JP5419057B2 - Method for producing high silica nanoporous material by high-temperature acid treatment of crystalline layered silicate and high silica nanoporous material - Google Patents

Method for producing high silica nanoporous material by high-temperature acid treatment of crystalline layered silicate and high silica nanoporous material Download PDF

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JP5419057B2
JP5419057B2 JP2006326396A JP2006326396A JP5419057B2 JP 5419057 B2 JP5419057 B2 JP 5419057B2 JP 2006326396 A JP2006326396 A JP 2006326396A JP 2006326396 A JP2006326396 A JP 2006326396A JP 5419057 B2 JP5419057 B2 JP 5419057B2
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拓史 池田
俊介 茅森
富士夫 水上
靖則 近江
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本発明は、高シリカナノ多孔体の製造方法及びその高シリカナノ多孔体に関するものであり、更に詳しくは、結晶性層状ケイ酸塩の高温酸処理による新規高シリカナノ多孔体の製造方法及びその高シリカナノ多孔体に関するものである。本発明は、例えば、親水性分離剤、吸着剤、形状選択性固体触媒、イオン交換剤、クロマトグラフィー充填剤、化学反応場、建築材などに用いることのできる、耐熱性に優れた高シリカゼオライトを得るための前駆体化合物となる新規な結晶性層状ケイ酸塩を提供し、この新規な結晶性層状ケイ酸塩について、既存の結晶性層状ケイ酸塩を原料に用い、固相から固相への相転移反応させることによる新規高シリカナノ多孔体の迅速な製造方法、及びその高シリカナノ多孔体を提供するものである。   The present invention relates to a method for producing a high silica nanoporous material and the high silica nanoporous material, and more specifically, a method for producing a novel high silica nanoporous material by high-temperature acid treatment of crystalline layered silicate and the high silica nanoporous material. It is about the body. The present invention is a high silica zeolite excellent in heat resistance that can be used for, for example, a hydrophilic separating agent, an adsorbent, a shape-selective solid catalyst, an ion exchange agent, a chromatography filler, a chemical reaction field, and a building material. The present invention provides a novel crystalline layered silicate that serves as a precursor compound for obtaining a new crystalline layered silicate, and the existing crystalline layered silicate is used as a raw material from the solid phase to the solid phase. The present invention provides a rapid method for producing a novel high-silica nanoporous material by subjecting it to a phase transition reaction, and the high-silica nanoporous material.

ゼオライトは、原子レベルで規則的に配列したマイクロ孔（３−２０Å）を有し、骨格構造の構成元素がＳｉ、Ａｌ、Ｏからなるアルミノシリケート型、Ｓｉ、Ｏのみからなるハイシリカ（ピュアシリカ）型に主に分類することができる。ゼオライトは、形状選択的な、あるいは骨格構造に起因した化学的・物理的吸着作用を持つことより、例えば、モレキュラーシーブ（分子ふるい）、分離吸着剤、イオン交換体、触媒としての機能を有する。天然及び合成ゼオライトとして、１６０種類以上の構造が知られており、それと骨格元素の組成を組み合わせることで、目的に合わせた化学的性質や構造安定性、耐熱性を兼ね備えた多孔質材料として、石油化学を中心とする幅広い産業分野で用いられている。   Zeolite has micropores (3-20Å) regularly arranged at the atomic level, and the aluminosilicate type whose constituent elements of the skeletal structure are composed of Si, Al, O, and high silica (pure silica) composed only of Si, O. Mainly can be classified into types. Zeolite has a chemical / physical adsorption action that is shape-selective or due to a skeletal structure, and thus functions as, for example, a molecular sieve (molecular sieve), a separate adsorbent, an ion exchanger, and a catalyst. More than 160 types of structures are known as natural and synthetic zeolites, and by combining them with the composition of skeleton elements, as a porous material that combines chemical properties, structural stability, and heat resistance according to the purpose, petroleum It is used in a wide range of industrial fields centered on chemistry.

ゼオライトは、一般に、水熱合成法、すなわち、大量の水とシリカ源、アルミニウム源、アルカリ金属及びアミン類などの有機構造規程剤；ＯＳＤＡ（生成するゼオライトの細孔を形成する鋳型剤）を所望の化学組成になるように調合し、オートクレーブ等の圧力容器にそれらを封じ込め、加熱することにより、自己圧下で製造されている。ここで、ＯＳＤＡは、生成するゼオライトの細孔を形成するための鋳型剤として機能し、主にアミン分子が用いられている。近年、触媒・材料分野では、より大孔径の高シリカゼオライトへの要望が高まっており、多くの研究がなされているが、製造コストやＯＳＤＡの設計・合成が容易ではないため、実用化可能なものは少ない。   Zeolite generally requires hydrothermal synthesis, that is, a large amount of water and silica source, aluminum source, alkali metal and amines and other organic structural control agents; OSDA (a templating agent that forms the pores of the resulting zeolite) They are prepared under a self-pressure by preparing them so as to have a chemical composition of, enclosing them in a pressure vessel such as an autoclave and heating them. Here, OSDA functions as a templating agent for forming pores of the generated zeolite, and amine molecules are mainly used. In recent years, in the field of catalysts and materials, there has been an increasing demand for a high-silica zeolite with a larger pore diameter, and many studies have been made, but it is not easy to design and synthesize the manufacturing cost and OSDA. There are few things.

近年、新しい試みとして、結晶性層状ケイ酸塩の層状構造を脱水重縮合反応により架橋することで、高シリカゼオライトを得る手法が報告されている（特許文献１〜４、非特許文献１、２）。例えば、結晶性層状ケイ酸塩ＰＬＳ−１は、ＣＤＯ型高シリカゼオライトの前駆体として最近見いだされ、このＰＬＳ−１を焼成するだけで、ＣＤＯ型高シリカゼオライトが得られる（特許文献５、８）。   In recent years, as a new attempt, a method for obtaining a high silica zeolite by crosslinking a layered structure of a crystalline layered silicate by a dehydration polycondensation reaction has been reported (Patent Documents 1 to 4, Non-Patent Documents 1 and 2). ). For example, crystalline layered silicate PLS-1 has recently been found as a precursor of CDO-type high silica zeolite, and CDO-type high silica zeolite can be obtained simply by calcining this PLS-1 (Patent Documents 5 and 8). ).

本発明で得られる、新規結晶性層状ケイ酸塩は、ＣＤＯ型高シリカゼオライトゼオライトに変換可能な前駆体であり、先のＰＬＳ−１と同様に、焼成するだけで、層間が脱水重縮合反応によって架橋し、そこに新たに細孔が形成されることで、ＣＤＯ型高シリカゼオライトゼオライトへと構造変化する。いずれの製法においても、前駆体ＰＬＳ−１からのみＣＤＯ型高シリカゼオライトが得られ、一般的な一段式の水熱合成法では得られていない。更に、池田らによって新規な結晶性層状ケイ酸塩ＰＬＳ−３、ＰＬＳ−４が合成され、これらは、ＰＬＳ−１と同様に、ゼオライト前駆体であり、加熱による脱水重縮合で、それぞれ高シリカＦＥＲ型、ＣＤＯ型ゼオライトが得られる（特許文献６、７）。   The novel crystalline layered silicate obtained in the present invention is a precursor that can be converted into a CDO-type high silica zeolite zeolite, and, just like PLS-1, the layers are dehydrated and polycondensed by firing. The structure is changed to a CDO type high silica zeolite zeolite by newly forming pores therein. In any of the production methods, CDO-type high silica zeolite is obtained only from the precursor PLS-1, and is not obtained by a general one-stage hydrothermal synthesis method. Furthermore, novel crystalline layered silicates PLS-3 and PLS-4 were synthesized by Ikeda et al., Which, like PLS-1, is a zeolite precursor, and each of which is a high silica by dehydration polycondensation by heating. FER type and CDO type zeolite can be obtained (Patent Documents 6 and 7).

