に位置していなくてはならない。
この制約のために、理論的に水を完全分解できる半導体
の種類は限られている。However, in order for photodecomposition of water to occur by the semiconductor photocatalyst, the bandwidth of the semiconductor must be equal to the electrolytic pressure of water (theoretical value 1.23 V + overvoltage 0.4 V = 1.63 V).
It must be larger, and moreover, the electrons of the conductor must be able to reduce water, and the holes in the valence band must be capable of oxidizing water. That is, the lower end of the conduction band must be located on the minus side of the hydrogen generation potential from water, and the upper end of the valence band must be located on the plus side of the oxygen generation potential.
Due to this limitation, the types of semiconductors that can completely decompose water theoretically are limited.
【０００５】ところで、光触媒、例えば金属化合物（Ｔ
ｉＯ2）を主体とする光触媒の製造方法としては、無機
材料粉末を用いて、直接高温焼結させる方法、化学処理
により、半導体に一層優れた光応答性を付与するため
に、半導体に金属又は金属化合物の水溶液を吸着させた
のち、この半導体に吸着した金属又は金属化合物を酸
化、還元あるいは還元後に一部酸化する方法、ゾル−ゲ
ル方法などがこれまで知られている。A photocatalyst such as a metal compound (T
As a method for producing a photocatalyst mainly composed of iO 2 ), a method of directly sintering a high temperature using an inorganic material powder, and a method of imparting a more excellent photoresponsiveness to a semiconductor by a chemical treatment by using a metal or metal A method of adsorbing an aqueous solution of a metal compound and then oxidizing, reducing or partially oxidizing the metal or the metal compound adsorbed on the semiconductor, a sol-gel method, and the like have been known.
【０００６】しかしながら、光応答性半導体特性を有す
る金属化合物を用いた光触媒においては、半導体のバン
ド幅が大きすぎるため、太陽光の可視光部分を吸収でき
ず、ほぼ近紫外光のみが反応に寄与し、また、光エネル
ギーによる励起により生じた電子と正孔が容易に再結合
するために、種々の反応系における反応量子収率が低い
という欠点がある。However, in a photocatalyst using a metal compound having photoresponsive semiconductor characteristics, the visible light portion of sunlight cannot be absorbed because the bandwidth of the semiconductor is too large, and almost only near-ultraviolet light contributes to the reaction. In addition, since electrons and holes generated by excitation by light energy easily recombine, there is a disadvantage that the reaction quantum yield in various reaction systems is low.
【０００７】最近、層状複合酸化物、例えば層状ペロブ
スカイト型のＫＣａ2Ｎｂ3Ｏ10などが、光応答性半導体
特性を有する光触媒として提案され、このような層状ペ
ロブスカイト型化合物は、用いる元素に種々の組合わせ
が可能であり、例えばＫ［Ｃａ2Ｎａn-3ＮｂnＯ3n+1］
で表わされる各種の化合物を調製することができるとい
う利点を有している。Recently, layered composite oxides such as layered perovskite type KCa 2 Nb 3 O 10 have been proposed as photocatalysts having photoresponsive semiconductor properties. Such layered perovskite type compounds have various elements used. Combinations are possible, for example, K [Ca 2 Na n-3 Nb n O 3n + 1 ]
Has the advantage that various compounds represented by the formula can be prepared.
【０００８】一般に、層状化合物を用いて、高機能の光
触媒、例えば可視光による水の水素と酸素への完全分解
触媒を調製する際には、層間をいかに修飾するかが、重
要な問題となるが、層状ペロブスカイトの場合には、層
間電荷密度が高いため、層間距離を拡大しにくく、層間
を修飾することが困難であり、高機能の光触媒が得られ
にくいという欠点がある。In general, when preparing a highly functional photocatalyst, for example, a catalyst for completely decomposing water into hydrogen and oxygen by visible light using a layered compound, how to modify the layers becomes an important issue. However, in the case of a layered perovskite, the interlayer charge density is high, so that it is difficult to increase the interlayer distance, it is difficult to modify the interlayer, and it is difficult to obtain a highly functional photocatalyst.
【０００９】[0009]
【発明が解決しようとする課題】本発明は、このような
事情のもとで、層状化合物の層間距離を拡大して層間を
修飾し、高機能光触媒として有用な層状化合物を効率よ
く製造する方法を提供することを目的としてなされたも
のである。SUMMARY OF THE INVENTION Under such circumstances, the present invention provides a method for efficiently producing a layered compound useful as a high-performance photocatalyst by increasing the interlayer distance of the layered compound and modifying the layers. The purpose of this is to provide.
【００１０】[0010]
【課題を解決するための手段】本発明者らは、層状化合
物の層間を修飾する方法について鋭意研究を重ねた結
果、高温反応により調製した層状ペロブスカイト型化合
物を用い、これをプロトン交換処理したのち、長鎖アル
キルアミンのインターカレーション処理、テトラアルコ
キシシランによる処理及び焼成処理を順次施すことによ
り、層間にシリカの支柱を有する層間架橋構造の層状化
合物が容易に得られることを見出し、この知見に基づい
て本発明を完成するに至った。Means for Solving the Problems The inventors of the present invention have conducted intensive studies on a method of modifying the interlayer of a layered compound, and as a result, used a layered perovskite compound prepared by a high-temperature reaction, and subjected to a proton exchange treatment. It has been found that by sequentially performing intercalation treatment of a long-chain alkylamine, treatment with tetraalkoxysilane, and calcination treatment, a layered compound having an interlayer cross-linked structure having pillars of silica between layers can be easily obtained. Based on this, the present invention has been completed.