また、これらの結晶性層状ケイ酸塩の層間を脱水重縮合させるのではなく、ＳｉＯ４四面体を挿入して架橋させること、より大きな細孔を形成できることが最近報告された。そのイメージは、図９に示すように、縮合させてゼオライトを形成した場合よりも細孔径を拡張させられるメリットがある。また、４配位官能基であるＳｉの２つは骨格と結合するが、残り２つはシラノール基として残ることから、高シリカゼオライトに比べ親水性となることが予想される。実例として、ＭＷＷ型ゼオライトは、基本骨格がある結晶方位に対して剥離しやすく層状化合物になることが知られている。 In addition, it has recently been reported that larger pores can be formed by inserting and cross-linking SiO 4 tetrahedrons instead of dehydrating polycondensation between the layers of these crystalline layered silicates. The image has an advantage that the pore diameter can be expanded as compared with the case where zeolite is formed by condensation as shown in FIG. In addition, although two of the tetracoordinate functional groups, Si, are bonded to the skeleton, the remaining two remain as silanol groups, so that they are expected to be more hydrophilic than high silica zeolite. As an example, it is known that MWW-type zeolite is easily separated from a crystal orientation with a basic skeleton and becomes a layered compound.

辰巳らは、Ｔｉを含有したＴｉ−ＭＷＷの層状前駆体（Ｔｉ−ＭＷＷ（Ｐ）と呼ぶ）を強酸を用いて還流操作を行うことで、ＳｉＯ４四面体が層間に挿入され（一般にシリル化と呼ぶ）、触媒活性の高い高次構造体Ｔｉ−ＹＮＵ−１を報告している。後に、寺崎らの高分解能電子顕微鏡観察から、Ｔｉ−ＹＮＵ−１がＴｉ−ＭＷＷ（Ｐ）の層間がシリル化されより大きな細孔が形成されたものであることを示唆している（非特許文献３〜５）。 Sakai et al. Introduced a Ti-MWW layered precursor containing Ti (referred to as Ti-MWW (P)) using a strong acid to perform a reflux operation, whereby a SiO 4 tetrahedron was inserted between the layers (generally silylated). Report higher-order structure Ti-YNU-1 having a high catalytic activity. Later, high-resolution electron microscopic observation by Terasaki et al. Suggests that Ti-YNU-1 was silylated between Ti-MWW (P) layers to form larger pores (non-patented). Literature 3-5).

これらは、結晶性層状ケイ酸塩をシリル化することで、大きな細孔持った高機能触媒にできるという付加価値を持たせられる点で全く新しい試みであり、層状ケイ酸塩のより高度な利用法である。しかし、最初に報告された強酸条件下での還流操作のみで得られるＴｉ−ＹＮＵ−１と、ジエトキシジメチルシランを層間架橋剤に用い酸処理することで得られるシリル化されたＰＬＳ−１、ＰＲＥＦＥＲ、ＭＷＷ（Ｐ）で何が違うのか明確ではなく、層間架橋剤を用いることの優位性が明らかではない。層状骨格末端のシラノール基にどれだけの量のＳｉＯ４四面体が架橋されているのかが明らかではない。 These are completely new attempts in terms of the added value of being able to make high-functional catalysts with large pores by silylated crystalline layered silicates, and more advanced use of layered silicates. Is the law. However, the first reported Ti-YNU-1 obtained only by reflux operation under strong acid conditions, and silylated PLS-1 obtained by acid treatment using diethoxydimethylsilane as an interlayer crosslinking agent, It is not clear what is different between PREFER and MWW (P), and the advantage of using an interlayer crosslinking agent is not clear. It is not clear how much SiO 4 tetrahedron is cross-linked to the silanol group at the end of the layered skeleton.

産業利用を目指した高シリカナノ多孔体の合成においては、低コストで、調製法がより簡便かつ再現性の高い方法が好ましい。また、層間を架橋する最小構成単位として、ＳｉＯ４四面体を規則的に導入することは、従来の粘土化合物で多く見られる有機分子で架橋した多孔体と異なり、非常に高い次元で規則化されていることが期待される。 In the synthesis of a high-silica nanoporous material aimed at industrial use, a low-cost, simpler preparation method and higher reproducibility are preferred. In addition, the regular introduction of SiO 4 tetrahedron as a minimum structural unit for cross-linking between layers is ordered at a very high dimension, unlike porous bodies cross-linked with organic molecules often found in conventional clay compounds. It is expected that

これをきっかけに、結晶性層状ケイ酸塩ＰＲＥＦＥＲ、ＰＬＳ−１，ＭＷＷ（Ｐ）に、意図的に単一のＳｉＯ４四面体を有したジエトキシジメチルシランを層間架橋剤として導入し、Ｔｉ−ＹＮＵ−１と同様に、シリル化された高次多孔体ができることを報告している（非特許文献６〜９）。 As a result, diethoxydimethylsilane having a single SiO 4 tetrahedron was intentionally introduced into the crystalline layered silicate PREFER, PLS-1, MWW (P) as an interlayer crosslinking agent, and Ti— Similar to YNU-1, it has been reported that silylated higher-order porous bodies can be formed (Non-Patent Documents 6 to 9).

特開２００４−１７５６６１号公報JP 2004-175661 A 特開２００５−０４１７６３号公報JP 2005-041763 A 特開２００４−３３９０４４号公報JP 2004-339044 A 特開２００５−１９４１１３号公報JP 2005-194113 A 特願２００６−１６８２０９号Japanese Patent Application No. 2006-168209 特願２００６−３０６０４１号Japanese Patent Application No. 2006-306041 特願２００６−３２６３９５号Japanese Patent Application No. 2006-326395 特願２００６−２２２８１４号Japanese Patent Application No. 2006-222814 T. Ikeda, Y. Akiyama, Y. Oumi, A. Kawai, F. Mizukami, Angew. Chem. Int. Ed., 43. 4892-4895 (2004)T. Ikeda, Y. Akiyama, Y. Oumi, A. Kawai, F. Mizukami, Angew. Chem. Int. Ed., 43. 4892-4895 (2004) T. Ikeda, Y. Oumi, E. Hida, T. Yokoyama, T. Sano and F. Mizukami, Studies in Surface Science and Catalysis, 158A, 223-230 (2005)T. Ikeda, Y. Oumi, E. Hida, T. Yokoyama, T. Sano and F. Mizukami, Studies in Surface Science and Catalysis, 158A, 223-230 (2005) W. Fan, P. Wu, S. Namba, and T. Tatsumi, Angew. Chem. Int. Ed., 43. 236-240 (2004)W. Fan, P. Wu, S. Namba, and T. Tatsumi, Angew. Chem. Int. Ed., 43. 236-240 (2004) J. Ruan, P. Wu, B. Slater, and O. Terasaki, Angew. Chem. Int. Ed., 44. 6719-6723 (2005)J. Ruan, P. Wu, B. Slater, and O. Terasaki, Angew. Chem. Int. Ed., 44. 6719-6723 (2005) J. Ruan, P. Wu, B. Slater, and O. Terasaki, Abstract of ZMPC2006, P2045 (2006)J. Ruan, P. Wu, B. Slater, and O. Terasaki, Abstract of ZMPC2006, P2045 (2006) P. Wu, J. Ruan , L. Wang, L. Wu, Y. Wang, Y. Liu, S. Inagaki, M. Hayashi, W. Fan, M. He, O. Terasaki and T. Tatsumi, Abstract of ZMPC2006, OC213 (2006)P. Wu, J. Ruan, L. Wang, L. Wu, Y. Wang, Y. Liu, S. Inagaki, M. Hayashi, W. Fan, M. He, O. Terasaki and T. Tatsumi, Abstract of ZMPC2006, OC213 (2006) S. Inagaki, P. Wu, Y. Kubota and T. Tatsumi, Abstract of ZMPC2006, P2127 (2006)S. Inagaki, P. Wu, Y. Kubota and T. Tatsumi, Abstract of ZMPC2006, P2127 (2006) L. Schreyeck, P. Caullet, J. C. Mougenel, J. L. Guth, B. Marler, Microporous Mater. 1996, 6, 259-271L. Schreyeck, P. Caullet, J. C. Mougenel, J. L. Guth, B. Marler, Microporous Mater. 1996, 6, 259-271 L. Schreyeck, P. Caullet, J. C. Mougenel, J. L. Guth, B. Marler, Stud. Surf. Sci. Catal. 1997, 105, 1949-1956L. Schreyeck, P. Caullet, J. C. Mougenel, J. L. Guth, B. Marler, Stud. Surf. Sci. Catal. 1997, 105, 1949-1956 Fathi Kooli, Yoshimichi Kiyozumi, Vicente Rives and Fujio Mizukami, Langmuir 2002, 18, 4103-4110Fathi Kooli, Yoshimichi Kiyozumi, Vicente Rives and Fujio Mizukami, Langmuir 2002, 18, 4103-4110

このような状況の中で、本発明者らは、上記従来技術に鑑みて、従来のシリル化技術を詳細に検討し、これまでに報告されていない新規な結晶性層状ケイ酸塩によるシリル化を検討し、合成と分析・解析を行っていく過程で、結晶性層状ケイ酸塩ＰＬＳ−１、ＰＬＳ−３、ＰＬＳ−４、ＰＲＥＦＥＲを、従来よりも簡便に、すなわち、一切の層間架橋剤を用いず、塩酸又は硝酸等の酸で短時間に、高温酸処理させるだけで、層間がＳｉＯ４四面体によって規則的に架橋され、更に、シラノール基を有した高シリカナノ多孔体が得られることを突き止め、本発明を完成するに至った。 Under such circumstances, the present inventors have examined the conventional silylation technology in detail in view of the above-described conventional technology, and silylation with a novel crystalline layered silicate that has not been reported so far. In the process of synthesis, analysis and analysis, crystalline layered silicates PLS-1, PLS-3, PLS-4, PREFER can be used more easily than conventional, that is, any interlayer cross-linking agent. The layer is regularly cross-linked by SiO 4 tetrahedron, and a high silica nanoporous body having silanol groups can be obtained simply by high-temperature acid treatment with an acid such as hydrochloric acid or nitric acid in a short time without using As a result, the present invention has been completed.

本発明は、上記従来の技術を踏まえ、より簡便な方法による原子レベルで架橋された結晶性層状ケイ酸塩を母体とする高シリカナノ多孔体の調製法を確立するとともに、より多くの結晶性層状ケイ酸塩でも有効であることを検証し、新たな高シリカナノ多孔体の製造方法、及びその高シリカナノ多孔体を提供することを目的とするものである。   The present invention establishes a method for preparing a high-silica nanoporous material based on a crystalline layered silicate crosslinked at an atomic level by a simpler method based on the above-described conventional technique, and more crystalline layered materials. The object of the present invention is to verify that silicate is also effective, and to provide a new method for producing a high silica nanoporous material and the high silica nanoporous material.

上記課題を解決するための本発明は、以下の技術的手段から構成される。
すなわち、本発明は、（１）隣接する層状骨格構造がＳｉＯ４ 四面体部位で架橋されたことで、層間にミクロ孔が形成された構造を有し、親水性を有し、架橋部位が、化学式Ｏ２Ｓｉ（ＯＨ）２で表される局所構造であり、かつその耐熱性が少なくとも６００℃以上であり、表１に示される回折ピーク位置と相対強度の関係を有する、高シリカナノ多孔体ＡＰＺ−１、を提供する。 The present invention for solving the above-described problems comprises the following technical means.
That is, the present invention is (1) having a structure in which the adjacent layered skeleton structure is cross-linked at the SiO 4 tetrahedral site, thereby forming micropores between the layers, has hydrophilicity, and the cross-linked site is a local structure represented by the chemical formula O 2 Si (OH) 2, and its heat resistance Ri der least 600 ° C. or higher, that have a relationship of diffraction peak positions and relative intensities shown in Table 1, high silica A porous body APZ-1 is provided.

また、本発明は、（２）窒素ガス吸着から細孔径８．６Åのミクロ孔及びＳＢＥＴ＝２５０ｍ２／ｇの比表面積を有する、上記（１）記載の高シリカナノ多孔体ＡＰＺ−１、及び、（３）水蒸気吸着からＳＢＥＴ＝１９０ｍ２／ｇの比表面積を有する、上記（１）記載の高シリカナノ多孔体ＡＰＺ−１、を提供する。更に、本発明は、（４）隣接する層状骨格構造がＳｉＯ４ 四面体部位で架橋されたことで、層間にミクロ孔が形成された構造を有し、親水性を有し、架橋部位が、化学式Ｏ２Ｓｉ（ＯＨ）２で表される局所構造であり、かつその耐熱性が少なくとも６００℃以上であり、表２に示される回折ピーク位置と相対強度の関係を有する、高シリカナノ多孔体ＡＰＺ−２、を提供する。 In addition, the present invention provides ( 2 ) a high-silica nanoporous material APZ-1 according to the above (1) having a micropore having a pore diameter of 8.6 mm and a specific surface area of S BET = 250 m 2 / g from nitrogen gas adsorption, ( 3 ) The high silica nanoporous material APZ-1 according to the above (1) having a specific surface area of S BET = 190 m 2 / g from water vapor adsorption. Furthermore, the present invention has a structure in which ( 4 ) adjacent layered skeleton structures are crosslinked at SiO 4 tetrahedral sites, thereby forming micropores between layers, have hydrophilicity, and have a crosslinked site. a local structure represented by the chemical formula O 2 Si (OH) 2, and its heat resistance Ri der least 600 ° C. or higher, that have a relationship of diffraction peak positions and relative intensities shown in Table 2, high silica A porous body APZ-2 is provided.

また、本発明は、（５）窒素ガス吸着から細孔径８．６Åのミクロ孔及びＳＢＥＴ＝５１０ｍ２／ｇの比表面積を有する高シリカナノ多孔体ＡＰＺ−２、及び、（６）水蒸気吸着からＳＢＥＴ＝１２０ｍ２／ｇの比表面積を有する、上記（４）記載の高シリカナノ多孔体ＡＰＺ−２、を提供する。更に、本発明は、（７）隣接する層状骨格構造がＳｉＯ４ 四面体部位で架橋されたことで、層間にミクロ孔が形成された構造を有し、親水性を有し、架橋部位が、化学式Ｏ２Ｓｉ（ＯＨ）２で表される局所構造であり、かつその耐熱性が少なくとも６００℃以上であり、表３に示される回折ピーク位置と相対強度の関係を有する、高シリカナノ多孔体ＡＰＺ−３、を提供する。 The present invention also relates to ( 5 ) nitrogen gas adsorption, high-silica nanoporous material APZ-2 having a micropore with a pore size of 8.6 mm and a specific surface area of S BET = 510 m 2 / g, and ( 6 ) water vapor adsorption. The high silica nanoporous material APZ-2 according to the above ( 4 ), which has a specific surface area of S BET = 120 m 2 / g. Furthermore, the present invention has a structure in which ( 7 ) adjacent layered skeletal structure is cross-linked at the SiO 4 tetrahedron site, so that micropores are formed between the layers, has hydrophilicity, and the cross-linked site is a local structure represented by the chemical formula O 2 Si (OH) 2, and its heat resistance Ri der least 600 ° C. or higher, that have a relationship of diffraction peak positions and relative intensities shown in Table 3, high silica A porous body APZ-3 is provided.

また、本発明は、（８）アルゴンガス吸着から細孔径９．０Åのミクロ孔及びＳＢＥＴ＝３４０ｍ２／ｇの比表面積を有する、上記（７）記載の高シリカナノ多孔体ＡＰＺ−３、及び、（９）水蒸気吸着からＳＢＥＴ＝１２０ｍ２／ｇの比表面積を有する、上記（７）記載の高シリカナノ多孔体ＡＰＺ−３、を提供する。更に、本発明は、（１０）隣接する層状骨格構造がＳｉＯ４ 四面体部位で架橋されたことで、層間にミクロ孔が形成された構造を有し、親水性を有し、架橋部位が、化学式Ｏ２Ｓｉ（ＯＨ）２で表される局所構造であり、かつその耐熱性が少なくとも６００℃以上であり、表４に示される回折ピーク位置と相対強度の関係を有する、高シリカナノ多孔体ＡＰＺ−４、を提供する。 In addition, the present invention provides ( 8 ) a high-silica nanoporous material APZ-3 according to the above ( 7 ) having a micropore having a pore diameter of 9.0 mm and a specific surface area of S BET = 340 m 2 / g from the adsorption of argon gas, ( 9 ) The high silica nanoporous material APZ-3 according to ( 7 ), which has a specific surface area of S BET = 120 m 2 / g from water vapor adsorption. Furthermore, the present invention has a structure in which ( 10 ) adjacent layered skeleton structures are crosslinked at SiO 4 tetrahedral sites, thereby forming micropores between layers, have hydrophilicity, and have a crosslinked site. a local structure represented by the chemical formula O 2 Si (OH) 2, and its heat resistance Ri der least 600 ° C. or higher, that have a relationship of diffraction peak positions and relative intensities shown in Table 4, high silica A porous body APZ-4 is provided.