【００１１】すなわち、本発明は、一般式 Ｋ［Ｃａ2Ｎａn-3ＮｂnＯ3n+1］ （Ｉ） （式中のｎは３〜６の数であり、Ｎｂは１０原子％以下
の割合でＮｉ、Ｖ、Ｃｕ、Ｃｒ及びＷの中から選ばれた
少なくとも１種の金属と置換されていてもよい）で表わ
される層状ペロブスカイト型化合物をプロトン交換処理
したのち、長鎖アルキルアミンをインターカレートし、
次いでテトラアルコキシシランを反応させ、さらに酸素
含有ガス雰囲気下、４００〜６００℃の温度で焼成処理
して層間にシリカの支柱を形成させることを特徴とする
層間架橋構造を有する層状化合物の製造方法を提供する
ものである。That is, the present invention relates to a compound represented by the general formula: K [Ca 2 Na n-3 Nb n O 3n + 1 ] (I) wherein n is a number of 3 to 6, and Nb is 10 atom% or less. May be substituted with at least one metal selected from the group consisting of Ni, V, Cu, Cr and W), after proton exchange treatment of the layered perovskite compound represented by Calate and
Next, a method for producing a layered compound having an interlayer crosslinked structure, characterized by reacting tetraalkoxysilane and further baking at a temperature of 400 to 600 ° C. under an oxygen-containing gas atmosphere to form a pillar of silica between layers. To provide.
【００１２】[0012]
【発明の実施の形態】本発明方法においては、層状化合
物として、前記一般式（Ｉ）で表わされる層状ペロブス
カイト型化合物が用いられるが、この層状ペロブスカイ
ト型化合物は、１１５０〜１３５０℃の高温反応によっ
て調製したものが好ましい。一般式（Ｉ）におけるＮｂ
は、１０原子％以下の割合でＮｉ、Ｖ、Ｃｕ、Ｃｒ又は
Ｗ、あるいはこれらを２種以上組み合わせたものと置換
されていてもよい。BEST MODE FOR CARRYING OUT THE INVENTION In the method of the present invention, a layered perovskite compound represented by the general formula (I) is used as a layered compound. Those prepared are preferred. Nb in the general formula (I)
May be substituted with Ni, V, Cu, Cr or W or a combination of two or more of them at a ratio of 10 atomic% or less.
【００１３】前記一般式（Ｉ）で表わされる層状ペロブ
スカイト型化合物は、通常用いられている方法、例えば
酸化ニオブ粉末、炭酸カルシウム粉末、炭酸カリウム粉
末及び場合により用いられる炭酸ナトリウム粉末を、そ
れぞれ所定の割合で混合し、この粉末混合物を、空気な
どの酸素含有ガス雰囲気下に、前記範囲の温度で焼成す
ることにより調製される。なお、一般式（Ｉ）におい
て、ｎが３より大きく６以下の化合物（ナトリウムを含
む化合物）を調製する場合には、ＮａＮｂＯ3とＫＣａ2
Ｎｂ3Ｏ10をあらかじめ調製しておき、これらを所望の
割合で含有する粉末混合物を、空気などの酸素含有ガス
雰囲気下に、前記範囲の温度で焼成することにより、調
製するのが有利である。The layered perovskite compound represented by the general formula (I) can be prepared by a commonly used method such as a niobium oxide powder, a calcium carbonate powder, a potassium carbonate powder, and a sodium carbonate powder optionally used, respectively. The powder mixture is prepared by baking at a temperature within the above range under an atmosphere containing an oxygen-containing gas such as air. In the case of preparing a compound (compound containing sodium) in which n is greater than 3 and 6 or less in the general formula (I), NaNbO 3 and KCa 2
It is advantageous to prepare Nb 3 O 10 in advance, and calcinate a powder mixture containing these at a desired ratio in an atmosphere of an oxygen-containing gas such as air at a temperature in the above range. .
【００１４】本発明方法においては、このようにして調
製された前記一般式（Ｉ）で表わされる層状ペロブスカ
イト型化合物に対し、まず、プロトン交換処理を施すこ
とが必要である。このプロトン交換処理は、酸溶液例え
ば適当な濃度の硝酸水溶液中で該層状ペロブスカイト型
化合物を、常温にて５０〜１００時間程度かきまぜるこ
とにより行うことができる。この処理により、層状ペロ
ブスカイト型化合物は、一般式 Ｈ［Ｃａ2Ｎａn-3ＮｂnＯ3n+1］ （ＩＩ） 又は電子価を考慮した場合、 Ｈ+［Ｃａ2Ｎａn-3ＮｂnＯ3n+1］- （ＩＩ′） （式中のｎは前記と同じ意味をもつ）で表わされる化合
物に変換される。In the method of the present invention, it is necessary to first subject the layered perovskite compound represented by the general formula (I) thus prepared to a proton exchange treatment. This proton exchange treatment can be carried out by stirring the layered perovskite compound in an acid solution, for example, an aqueous solution of nitric acid of an appropriate concentration at room temperature for about 50 to 100 hours. By this treatment, the layered perovskite compound is converted into a compound represented by the general formula H [Ca 2 Na n-3 Nb n O 3n + 1 ] (II) or H + [Ca 2 Nan -3 Nb n O 3n + 1 ] - (II ') (wherein n has the same meaning as described above).