また、本発明は、（１１）窒素ガス吸着から細孔径９．０Åのミクロ孔及びＳＢＥＴ＝３３０ｍ２／ｇの比表面積を有する、上記（１０）記載の高シリカナノ多孔体ＡＰＺ−４、及び、（１２）水蒸気吸着からＳＢＥＴ＝１６０ｍ２／ｇの比表面積を有する、上記（１０）記載の高シリカナノ多孔体ＡＰＺ−４、を提供する。更に、本発明は、（１３）上記（１）から（１２）のいずれか一項に記載の高シリカナノ多孔体を製造する方法であって、結晶性層状ケイ酸塩ＰＬＳ−１、ＰＬＳ−３、ＰＬＳ−４、又はＰＲＥＦＥＲを高温酸処理することを特徴とする高シリカナノ多孔体の製造方法、及び（１４）上記結晶性層状ケイ酸塩を、塩酸又は硝酸水溶液中で、加熱温度１６０−１８０℃、加熱時間１−２４時間の条件で高温酸処理する、（１３）記載の高シリカナノ多孔体の製造方法、を提供するものである。 The present invention also provides ( 11 ) a high-silica nanoporous material APZ-4 according to the above ( 10 ) having a micropore having a pore size of 9.0 mm from nitrogen gas adsorption and a specific surface area of S BET = 330 m 2 / g, and ( 12 ) The high silica nanoporous material APZ-4 according to ( 10 ), which has a specific surface area of S BET = 160 m 2 / g from water vapor adsorption. Furthermore, the present invention provides ( 13 ) a method for producing a high silica nanoporous material according to any one of (1) to ( 12 ) above, wherein the crystalline layered silicate PLS-1 and PLS-3 are produced. , PLS-4, or PREFER by high-temperature acid treatment, and ( 14 ) the crystalline layered silicate is heated in a hydrochloric acid or nitric acid aqueous solution at a heating temperature of 160-180 The method for producing a high silica nanoporous material according to ( 13 ), which is subjected to high-temperature acid treatment under the conditions of ° C and heating time of 1 to 24 hours.

次に、本発明について更に詳細に説明する。
本発明で用いる結晶性層状ケイ酸塩ＰＬＳ−１、ＰＬＳ−３、ＰＬＳ−４、ＰＲＥＦＥＲは、文献に示される製法で合成した（ＰＬＳ−１：特開２００４−１７５６６１号公報、特開２００５−０４１７６３号公報、特開２００４−３３９０４４号公報、特開２００５−１９４１１３号公報、特願２００６−１６８２０９号、特願２００６−２２２８１４号、T. Ikeda, Y. Akiyama, Y. Oumi, A. Kawai, F. Mizukami, Angew. Chem. Int. Ed., 43. 4892-4895 (2004)、T. Ikeda, Y. Oumi, E. Hida, T. Yokoyama, T. Sano and F. Mizukami, Studies in Surface Science and Catalysis, 158A, 223-230 (2005)。ＰＬＳ−３：非特許文献８、９、特願２００６−３０６０４１号。ＰＬＳ−４：非特許文献１０、特願２００６−３２６３９５号。ＰＲＥＦＥＲ： L. Schreyeck, P. Caullet, J. C. Mougenel, J. L. Guth, B. Marler, Microporous Mater. 1996, 6, 259-271、L. Schreyeck, P. Caullet, J. C. Mougenel, J. L. Guth, B. Marler, Stud. Surf. Sci. Catal. 1997, 105, 1949-1956）。 Next, the present invention will be described in more detail.
The crystalline layered silicates PLS-1, PLS-3, PLS-4, and PREFER used in the present invention were synthesized by a production method described in the literature (PLS-1: JP 2004-175661 A, JP 2005-2005 A). No. 041763, JP 2004-339044, JP 2005-194113, JP 2006-168209, JP 2006-222814, T. Ikeda, Y. Akiyama, Y. Oumi, A. Kawai, F. Mizukami, Angew. Chem. Int. Ed., 43. 4892-4895 (2004), T. Ikeda, Y. Oumi, E. Hida, T. Yokoyama, T. Sano and F. Mizukami, Studies in Surface Science and Catalysis, 158A, 223-230 (2005) PLS-3: Non-Patent Documents 8 and 9, Japanese Patent Application No. 2006-306041 PLS-4: Non-Patent Document 10, Japanese Patent Application No. 2006-326395. Schreyeck, P. Caullet, JC Mougenel, JL Guth, B. Marler, Microporous Mater. 1996, 6, 259-271, L. Schreyeck, P. Caullet, JC Mougenel, JL Guth, B. Marler, Stud. Surf. Sci. Catal. 1997, 105, 1949-1956).

本発明の方法で用いる４種類の結晶性層状ケイ酸塩は、いかなる方法で合成されたものでも構わないが、上記の文献で定義された結晶構造を有していることが必要条件である。次に、本発明で目的とする各生成物の製造例について説明するが、本発明は、これらに制限されるものではなく、製造条件は、当該製造例に準じて任意に設定することができる。   The four types of crystalline layered silicates used in the method of the present invention may be synthesized by any method, but it is a necessary condition that they have a crystal structure defined in the above literature. Next, production examples of each product intended in the present invention will be described, but the present invention is not limited to these, and the production conditions can be arbitrarily set according to the production examples. .

高シリカナノ多孔体ＡＰＺ−１：
先の特許文献１−４及び８に基づいて、水熱合成で得られた結晶性層状ケイ酸塩ＰＬＳ−１を、一例としてその１．０ｇを１Ｍ塩酸水溶液（和光純薬工業株式会社製）１８ｍｌとともに、ＰＥＦＥテフロン（登録商標）内筒容器を持った内容量２３ｍｌのオートクレーブ（Ｐａｒｒ社製）に加える。これに、例えば、加熱温度１７０℃、加熱時間２４時間の条件で、高温酸処理を行う。次に、オートクレーブから生成物を取り出した後、蒸留水で十分濾過・洗浄し、例えば、６０℃で１２時間乾燥させる。この生成物は、表１に示される回折ピーク位置と相対強度の関係を持ち、図１に代表される粉末Ｘ線回折図形によって示される、高シリカナノ多孔体（ＡＰＺ−１：Ａｔｏｍｉｃ Ｐｉｌｌａｒｅｄ Ｚｅｏｌｉｔｅ−１）である。上記の製造条件は、上記製造例に準じて任意に設定することができる。 High silica nanoporous material APZ-1:
As an example, 1.0 g of the crystalline layered silicate PLS-1 obtained by hydrothermal synthesis based on the previous Patent Documents 1-4 and 8 is 1M hydrochloric acid aqueous solution (manufactured by Wako Pure Chemical Industries, Ltd.). Along with 18 ml, add to a 23 ml autoclave (Parr) with a PEFE Teflon (registered trademark) inner cylinder. For example, high-temperature acid treatment is performed under the conditions of a heating temperature of 170 ° C. and a heating time of 24 hours. Next, after removing the product from the autoclave, it is sufficiently filtered and washed with distilled water, and dried at, for example, 60 ° C. for 12 hours. This product has a relationship between the diffraction peak position shown in Table 1 and the relative intensity, and is shown by a powder X-ray diffraction pattern represented by FIG. 1, which is a high silica nanoporous material (APZ-1: Atomic Pillared Zeolite-1). ). Said manufacturing conditions can be arbitrarily set according to the said manufacture example.

高シリカナノ多孔体ＡＰＺ−２：
先の非特許文献８、９に基づいて、得られた固相反応合成で得られた結晶性層状ケイ酸塩ＰＬＳ−３に当たるＣＤＯ型ゼオライトの前駆体となる化合物を、例えば、その一例として、その０．５ｇを１Ｍ塩酸水溶液（和光純薬工業株式会社製）１８ｍｌとともに、ＰＥＦＥテフロン（登録商標）内筒容器を持った内容量２３ｍｌのオートクレーブ（Ｐａｒｒ社製）に加える。これに、例えば、加熱温度１７０℃、加熱時間１８時間の条件で、高温酸処理を行う。次に、オートクレーブから生成物を取り出した後、蒸留水で十分濾過・洗浄し、例えば、６０℃で１２時間乾燥させる。この生成物は、表２に示される回折ピーク位置と相対強度の関係を持ち、図２に代表される粉末Ｘ線回折図形によって示される、高シリカナノ多孔体（ＡＰＺ−２：Ａｔｏｍｉｃ Ｐｉｌｌａｒｅｄ Ｚｅｏｌｉｔｅ−２）である。上記の製造条件は、上記製造例に準じて任意に設定することができる。 High silica nanoporous material APZ-2:
Based on the previous Non- Patent Documents 8 and 9 , for example, a compound that is a precursor of CDO-type zeolite corresponding to the crystalline layered silicate PLS-3 obtained by solid phase reaction synthesis, 0.5 g of the solution is added together with 18 ml of 1M aqueous hydrochloric acid (manufactured by Wako Pure Chemical Industries, Ltd.) to a 23 ml autoclave (manufactured by Parr) having a PEFE Teflon (registered trademark) inner cylinder. For example, high-temperature acid treatment is performed under the conditions of a heating temperature of 170 ° C. and a heating time of 18 hours. Next, after removing the product from the autoclave, it is sufficiently filtered and washed with distilled water, and dried at, for example, 60 ° C. for 12 hours. This product has a relationship between the diffraction peak position shown in Table 2 and the relative intensity, and is shown by a powder X-ray diffraction pattern represented by FIG. 2, which is a high silica nanoporous material (APZ-2: Atomic Pillared Zeolite-2). ). Said manufacturing conditions can be arbitrarily set according to the said manufacture example.

高シリカナノ多孔体ＡＰＺ−３：
先の非特許文献１０に基づいて、固相反応合成で得られた結晶性層状ケイ酸塩ＰＬＳ−４に当たるＣＤＯ型ゼオライトの前駆体となる化合物を、その一例として、その０．５１８ｇを１Ｍ塩酸水溶液（和光純薬工業株式会社製）１８ｍｌとともに、ＰＥＦＥテフロン（登録商標）内筒容器を持った内容量２３ｍｌのオートクレーブ（Ｐａｒｒ社製）に加える。これに、例えば、加熱温度１７０℃、加熱時間１−２４時間の条件で、高温酸処理を行う。次に、オートクレーブから生成物を取り出した後、蒸留水で十分濾過・洗浄し、例えば、６０℃で１２時間乾燥させる。この生成物は、表３に示される回折ピーク位置と相対強度の関係を持ち、図３に代表される粉末Ｘ線回折図形によって示される、高シリカナノ多孔体（ＡＰＺ−３：Ａｔｏｍｉｃ Ｐｉｌｌａｒｅｄ Ｚｅｏｌｉｔｅ−３）である。上記の製造条件は、上記製造例に準じて任意に設定することができる。 High silica nanoporous material APZ-3:
Based on the previous Non- Patent Document 10 , a compound serving as a precursor of a CDO-type zeolite corresponding to the crystalline layered silicate PLS-4 obtained by solid-phase reaction synthesis is used as an example. Along with 18 ml of an aqueous solution (manufactured by Wako Pure Chemical Industries, Ltd.), the mixture is added to an autoclave (manufactured by Parr) having a capacity of 23 ml having a PEFE Teflon (registered trademark) inner cylinder. For example, high-temperature acid treatment is performed under the conditions of a heating temperature of 170 ° C. and a heating time of 1 to 24 hours. Next, after removing the product from the autoclave, it is sufficiently filtered and washed with distilled water, and dried at, for example, 60 ° C. for 12 hours. This product has a relationship between the diffraction peak position shown in Table 3 and the relative intensity, and is shown by a powder X-ray diffraction pattern represented by FIG. 3, which is a high silica nanoporous material (APZ-3: Atomic Pillar Zeolite-3). ). Said manufacturing conditions can be arbitrarily set according to the said manufacture example.

高シリカナノ多孔体ＡＰＺ−４：
先の非特許文献８、９に基づいて、水熱合成で得られた結晶性層状ケイ酸塩ＰＲＥＦＥＲを、その一例として、その０．５ｇを１Ｍ塩酸水溶液（和光純薬工業株式会社製）１８ｍｌとともに、ＰＥＦＥテフロン（登録商標）内筒容器を持った内容量２３ｍｌのオートクレーブ（Ｐａｒｒ社製）に加える。これに、例えば、加熱温度１７０℃、加熱時間６時間の条件で、高温酸処理を行う。次に、オートクレーブから生成物を取り出した後、蒸留水で十分濾過・洗浄し、例えば、６０℃で１２時間乾燥させる。この生成物は、表４に示される回折ピーク位置と相対強度の関係を持ち、図４に代表される粉末Ｘ線回折図形によって示される、高シリカナノ多孔体（ＡＰＺ−４：Ａｔｏｍｉｃ Ｐｉｌｌａｒｅｄ Ｚｅｏｌｉｔｅ−４）である。上記の製造条件は、上記製造例に準じて任意に設定することができる。 High silica nanoporous material APZ-4:
As an example of the crystalline layered silicate PREFER obtained by hydrothermal synthesis based on Non-Patent Documents 8 and 9, 0.5 g of the crystalline layered silicate PREFER is 18 ml of 1M hydrochloric acid aqueous solution (manufactured by Wako Pure Chemical Industries, Ltd.). At the same time, it is added to a 23 ml autoclave (manufactured by Parr) having a PEFE Teflon (registered trademark) inner cylinder container. For example, high-temperature acid treatment is performed under the conditions of a heating temperature of 170 ° C. and a heating time of 6 hours. Next, after removing the product from the autoclave, it is sufficiently filtered and washed with distilled water, and dried at, for example, 60 ° C. for 12 hours. This product has a relationship between the diffraction peak position shown in Table 4 and the relative intensity, and is shown by a powder X-ray diffraction pattern represented by FIG. 4, which is a high silica nanoporous material (APZ-4: Atomic Pillar Zeolite-4). ). Said manufacturing conditions can be arbitrarily set according to the said manufacture example.

このようにして作り出した化合物ＡＰＺ−１、ＡＰＺ−２、ＡＰＺ−３及びＡＰＺ−４が、層間が架橋された新規ナノ多孔体であることの証明は、２９Ｓｉ ＤＤＭＡＳ ＮＭＲ及び粉末ＸＲＤからの構造解析から示すことができる。なお、以下の解析データは、後述する実施例で得られた試料で解析し得たものである。 The proof that the compounds APZ-1, APZ-2, APZ-3 and APZ-4 thus produced are novel nanoporous materials with cross-linked layers is the structure from 29 Si DDMAS NMR and powder XRD. It can be shown from the analysis. In addition, the following analysis data can be analyzed with the sample obtained in the Example mentioned later.

２９Ｓｉ ＤＤＭＡＳ ＮＭＲより解析したＳｉ周りのＯの配位環境を図１０に示す。それぞれのスペクトル中には、Ｑ２（−９０．０〜−９１．４ｐｐｍ）、Ｑ３（−１０２．５〜−１０３．６ｐｐｍ）及びＱ４構造に帰属されるピーク（−１１２．４〜−１１３．６ｐｐｍ）が観測された。Ｑ２の強度は、他に比べ非常に小さいことが特徴である。このＱ２は、層間を架橋する化学式ＳｉＯ２（ＯＨ）２で表される四面体部位の存在を表すものである。 FIG. 10 shows the coordination environment of O around Si analyzed by 29 Si DDMAS NMR. In each spectrum, Q2 (−90.0 to −91.4 ppm), Q3 (−102.5 to −103.6 ppm) and a peak attributed to the Q4 structure (−112.4 to −113.6 ppm) ) Was observed. The strength of Q2 is very small compared to the others. This Q2 represents the presence of a tetrahedral portion represented by the chemical formula SiO 2 (OH) 2 that crosslinks the layers.

通常、プロトンがその局所構造周りに多く存在する場合は、ＣＰ／ＭＡＳ法により感度を増強させることが可能である。そこで、４つのサンプルについて、２９Ｓｉ ＣＰ／ＭＡＳ ＮＭＲを測定したところ、図１０に示されるように、Ｑ２シグナル及びＱ３シグナルのＱ４シグナルに対する相対強度比が、増大することが分かった。 Usually, when many protons exist around the local structure, the sensitivity can be enhanced by the CP / MAS method. Therefore, when 29 Si CP / MAS NMR was measured for the four samples, it was found that the relative intensity ratio of the Q2 signal and the Q3 signal to the Q4 signal increased as shown in FIG.