【００１５】次いで、このプロトン交換層状化合物に長
鎖アルキルアミンをインターカレートする。この際用い
られる長鎖アルキルアミンとしては、炭素数５〜１５程
度のものが好ましく、特にｎ‐ヘキシルアミンが好適で
ある。このインターカレーション反応は、低級アルコー
ルなどの適当な溶媒中において、長鎖アルキルアミンと
前記プロトン変換層状化合物とを常温で５０〜２００時
間程度接触させることにより、行うことができる。この
反応により、層状化合物の層間に、長鎖アルキルアミン
がインターカレートされ、層間距離が拡大する。Next, a long-chain alkylamine is intercalated into the proton exchange layered compound. As the long-chain alkylamine used at this time, one having about 5 to 15 carbon atoms is preferable, and n-hexylamine is particularly preferable. This intercalation reaction can be performed by contacting the long-chain alkylamine with the above-mentioned proton conversion layered compound in a suitable solvent such as a lower alcohol at room temperature for about 50 to 200 hours. By this reaction, a long-chain alkylamine is intercalated between the layers of the layered compound, and the interlayer distance is increased.
【００１６】次に、このようにして長鎖アルキルアミン
がインターカレートされた層状化合物にテトラアルコキ
シシランを反応させる。この際用いられるテトラアルコ
キシシランとしては、アルコキシル基がメトキシ基、エ
トキシ基、ｎ‐プロポキシ基、イソプロポキシ基などの
低級アルコキシル基であるものが好ましく、特にテトラ
エトキシシランが好適である。この反応は、一般に４０
〜８０℃程度の温度において５０〜２００時間程度行わ
れる。Next, a tetraalkoxysilane is reacted with the layered compound in which the long-chain alkylamine has been intercalated as described above. As the tetraalkoxysilane used at this time, those in which the alkoxyl group is a lower alkoxyl group such as a methoxy group, an ethoxy group, an n-propoxy group, and an isopropoxy group are preferable, and tetraethoxysilane is particularly preferable. This reaction generally takes 40
This is performed at a temperature of about 80 ° C. for about 50 to 200 hours.
【００１７】最後に、空気などの酸素含有ガス雰囲気下
に、４００〜６００℃の範囲の温度において焼成処理
し、層間中の有機物を燃焼させる。この焼成処理によ
り、一般式 ＳｉＯ2−Ｃａ2Ｎａn-3ＮｂnＯ3n+1 （ＩＩＩ） （式中のｎは前記と同じ意味をもつ）で表わされ、層間
にシリカの支柱を有する層間架橋構造の層状化合物が得
られる。このものは多孔体であって、大きな表面積を有
するとともに、高温安定性も良好である。Finally, in an oxygen-containing gas atmosphere such as air, a baking treatment is performed at a temperature in the range of 400 to 600 ° C. to burn organic substances in the interlayer. By this calcination treatment, it is represented by the general formula SiO 2 —Ca 2 Na n-3 Nb n O 3n + 1 (III) (in the formula, n has the same meaning as described above), and has silica pillars between the layers. A layered compound having an interlayer crosslinked structure is obtained. This is a porous body, has a large surface area, and has good high-temperature stability.
【００１８】[0018]
【発明の効果】本発明によれば、層状ペロブスカイト型
化合物を用い、インターカレーション反応を利用して、
層間にシリカの支柱を有する層間架橋構造の層状化合物
からなる多孔体を効率よく製造することができる。この
ものは、高機能光触媒として、例えば光化学変換や光を
用いた合成化学分野、あるいは光触媒反応を利用した環
境汚染物質の除去処理分野などに有用である。According to the present invention, a layered perovskite type compound is used, and an intercalation reaction is used.
A porous body composed of a layered compound having an interlayer crosslinked structure having silica pillars between layers can be efficiently produced. This is useful as a highly functional photocatalyst, for example, in the field of synthetic chemistry using photochemical conversion or light, or in the field of removal of environmental pollutants using photocatalysis.