ここで、Ｑ２構造は１個のＳｉのまわりに２個のＳｉ−Ｏが存在し、Ｑ３構造は１個のＳｉのまわりに３個のＳｉ−Ｏが存在し、Ｑ４構造は４個のＳｉ−Ｏが存在していることを表す。Ｓｉは４官能性であるため、Ｑ２、Ｑ３構造の残りの官能基は、Ｓｉ−Ｏではなく、ＯがＯ−もしくはＯＨとなっている。通常、ゼオライトは、完全に閉じたＳｉ−Ｏネットワークであるので、全てがＱ４構造となる。 Here, the Q2 structure has two Si-Os around one Si, the Q3 structure has three Si-Os around one Si, and the Q4 structure has four Si-Os. -O represents the presence. Since Si is a tetrafunctional, Q2, Q3 remaining functional group of the structure, the Si-O without, O is O - has become or OH. Normally, zeolite is a completely closed Si—O network, so all have a Q4 structure.

なお、原料に用いた結晶性層状ケイ酸塩ＰＬＳ−１、ＰＬＳ−３、ＰＬＳ−４及びＰＲＥＦＥＲの２９Ｓｉ ＤＤＭＡＳ ＮＭＲスペクトルは、Ｑ３及びＱ４の２種類のシグナルだけ観測されることが明らかとなっている（非特許文献１及び２、特許文献６、特許文献７、非特許文献８及び９）。以上のことから、Ｑ２シグナルは、ＳｉＯ２（ＯＨ）２四面体となる局所構造を表すものであり、このシグナルが観測されたことは、層間が、ＳｉＯ２（ＯＨ）２四面体により部分的に架橋されたことを示唆している。 In addition, it becomes clear that only two types of signals Q3 and Q4 are observed in the 29 Si DDMAS NMR spectra of the crystalline layered silicates PLS-1, PLS-3, PLS-4 and PREFER used as raw materials. (Non-patent documents 1 and 2, Patent document 6, Patent document 7, Non-patent documents 8 and 9). From the above, the Q2 signal represents a local structure that becomes a SiO 2 (OH) 2 tetrahedron, and this signal was observed because the interlayer was partially separated by the SiO 2 (OH) 2 tetrahedron. It is suggested that it was crosslinked.

更に、この４つの新規ナノ多孔体についての１３Ｃ ＣＰ／ＭＡＳ ＮＭＲスペクトルを図１１に示す。ＰＬＳ−１では、有機構造規程剤にテトラメチアンモニウムが、ＰＬＳ−３では、テトラエチルアンモニウムが、ＰＬＳ−４では、ジエチルジメチルアンモニウムが、そして、ＰＲＥＦＥＲには、４−アミノ−２，２，６，６−テトラメチルピペリジンが、それぞれ結晶内に含まれているが、高温酸処理によって、それらに由来するピークは殆ど観測されていないか、非常に弱いピーク強度しか観測されない。このことから、高温酸処理によって、有機構造規程剤は生成物結晶内から分解又は脱離したと考えられる。 Further, FIG. 11 shows 13 C CP / MAS NMR spectra of these four novel nanoporous materials. In PLS-1, tetramethammonium is used as the organic structural control agent, tetraethylammonium is used in PLS-3, diethyldimethylammonium is used in PLS-4, and 4-amino-2,2,6, is used in PREFER. Although 6-tetramethylpiperidine is contained in each crystal, few peaks are observed or only very weak peak intensities are observed by high-temperature acid treatment. From this, it is considered that the organic structural control agent was decomposed or eliminated from the product crystal by the high temperature acid treatment.

更に、この４つの新規ナノ多孔体について、ＴＧ−ＤＴＡによる熱測定を行ったところ、図１２に示すように、どれも室温から３００℃にかけて、吸着水の脱離に由来する緩やかな重量減少が観測された。ＡＰＺ−１及びＡＰＺ−２では、２５０−４００℃にかけて、小さな発熱ピークが観測されたが、約２ｗｔ％未満の重量減少でしかなく、他の２つでは、発熱ピークは観測されなかった。これは、用いた４種の層状ケイ酸塩の本来の熱重量減少（約１５〜２３％）に比べると少なく、また、顕著な発熱ピークを示していないことから、有機構造規程剤の脱離・燃焼も非常に少ないことを意味している。これは、１３Ｃ ＣＰ／ＭＡＳ ＮＭＲの結果ともつじつまが良く合っている。 Furthermore, when these four novel nanoporous materials were subjected to thermal measurement by TG-DTA, as shown in FIG. 12, there was a gradual weight loss resulting from desorption of adsorbed water from room temperature to 300 ° C. Observed. In APZ-1 and APZ-2, a small exothermic peak was observed from 250 to 400 ° C., but the weight loss was less than about 2 wt%, and in the other two, no exothermic peak was observed. This is less than the original thermal weight loss (about 15 to 23%) of the four layered silicates used, and because it does not show a significant exothermic peak, the desorption of the organic structural control agent・ It means that there is very little combustion. This is in good agreement with the 13 C CP / MAS NMR results.

更に、この４つの新規ナノ多孔体について、ＳＥＭ観察を行ったところ、図１３に示されるように、ＡＰＺ−１からＡＰＺ−３までは、サブミクロンレベルの板状の結晶が凝集していて、高温酸処理前の層状ケイ酸塩のモルフォロジーと大きな差はない。また、もともと大きな結晶サイズを有したＰＲＥＦＥＲから得られるＡＰＺ−４では、結晶表面に小さな多数の付着物が観測される。   Furthermore, when SEM observation was performed on these four novel nanoporous bodies, as shown in FIG. 13, submicron level plate-like crystals were aggregated from APZ-1 to APZ-3. There is no significant difference from the morphology of layered silicate before high temperature acid treatment. In APZ-4 obtained from PREFER having a large crystal size, a large number of small deposits are observed on the crystal surface.

また、粉末ＸＲＤデータに基づくリートベルト法による結晶構造精密化から、ＡＰＺ−１からＡＰＺ−４について、図２、図４、図６及び図８に示される概念構造に類似した結晶構造モデルを得た。これによって、ＳｉＯ２（ＯＨ）２四面体が、層間に架橋した構造を形成していることが明らかである。このときの結晶学データを、表５に示す。 Further, from the refinement of the crystal structure by the Rietveld method based on the powder XRD data, a crystal structure model similar to the conceptual structure shown in FIGS. 2, 4, 6 and 8 is obtained for APZ-1 to APZ-4. It was. As a result, it is clear that the SiO 2 (OH) 2 tetrahedron forms a cross-linked structure between layers. The crystallographic data at this time is shown in Table 5.

このようにして作り出した化合物が細孔構造を持ったナノ多孔体であることの証明は、このナノ多孔体の窒素ガスの等温吸着性を示せば良い。加熱温度４００℃、２４時間の真空脱気による前処理を行った後、測定した吸着等温曲線を図１４に示す。本発明で得られた新規ナノ多孔体ＡＰＺは、気体の吸着性能が高いことを示し、ＢＥＴ比表面積と細孔容積及び、ＮＬＤＦＴ（非線形密度汎関数法）による解析から見積もられたミクロ細孔径は、表６のように与えられた。ＳＥＭ観察の結果と併せて、相対圧の大きな領域（Ｐ／Ｐ０〜１）での吸着量の増加が著しいことから、外表面による吸着が非常に大きいことが理解される。 In order to prove that the compound thus produced is a nanoporous body having a pore structure, it is only necessary to show the isothermal adsorption of nitrogen gas in the nanoporous body. FIG. 14 shows a measured adsorption isotherm after pretreatment by vacuum degassing at a heating temperature of 400 ° C. for 24 hours. The novel nanoporous material APZ obtained in the present invention shows high gas adsorption performance, and the micropore diameter estimated from the BET specific surface area, pore volume, and analysis by NLDFT (nonlinear density functional theory) Are given as in Table 6. Together with the results of SEM observation, the increase in the amount of adsorption in the region where the relative pressure is large (P / P 0 to 1) is significant.

また、結晶サイズが小さいものほどその傾向が強いことが示される。更に、ＡＰＺ−１では、吸着・脱着にヒステリシスが見られることから、メソ孔程度の空隙ができていることを意味する。層状骨格が一部剥離したためにできたものと考えられる。更に、ＡＰＺ−１からＡＰＺ−４は、架橋部位に孤立シラノール基（水酸基）を持つことから、親水性の特徴を有する。これは、水蒸気吸着を行うことで明らかとなった。図１５に示されるように、結晶１ｇあたり最大で０．２−０．３５ｇの高い水吸着能を示すことが分かった。このときのＢＥＴ比表面積は、表７で与えられる。   Moreover, it is shown that the tendency is so strong that a crystal | crystallization size is small. Furthermore, in APZ-1, since hysteresis is observed in adsorption / desorption, it means that voids of about mesopores are formed. It is considered that the layered skeleton was partially peeled off. Furthermore, APZ-1 to APZ-4 have an isolated silanol group (hydroxyl group) at the cross-linked site, and thus have hydrophilic characteristics. This became clear by performing water vapor adsorption. As shown in FIG. 15, it was found that a maximum water adsorption capacity of 0.2 to 0.35 g per 1 g of crystals was exhibited. The BET specific surface area at this time is given in Table 7.

更に、この高シリカナノ多孔体ＡＰＺ−１は、用いた結晶性層状ケイ酸塩ＰＬＳ−１の結晶サイズやモルフォロジーを大きく変化させることが可能である（（実施例４）を参照）。これによる吸着特性の違いを調べるために、窒素ガス吸着及び水蒸気吸着を行うことで、図１６に示される等温曲線が得られる。大きな結晶を使って調製したＡＰＺ−１では、窒素ガス吸着測定からは、吸着と脱着との間に大きなヒステリシスが観測される。ＮＬＤＦＴ解析から細孔分布を見積もったところ、９．０Åのミクロ孔以外に、１．８ｎｍ付近と５．３ｎｍ付近にメソ孔があることが示唆された。一方、水蒸気吸着等温曲線によると、２つのサンプルとも基本的に同じ傾向を示す。しかし、相対圧の大きな領域（Ｐ／Ｐ０≒１）での吸着量の増加は、高密度凝集結晶の方が顕著であることから、結晶サイズが小さいことによる粒子間空隙への吸着が支配的であると考えられる。 Furthermore, this high silica nanoporous material APZ-1 can greatly change the crystal size and morphology of the crystalline layered silicate PLS-1 used (see (Example 4)). In order to examine the difference in the adsorption characteristics due to this, nitrogen gas adsorption and water vapor adsorption are performed, and the isothermal curve shown in FIG. 16 is obtained. In APZ-1 prepared using large crystals, a large hysteresis is observed between adsorption and desorption from nitrogen gas adsorption measurement. When the pore distribution was estimated from the NLDFT analysis, it was suggested that there were mesopores in the vicinity of 1.8 nm and 5.3 nm in addition to the 9.0 mm micropores. On the other hand, according to the water vapor adsorption isotherm, the two samples basically show the same tendency. However, the increase in the amount of adsorption in the region where the relative pressure is large (P / P 0 ≈1) is more noticeable in the high-density agglomerated crystal, and the adsorption to the interparticle void due to the small crystal size is dominant. It is considered to be appropriate.

本発明の新規ナノ多孔体ＡＰＺは、６００℃以上の耐熱性を有する。ナノ多孔体ＡＰＺの耐熱性について検討するために、電気炉を用いて、２Ｌ／ｍｉｎの空気流通下で、１℃／ｍｉｎの昇温速度にて６０℃から６００℃まで昇温し、２時間保持の熱処理（焼成）を行ったときのＡＰＺ−１の構造変化を示す粉末ＸＲＤパターンを図１７に示す。６００℃の焼成後も、やや結晶性が低下するものの、ＡＰＺ−１の構造が保持されていることが分かる。この他、ＡＰＺ−２、ＡＰＺ−３、ＡＰＺ−４においても、図１８に示すように、６００℃の焼成後も構造が保たれていることが確認される。また、吸着測定において、４００℃の前処理後でも高いガス吸着能を示しており、結晶性の低下が僅かであることから、６００℃以上の耐熱性を有していると言える。   The novel nanoporous material APZ of the present invention has a heat resistance of 600 ° C. or higher. In order to examine the heat resistance of the nanoporous material APZ, the temperature was increased from 60 ° C. to 600 ° C. at a temperature increase rate of 1 ° C./min under an air flow of 2 L / min using an electric furnace for 2 hours. FIG. 17 shows a powder XRD pattern showing the structural change of APZ-1 when holding heat treatment (firing) is performed. It can be seen that the structure of APZ-1 is maintained even after baking at 600 ° C., although the crystallinity is slightly lowered. In addition, in APZ-2, APZ-3, and APZ-4, as shown in FIG. 18, it is confirmed that the structure is maintained even after baking at 600 ° C. Further, in the adsorption measurement, a high gas adsorbing ability is exhibited even after the pretreatment at 400 ° C., and the crystallinity is slightly lowered.

本発明により、次のような効果が奏される。
（１）本発明の新規ナノ多孔体ＡＰＺシリーズは、既知・既存のケイ素５員環構造からなるシリカ含有量が高い結晶性層状ケイ酸塩を母体とし、例えば、親水性分離剤、吸着剤、金属担持用固体、形状選択性固体触媒、イオン交換剤、クロマトグラフィー充填剤材料及び化学反応場など、広範な用途に利用可能である。
（２）本発明のナノ多孔体は、高シリカ型に特徴的な耐熱性と耐薬品性の性質を持ちながらも、高い結晶性や高親水性及び高いガス吸着能を示す。
（３）類縁構造として同じ骨格構造を持ったＣＤＯ型、ＦＥＲ型ゼオライトなどと併用することで、高シリカ型ながら性質の異なるハイブリッド膜材料など、近年研究が盛んな新しいゼオライト応用への展開も望める。
（４）ＡＰＺシリーズの合成は、既存の結晶性層状ケイ酸塩を合成温度に近い温度条件で短時間酸処理するだけでナノ多孔体ＡＰＺが得られることが大きな特徴である。
（５）本発明は、既存の高シリカ型ゼオライトと性質を異にする新規結晶性高シリカナノ多孔体の製造技術として高い優位性を有するものである。 The present invention has the following effects.
(1) The novel nanoporous material APZ series of the present invention is based on a known and existing crystalline layered silicate having a high silica content consisting of a silicon five-membered ring structure. For example, a hydrophilic separator, an adsorbent, It can be used in a wide range of applications such as solids for metal support, shape selective solid catalysts, ion exchangers, chromatographic filler materials and chemical reaction fields.
(2) The nanoporous material of the present invention exhibits high crystallinity, high hydrophilicity, and high gas adsorption ability while having the heat resistance and chemical resistance properties characteristic of a high silica type.
(3) Use in combination with CDO-type and FER-type zeolites that have the same skeleton structure as related structures, and can be expected to expand into new zeolite applications that have been actively researched in recent years, such as high-silica type hybrid membrane materials with different properties. .
(4) The synthesis of the APZ series is characterized in that the nanoporous material APZ can be obtained simply by acid-treating an existing crystalline layered silicate under a temperature condition close to the synthesis temperature.
(5) The present invention has a high advantage as a technique for producing a novel crystalline high silica nanoporous material having properties different from those of existing high silica type zeolite.

次に、本発明を実施例に基づいて具体的に説明するが、本発明は、以下の実施例によって何ら限定されるものではない。
以下、粉末Ｘ線回折（ＸＲＤ）パターンは、マックサイエンス社Ｍ２１Ｘを使用し、波長にＣｕＫα線を用いて、２θ＝３−６０゜の範囲を０．０２間隔のステップスキャン法で測定した。ＳＥＭ像観察には、ＨＩＴＡＣＨＩ Ｓ−８００を用い、あらかじめ試料をイオンコートした後、加速電圧１５ｋＶで観察した。２９Ｓｉ ＤＤＭＡＳ ＮＭＲ、１３Ｃ ＣＰ／ＭＡＳ ＮＭＲの測定には、ブルカーバイオスピン社ＡＶＡＮＣＥ４００ＷＢを使用した。全ての測定で、７ｍｍプローブを用い、ＭＡＳ回転数を５ｋＨｚとした。ケミカルシフトの補正は、Ｈ、Ｓｉ核にテトラメチルシランを、また、Ｃ核にはグリシンを用いて行った。窒素ガス吸着測定には、カンタクローム社製のＡｕｔｏｓｏｒｂ １−ＭＰを用い、加熱温度４００℃、２４時間の真空脱気による前処理を行った後、液体窒素温度７７Ｋ下で測定を行った。 EXAMPLES Next, although this invention is demonstrated concretely based on an Example, this invention is not limited at all by the following Examples.
Hereinafter, the powder X-ray diffraction (XRD) pattern was measured using a Mac Science M21X, using CuKα rays as a wavelength, and a range of 2θ = 3-60 ° by a step scan method with an interval of 0.02. For SEM image observation, HITACHI S-800 was used, and the sample was previously ion-coated and then observed at an acceleration voltage of 15 kV. Bruker BioSpin AVANCE400WB was used for measurement of 29 Si DDMAS NMR and 13 C CP / MAS NMR. In all measurements, a 7 mm probe was used and the MAS rotation speed was 5 kHz. The chemical shift was corrected using tetramethylsilane for the H and Si nuclei and glycine for the C nuclei. For nitrogen gas adsorption measurement, Autosorb 1-MP manufactured by Cantachrome Co., Ltd. was used, and after pretreatment by vacuum degassing at a heating temperature of 400 ° C. for 24 hours, measurement was performed at a liquid nitrogen temperature of 77K.