【００１９】[0019]
【実施例】次に、本発明を実施例により、さらに詳細に
説明するが、本発明は、これらの例によってなんら限定
されるものではない。Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
【００２０】参考例１ ＫＣａ2Ｎｂ3Ｏ10の調製 酸化ニオブ（Ｖ）粉末［和光純薬工業（株）製、純度９
９．９％］０．０３モル、炭酸カルシウム粉末［和光純
薬工業（株）製、試薬特級］０．０４モル及び炭酸カリ
ウム粉末［片山化学工業（株）製、試薬一級］０．０１
１モルをよく混合したのち、空気中で１２００℃にて７
時間焼成して得られたものを粉砕し、再び空気中で１２
００℃にて７時間焼成した。次いで、これを蒸留水で十
分に洗浄したのち、１１０℃で乾燥処理して、ＫＣａ2
Ｎｂ3Ｏ10粉末を調製した。このもののＸ線回折図を図
１にａとして示す。Reference Example 1 Preparation of KCa 2 Nb 3 O 10 Niobium (V) oxide powder [purity 9 manufactured by Wako Pure Chemical Industries, Ltd.]
9.9%] 0.03 mol, calcium carbonate powder [manufactured by Wako Pure Chemical Industries, Ltd., reagent grade] 0.04 mol and potassium carbonate powder [Katayama Chemical Industry Co., Ltd., reagent first grade] 0.01
After thoroughly mixing 1 mol, the mixture was heated at 1200 ° C in air for 7 minutes.
The product obtained by firing for hours is crushed,
It was baked at 00 ° C. for 7 hours. Next, this was sufficiently washed with distilled water, and then dried at 110 ° C. to obtain KCa 2
Nb 3 O 10 powder was prepared. The X-ray diffraction pattern of this is shown in FIG.
【００２１】参考例２ ＫＣａ2ＮａＮｂ4Ｏ13の調製 酸化ニオブ（Ｖ）粉末［和光純薬工業（株）製、純度９
９．９％］０．０４５モル、炭酸カルシウム粉末［和光
純薬工業（株）製、試薬特級］０．０６モル及び炭酸カ
リウム粉末［片山化学工業（株）製、試薬一級］０．１
６５モルをよく混合したのち、空気中で１０００℃にて
２０時間焼成して得られたものを粉砕し、再び空気中で
１０００℃にて２０時間焼成した。次いで、これを蒸留
水で十分に洗浄したのち、５００℃で３時間乾燥処理し
て、ＫＣａ2Ｎｂ3Ｏ10粉末を調製した。一方、酸化ニオ
ブ（Ｖ）粉末［和光純薬工業（株）製、純度９９．９
％］０．０２モルと炭酸ナトリウム粉末［和光純薬工業
（株）製、試薬一級］０．０２モルとをよく混合したの
ち、空気中で１０５０℃にて６時間焼成してＮａＮｂＯ
3粉末を得た。このようにして得られたＫＣａ2Ｎｂ3Ｏ
10粉末０．０２５モルとＮａＮｂＯ3粉末０．０２５モ
ルとをよく混合したのち、空気中で１２３０℃にて１０
時間焼成して、ＫＣａ2ＮａＮｂ4Ｏ13粉末を調製した。
このもののＸ線回折図を図１にｂとして示す。Reference Example 2 Preparation of KCa 2 NaNb 4 O 13 Niobium (V) oxide powder [purity 9 manufactured by Wako Pure Chemical Industries, Ltd.]
9.9%] 0.045 mol, calcium carbonate powder [manufactured by Wako Pure Chemical Industries, Ltd., reagent grade] 0.06 mol and potassium carbonate powder [Katayama Chemical Industry Co., Ltd., reagent first grade] 0.1
After well mixing 65 moles, the mixture was calcined in air at 1000 ° C. for 20 hours, and the resultant was pulverized and calcined again in air at 1000 ° C. for 20 hours. Next, this was sufficiently washed with distilled water and then dried at 500 ° C. for 3 hours to prepare a KCa 2 Nb 3 O 10 powder. On the other hand, niobium (V) oxide powder [manufactured by Wako Pure Chemical Industries, Ltd., purity 99.9]
%] And 0.02 mol of sodium carbonate powder [Wako Pure Chemical Industries, Ltd., first class reagent] are mixed well, and then calcined in air at 1050 ° C. for 6 hours to obtain NaNbO.
3 powders were obtained. The thus obtained KCa 2 Nb 3 O
After thoroughly mixing 0.025 mol of 10 powder and 0.025 mol of NaNbO 3 powder, 10
After calcining for hours, a KCa 2 NaNb 4 O 13 powder was prepared.
The X-ray diffraction pattern of this is shown as b in FIG.
【００２２】参考例３ ＫＣａ2Ｎａ2Ｎｂ5Ｏ16の調製 参考例２で得たＫＣａ2ＮａＮｂ4Ｏ13粉末０．０１モル
と参考例２で得たＮａＮｂＯ3粉末０．０１モルとをよ
く混合して、空気中で１２６０℃にて１５時間焼成した
のち、粉砕し、再度空気中で１３００℃にて１０時間焼
成して、ＫＣａ2Ｎａ2Ｎｂ5Ｏ16粉末を調製した。このも
ののＸ線回折図を図１にｃとして示す。Reference Example 3 Preparation of KCa 2 Na 2 Nb 5 O 16 0.01 mol of KCa 2 NaNb 4 O 13 powder obtained in Reference Example 2 and 0.01 mol of NaNbO 3 powder obtained in Reference Example 2 were well mixed. After mixing and firing in air at 1260 ° C. for 15 hours, the mixture was pulverized and fired again in air at 1300 ° C. for 10 hours to prepare KCa 2 Na 2 Nb 5 O 16 powder. The X-ray diffraction pattern of this is shown as c in FIG.
【００２３】参考例４ ＫＣａ2Ｎａ3Ｎｂ6Ｏ19の調製 参考例２で得たＫＣａ2ＮａＮｂ4Ｏ13粉末０．０１モル
と参考例２で得たＮａＮｂＯ3粉末０．０２モルとをよ
く混合して、空気中で１３２０℃にて５時間焼成したの
ち、粉砕し、再度空気中で１３２０℃にて５時間焼成し
て、ＫＣａ2Ｎａ3Ｎｂ6Ｏ19粉末を調製した。このもの
のＸ線回折図を図１にｄとして示す。Reference Example 4 Preparation of KCa 2 Na 3 Nb 6 O 19 0.01 mol of the KCa 2 NaNb 4 O 13 powder obtained in Reference Example 2 and 0.02 mol of the NaNbO 3 powder obtained in Reference Example 2 were well mixed. After mixing and calcining in air at 1320 ° C. for 5 hours, it was pulverized and calcined again in air at 1320 ° C. for 5 hours to prepare KCa 2 Na 3 Nb 6 O 19 powder. The X-ray diffraction pattern of this is shown in FIG. 1 as d.
【００２４】上記参考例１〜４から、一般式（Ｉ）で示
されるＫ[Ｃａ2Ｎａn-3ＮｂnＯ3n+1］（ｎ＝３〜６）に
おいて、骨格の［Ｃａ2Ｎａn-3ＮｂnＯ3n+1］部分と層
間のＫ部分を組み合わせて層状ペロブスカイト型化合物
になり、ｎを増加すると骨格部分の厚みが増加する。Ｘ
線回折により同定したところ、ｎが３から４，５，６に
なると、層間距離は、それぞれ２．９４ｎｍ、３．７２
ｎｍ、４．４７ｎｍ及び５．２４ｎｍの順に増加したこ
とが分かった。すなわち、参考例で得られた層状ペロブ
スカイト型化合物は、その骨格の修飾を可能にするもの
である。From the above Reference Examples 1-4, in K [Ca 2 Na n-3 Nb n O 3n + 1 ] (n = 3-6) represented by the general formula (I), the skeleton of [Ca 2 Na n] -3 Nb n O 3n + 1] by combining the partial and K portion of the interlayer becomes a layered perovskite type compound, the thickness of the skeletal portion is increased when increasing n. X
As a result of identification by line diffraction, when n changes from 3 to 4, 5, and 6, the interlayer distances are 2.94 nm and 3.72, respectively.
nm, 4.47 nm, and 5.24 nm. That is, the layered perovskite-type compound obtained in the reference example allows modification of its skeleton.
【００２５】実施例１ 参考例１で調製したＫＣａ2Ｎｂ3Ｏ10２．５ｇを６規定
硝酸［和光純薬工業（株）製、試薬特級］水溶液１００
ｍｌ中に入れて、室温でかきまぜながら、３日間プロト
ン交換させたのち、ろ過、洗浄及び乾燥処理してＨＣａ
2Ｎｂ3Ｏ10粉末を得た。Example 1 2.5 g of KCa 2 Nb 3 O 10 prepared in Reference Example 1 was treated with 6N nitric acid [Wako Pure Chemical Industries, Ltd., reagent grade] aqueous solution 100
The mixture was proton-exchanged for 3 days while stirring at room temperature, and then filtered, washed and dried to give HCa.
2 Nb 3 O 10 powder was obtained.
【００２６】このようにして得たＨＣａ2Ｎｂ3Ｏ10粉末
２．２ｇを、ｎ‐ヘキシルアミン［和光純薬工業（株）
製、試薬一級］５０ｍｌとエタノール［和光純薬工業
（株）製、試薬特級］２５ｍｌとの混合溶液中に入れ、
室温でかきまぜながら７日間反応させたのち、ろ過、洗
浄及び乾燥処理して［Ｃ6Ｈ13ＮＨ3］［Ｃａ2Ｎｂ
3Ｏ10］粉末を得た。2.2 g of the HCa 2 Nb 3 O 10 powder thus obtained was mixed with n-hexylamine [Wako Pure Chemical Industries, Ltd.]
, Reagent first grade] 50 ml and ethanol [Wako Pure Chemical Industries, Ltd., reagent special grade] 25 ml mixed solution,
After reacting for 7 days while stirring at room temperature, the mixture was filtered, washed and dried to obtain [C 6 H 13 NH 3 ] [Ca 2 Nb].
[3 O 10 ] powder was obtained.
【００２７】このようにして得た［Ｃ6Ｈ13ＮＨ3］［Ｃ
ａ2Ｎｂ3Ｏ10］粉末２．０ｇをテトラエトキシシラン
［和光純薬工業（株）製、試薬特級］５０ｍｌ中に入
れ、６５℃でかきまぜながら３日間反応させたのち、ろ
過し、エタノールで洗浄後、乾燥した。これによりテト
ラエトキシシランを層間に導入することができた。次い
で、これを空気中で５００℃にて焼成することにより、
層間にシリカの支柱を形成させ、層間架橋構造の層状化
合物であるＳｉＯ2−Ｃａ2Ｎｂ3Ｏ10を製造した。な
お、ｎ‐ヘキシルアミンによるインターカレーション反
応を行うと層間距離が１．４７ｎｍから２．８７ｎｍに
なり、さらにテトラエトキシシランにより支柱を形成さ
せると、層間距離は３．０３ｎｍになった。[C 6 H 13 NH 3 ] [C
a 2 Nb 3 O 10 ] powder in 50 ml of tetraethoxysilane [Wako Pure Chemical Industries, Ltd., reagent grade] was stirred at 65 ° C. for 3 days, followed by filtration and ethanol. After washing, it was dried. Thereby, tetraethoxysilane could be introduced between the layers. Next, by firing this at 500 ° C. in air,
Silica pillars were formed between the layers to produce SiO 2 —Ca 2 Nb 3 O 10 , which is a layered compound having an interlayer crosslinked structure. When an intercalation reaction with n-hexylamine was performed, the interlayer distance was changed from 1.47 nm to 2.87 nm, and when pillars were formed using tetraethoxysilane, the interlayer distance was 3.03 nm.
【００２８】実施例２ 参考例２で調製したＫＣａ2ＮａＮｂ4Ｏ13粉末を用い、
実施例１と同様の方法により、層間にシリカの支柱を形
成させ、層間架橋構造の層間化合物であるＳｉＯ2−Ｃａ
2ＮａＮｂ4Ｏ13を調製した。なお、ｎ‐ヘキシルアミン
によるインターカレーション反応を行うと層間距離が
１．８６ｎｍから３．３０ｎｍになり、テトラエトキシ
シランにより支柱を形成させると、層間距離は３．４０
ｎｍになった。Example 2 Using the KCa 2 NaNb 4 O 13 powder prepared in Reference Example 2,
In the same manner as in Example 1, silica pillars were formed between the layers, and SiO 2 —Ca as an interlayer compound having an interlayer crosslinking structure was formed.
2 NaNb 4 O 13 was prepared. When an intercalation reaction with n-hexylamine is performed, the interlayer distance is changed from 1.86 nm to 3.30 nm, and when pillars are formed with tetraethoxysilane, the interlayer distance is 3.40.
nm.
【００２９】実施例３ 酸化ニオブ（Ｖ）粉末［和光純薬工業（株）製、純度９
９．９％］０．０２９モル、炭酸カルシウム粉末［和光
純薬工業（株）製、試薬特級］０．０４モル、炭酸カリ
ウム粉末［片山化学工業（株）製、試薬一級］０．０１
１モル及び硝酸クロム９水和物［Ｃｒ（ＮＯ3）3・９Ｈ
2Ｏ］粉末［片山化学工業（株）製、試薬特級］０．０
０２モルを蒸留水１００ｍｌに加え、かき混ぜながら蒸
発乾固した。得られた固形物を１１０℃で乾燥させたの
ち、空気中で１２００℃にて５時間焼成して得られたも
のを粉砕した。この粉砕物を空気中で１２００℃にて１
０時間焼成し、蒸留水で十分に洗浄後、１１０℃で乾燥し
て、ＫＣａ2Ｎｂ2.9Ｃｒ0.1Ｏ10粉末を調製した。Example 3 Niobium (V) oxide powder [purity 9 manufactured by Wako Pure Chemical Industries, Ltd.]
9.9%] 0.029 mol, calcium carbonate powder [Wako Pure Chemical Industries, Ltd., reagent grade] 0.04 mol, potassium carbonate powder [Katayama Chemical Industry Co., Ltd., reagent first grade] 0.01
1 mol of chromium nitrate nonahydrate [Cr (NO 3) 3 · 9H
2 O] powder [Katayama Chemical Industry Co., Ltd., reagent grade] 0.0
02 mol was added to 100 ml of distilled water and evaporated to dryness while stirring. After the obtained solid was dried at 110 ° C., it was baked in air at 1200 ° C. for 5 hours, and the obtained solid was pulverized. This pulverized material is placed in air at 1200 ° C. for 1 hour.
After baking for 0 hour, washing sufficiently with distilled water, and drying at 110 ° C., KCa 2 Nb 2.9 Cr 0.1 O 10 powder was prepared.
【００３０】このようにして得たＫＣａ2Ｎｂ2.9Ｃｒ
0.1Ｏ10粉末４．０ｇを６規定の硝酸［和光純薬工業
（株）製、試薬特級］水溶液１５０ｍｌ中に入れ、室温
でかきまぜながら３日間プロトン交換させたのち、ろ
過、洗浄、乾燥して、ＨＣａ2Ｎｂ2.9Ｃｒ0.1Ｏ10粉末を
得た。次いで、このＨＣａ2Ｎｂ2.9Ｃｒ0.1Ｏ10粉末
２．８ｇを、ｎ‐ヘキシルアミン［和光純薬工業（株）
製、試薬一級］８０ｍｌとエタノール［和光純薬工業
（株）製、試薬特級］４０ｍｌとの混合溶液中に入れ、
室温でかきまぜながら７日間反応させたのち、ろ過、洗
浄及び乾燥処理して[Ｃ6Ｈ13ＮＨ3]［Ｃａ2Ｎｂ2.9Ｃｒ
0.1Ｏ10］粉末を得た。次に、この［Ｃ6Ｈ13ＮＨ3］
［Ｃａ2Ｎｂ2.9Ｃｒ0.1Ｏ10］粉末２．０ｇをテトラエ
トキシシラン［和光純薬工業（株）製、試薬特級］５０
ｍｌ中に入れ、６５℃でかきまぜながら７日間（その間
にテトラエトキシシラン２０ｍｌを２回添加した）反応
させたのち、ろ過し、エタノールで洗浄後、乾燥した。
次いで、空気中で５００℃に焼成することにより、層間
にシリカの支柱を形成させ、層間架橋構造の層状化合物
であるＳｉＯ2−Ｃａ2Ｎｂ2.9Ｃｒ0.1Ｏ10を製造した。
なお、ｎ‐ヘキシルアミンによるインターカレーション
反応を行うと層間距離が１．４６ｎｍから２．７３ｎｍ
になり、さらにテトラエトキシシランにより支柱を形成
させると、層間距離は２．９５ｎｍになった。また、温
度を変え、４００℃、５００℃及び６００℃で焼成する
と、層間距離は、それぞれ２．６１ｎｍ、２．４５ｎ
ｍ、２．３９ｎｍとなり、有機物を燃焼させることでや
や小さくなったことが認められたが、高表面積（５００
℃で焼成したものは２９２ｍ2／ｇ）を有し、かつ高温
安定性も認められた。以上の各実施例で得たＸ線回折図
を図２及び図３に示す。図２は、ＫＣａ2Ｎｂ3Ｏ10につ
いての未処理物（ａ）、（ａ）を６Ｎ硝酸水溶液で処理
したもの（ｂ）、（ｂ）をヘキシルアミンを用いてイン
ターカレートしたもの（ｃ）、（ｃ）のヘキシルアミン
をテトラエトキシシランで置換したもの（ｄ）、（ｄ）
を３３０℃で焼成したもの（ｅ）及び（ｄ）を５００℃
で焼成したもの（ｆ）である。また、図３は、ＫＣａ2
ＮａＮｂ4Ｏ13についての未処理物（ａ）、（ａ）を６
Ｎ硝酸水溶液で処理したもの（ｂ）、（ｂ）をヘキシル
アミンを用いてインターカレートしたもの（ｃ）、
（ｃ）のヘキシルアミンをテトラエトキシシランで置換
したもの（ｄ）、（ｄ）を３３０℃で焼成したもの
（ｅ）及び（ｄ）を５００℃で焼成したもの（ｆ）であ
る。The thus obtained KCa 2 Nb 2.9 Cr
4.0 g of 0.1 O 10 powder was placed in 150 ml of 6N nitric acid [Wako Pure Chemical Industries, Ltd., reagent grade] aqueous solution, and stirred at room temperature for 3 days for proton exchange, followed by filtration, washing and drying. And HCa 2 Nb 2.9 Cr 0.1 O 10 powder. Next, 2.8 g of the HCa 2 Nb 2.9 Cr 0.1 O 10 powder was added to n-hexylamine [Wako Pure Chemical Industries, Ltd.
, Reagent first grade] 80 ml and ethanol [Wako Pure Chemical Industries, Ltd., reagent special grade] 40 ml mixed solution,
After reacting for 7 days while stirring at room temperature, the mixture was filtered, washed and dried to obtain [C 6 H 13 NH 3 ] [Ca 2 Nb 2.9 Cr].
0.1 O 10 ] powder was obtained. Next, this [C 6 H 13 NH 3 ]
2.0 g of [Ca 2 Nb 2.9 Cr 0.1 O 10 ] powder was mixed with tetraethoxysilane [reagent grade, manufactured by Wako Pure Chemical Industries, Ltd.] 50
The reaction mixture was stirred for 7 days (while 20 ml of tetraethoxysilane was added twice) while stirring at 65 ° C., filtered, washed with ethanol and dried.
Next, by firing at 500 ° C. in air, pillars of silica were formed between the layers to produce SiO 2 —Ca 2 Nb 2.9 Cr 0.1 O 10 , which is a layered compound having an interlayer crosslinked structure.
When an intercalation reaction with n-hexylamine is performed, the interlayer distance becomes 1.46 nm to 2.73 nm.
Then, when pillars were formed with tetraethoxysilane, the interlayer distance became 2.95 nm. When the temperature is changed and firing is performed at 400 ° C., 500 ° C., and 600 ° C., the interlayer distances are 2.61 nm and 2.45 n, respectively.
m and 2.39 nm, which was recognized to be slightly reduced by burning the organic matter.
℃ those fired at has a 292m 2 / g), and was also observed high temperature stability. FIGS. 2 and 3 show X-ray diffraction diagrams obtained in the above examples. FIG. 2 shows an untreated product of KCa 2 Nb 3 O 10 (a), (a) treated with 6N nitric acid aqueous solution (b), and (b) intercalated with hexylamine (c) ), (C) wherein hexylamine is substituted with tetraethoxysilane (d), (d)
(E) and (d) fired at 330 ° C. at 500 ° C.
(F). FIG. 3 shows KCa 2
Untreated products (a) and (a) for NaNb 4 O 13
(B) treated with an N nitric acid aqueous solution, (b) intercalated with hexylamine (c),
(C) is hexylamine substituted with tetraethoxysilane (d), (d) baked at 330 ° C, (e) and (d) baked at 500 ° C (f).
【図１】 参考例１〜４で得た層状ペロブスカイト型化
合物のＸ線回折図。FIG. 1 is an X-ray diffraction diagram of a layered perovskite compound obtained in Reference Examples 1 to 4.
【図２】 ＫＣａ2Ｎｂ3Ｏ10及びその処理物のＸ線回折
図。FIG. 2 is an X-ray diffraction diagram of KCa 2 Nb 3 O 10 and a processed product thereof.
【図３】 ＫＣａ2ＮａＮｂ4Ｏ13及びその処理物のＸ線
回折図。FIG. 3 is an X-ray diffraction diagram of KCa 2 NaNb 4 O 13 and a processed product thereof.
Claims (2)
の割合でＮｉ、Ｖ、Ｃｕ、Ｃｒ及びＷの中から選ばれた
少なくとも１種の金属と置換されていてもよい）で表わ
される層状ペロブスカイト型化合物をプロトン交換処理
したのち、長鎖アルキルアミンをインターカレートし、
次いでテトラアルコキシシランを反応させ、さらに酸素
含有ガス雰囲気下、４００〜６００℃の温度で焼成処理
して層間にシリカの支柱を形成させることを特徴とする
層間架橋構造を有する層状化合物の製造方法。1. The general formula K [Ca 2 Na n-3 Nb n O 3n + 1 ] (wherein n is a number from 3 to 6, and Nb is Ni, V, Cu at a ratio of 10 atomic% or less. , Cr and W) may be substituted with at least one metal selected from the group consisting of :), a proton-exchange treatment of a layered perovskite compound represented by the formula:
A method for producing a layered compound having an interlayer cross-linking structure, comprising reacting tetraalkoxysilane and baking at a temperature of 400 to 600 ° C. in an oxygen-containing gas atmosphere to form pillars of silica between layers.
ｂＯ3とＫＣａ2Ｎｂ3Ｏ10とを１１５０〜１３５０℃の
温度で反応させることにより調製されたものである請求
項１記載の製造方法。2. The method according to claim 1, wherein the layered perovskite compound is NaN.
bO 3 and KCa 2 Nb 3 O 10 and the manufacturing method according to claim 1, wherein those prepared by reacting at a temperature of from 1150 to 1,350 ° C. a.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32549597A JP3146351B2 (en) | 1997-11-10 | 1997-11-10 | Method for producing layered compound having interlayer crosslinked structure |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32549597A JP3146351B2 (en) | 1997-11-10 | 1997-11-10 | Method for producing layered compound having interlayer crosslinked structure |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11139826A true JPH11139826A (en) | 1999-05-25 |
| JP3146351B2 JP3146351B2 (en) | 2001-03-12 |
Family
ID=18177524
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP32549597A Expired - Lifetime JP3146351B2 (en) | 1997-11-10 | 1997-11-10 | Method for producing layered compound having interlayer crosslinked structure |
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| Country | Link |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100425024B1 (en) * | 2001-11-01 | 2004-03-27 | 주식회사 성원인더스트리 | Hybrid material with multifunctional properties |
| JP2011184273A (en) * | 2010-03-11 | 2011-09-22 | National Institute For Materials Science | Organic solvent dispersion in which flaky perovskite oxide particle is blended and method for producing the same, and perovskite oxide thin film using the organic solvent dispersion and method for producing the same |
| WO2012157740A1 (en) * | 2011-05-19 | 2012-11-22 | 独立行政法人物質・材料研究機構 | High dielectric nanosheet laminate, high dielectric element and method for manufacturing high dielectric element |
-
1997
- 1997-11-10 JP JP32549597A patent/JP3146351B2/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100425024B1 (en) * | 2001-11-01 | 2004-03-27 | 주식회사 성원인더스트리 | Hybrid material with multifunctional properties |
| JP2011184273A (en) * | 2010-03-11 | 2011-09-22 | National Institute For Materials Science | Organic solvent dispersion in which flaky perovskite oxide particle is blended and method for producing the same, and perovskite oxide thin film using the organic solvent dispersion and method for producing the same |
| WO2012157740A1 (en) * | 2011-05-19 | 2012-11-22 | 独立行政法人物質・材料研究機構 | High dielectric nanosheet laminate, high dielectric element and method for manufacturing high dielectric element |
| JP2012240884A (en) * | 2011-05-19 | 2012-12-10 | National Institute For Materials Science | High dielectric nanosheet laminate, high dielectric element, and method for manufacturing high dielectric thin film element |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3146351B2 (en) | 2001-03-12 |
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