水蒸気吸着測定には、日本ベル株式会社製のＢＥＬＳＯＲＰ１８を用い、加熱温度４００℃、２４時間の真空脱気による前処理を行った後、室温にて測定を行った。熱分析には、ブルカーエイエックスエス社製のＴＧ−ＤＴＡ２０００を用いた。昇温速度を１０℃／ｍｉｎとし、６００℃まで加熱した。また、結晶構造解析では、高分解能粉末Ｘ線回折装置にブルカーエイエックスエス社製Ｄ８ ＡＤＶＡＮＣＥ Ｖαｒｉｏ−１により、波長ＣｕＫα１の特性Ｘ線を用いて測定を行い、得られた回折強度データについて、プログラムＲＩＥＴＡＮ−２０００を使ったリートベルト法により、構造解析を行った。 For the water vapor adsorption measurement, BELSORP18 manufactured by Nippon Bell Co., Ltd. was used, and after pretreatment by vacuum degassing at a heating temperature of 400 ° C. for 24 hours, the measurement was performed at room temperature. For thermal analysis, TG-DTA2000 manufactured by Bruker AXS was used. The heating rate was 10 ° C./min and heating was performed to 600 ° C. In addition, in the crystal structure analysis, measurement was performed using a characteristic X-ray having a wavelength CuKα 1 with a high resolution powder X-ray diffractometer using D8 ADVANCE Vαrio-1 manufactured by Bruker AXS Co. Structural analysis was performed by the Rietveld method using the program Rietan-2000.

高シリカナノ多孔体ＡＰＺ−１の製造
文献（特許文献１−４）に基づいて、水熱合成で得られた結晶性層状ケイ酸塩ＰＬＳ−１、１．０ｇを１Ｍ塩酸水溶液（和光純薬工業株式会社製）１８ｍｌとともに、ＰＥＦＥテフロン（登録商標）内筒容器を持った内容量２３ｍｌのオートクレーブ（Ｐａｒｒ社製）に加えた。これに、加熱温度１７０℃、加熱時間２４時間の条件で、高温酸処理を施した。次に、オートクレーブから生成物を取り出した後、蒸留水で十分濾過・洗浄し、６０℃で１２時間乾燥させた。 Production of High Silica Nanoporous Material APZ-1 Based on the literature (Patent Literatures 1-4) , 1.0 g of crystalline layered silicate PLS-1 obtained by hydrothermal synthesis was added to 1M hydrochloric acid aqueous solution (Wako Pure Chemical Industries, Ltd.). 18 ml) and a 23-ml autoclave (manufactured by Parr) having a PEFE Teflon (registered trademark) inner cylinder container. This was subjected to high-temperature acid treatment under the conditions of a heating temperature of 170 ° C. and a heating time of 24 hours. Next, after removing the product from the autoclave, it was sufficiently filtered and washed with distilled water, and dried at 60 ° C. for 12 hours.

この生成物としては、表１に示される回折ピーク位置と相対強度の関係を持ち、図１に代表される粉末Ｘ線回折図形によって示される、高シリカナノ多孔体（ＡＰＺ−１：Ａｔｏｍｉｃ Ｐｉｌｌａｒｅｄ Ｚｅｏｌｉｔｅ−１）が得られた。これは、表８に示されるＲｕｎ Ｎｏ．１に対応する。更に、調製時間や硝酸（和光純薬工業株式会社製）を用いた場合など、表８に示される調製条件（Ｒｕｎ Ｎｏ．２−１２、１４）で実施した場合について、生成物の粉末Ｘ線回折パターンを図１９及び図２０に示す。全てにおいて、生成物が高シリカナノ多孔体ＡＰＺ−１であることが確認された。   As this product, there is a relationship between the diffraction peak position shown in Table 1 and the relative intensity, and a high silica nanoporous material (APZ-1: Atomic Pillared Zeolite− shown by a powder X-ray diffraction pattern represented by FIG. 1 is used. 1) was obtained. This is due to the Run No. shown in Table 8. Corresponding to 1. Furthermore, the powder X-rays of the product in the case of carrying out under the preparation conditions (Run Nos. 2-12 and 14) shown in Table 8, such as the case of using preparation time and nitric acid (manufactured by Wako Pure Chemical Industries, Ltd.) The diffraction patterns are shown in FIGS. In all, it was confirmed that the product was a high silica nanoporous material APZ-1.

高シリカナノ多孔体ＡＰＺ−１の製造
上記実施例１における高シリカナノ多孔体ＡＰＺ−１の調製条件において、文献（特許文献５）に基づいて、固相反応で合成された結晶性層状ケイ酸塩ＰＬＳ−１を用いた以外は、実施例１と同じ条件で高シリカナノ多孔体の製造を行った（Ｒｕｎ Ｎｏ．１３）。図２０で示されるように、粉末Ｘ線回折パターンから、生成物が高シリカナノ多孔体ＡＰＺ−１であることが確認された。 Production of High Silica Nanoporous Material APZ-1 Crystalline Layered Silicate PLS Synthesized by Solid Phase Reaction Based on Literature (Patent Document 5) under the Preparation Conditions of High Silica Nanoporous Material APZ-1 in Example 1 above A high-silica nanoporous material was produced under the same conditions as in Example 1 except that -1 was used (Run No. 13). As shown in FIG. 20, it was confirmed from the powder X-ray diffraction pattern that the product was a high silica nanoporous material APZ-1.

高シリカナノ多孔体ＡＰＺ−１の製造
上記実施例１における高シリカナノ多孔体ＡＰＺ−１の調製条件において、添加物テトラメチルアンモニウムヒドロキシド五水和物（ＳＩＧＭＡ−ＡＬＤＲＩＣＨ Ｃｏｒｐ．ＳＩＧＭＡ−ＡＬＤＲＩＣＨ Ｊａｐａｎ Ｋ．Ｋ．社製）及びワコーゲルＱ−６３（和光純薬工業株式会社製）を添加物としてシリカ重量比に対して５％加えた以外は、実施例１と同じ条件（表９）で高シリカナノ多孔体の製造を行った（Ｒｕｎ Ｎｏ．１５、１６）。図２１で示されるように、粉末Ｘ線回折パターンから、生成物が高シリカナノ多孔体ＡＰＺ−１であることが確認された。 Production of High Silica Nanoporous Material APZ-1 In the preparation conditions of the high silica nanoporous material APZ-1 in Example 1 above, an additive tetramethylammonium hydroxide pentahydrate (SIGMA-ALDRICH Corp. SIGMA-ALDRICH Japan K.K. High silica nanoporous material under the same conditions as in Example 1 (Table 9) except that 5% of silica weight ratio was added as an additive to Wako Gel Q-63 (manufactured by Wako Pure Chemical Industries, Ltd.). (Run Nos. 15 and 16). As shown in FIG. 21, it was confirmed from the powder X-ray diffraction pattern that the product was a high silica nanoporous material APZ-1.

高シリカナノ多孔体ＡＰＺ−１の製造
上記実施例１における高シリカナノ多孔体ＡＰＺ−１の調製条件において、文献（特許文献８）に基づいて、アルカノールアミン添加物の導入により得られる、結晶サイズ及びモルフォロジーが異なった結晶性層状ケイ酸塩ＰＬＳ−１を用いた以外は、実施例１と同じ条件（表１０）で高シリカナノ多孔体の製造を行った（Ｒｕｎ Ｎｏ．１７、１８）。図２１で示されるように、粉末Ｘ線回折パターンから、生成物が高シリカナノ多孔体ＡＰＺ−１であることが確認された。 Production of high silica nanoporous material APZ-1 Crystalline size and morphology obtained by introducing an alkanolamine additive based on the literature (Patent Document 8) under the preparation conditions of high silica nanoporous material APZ-1 in Example 1 above A high-silica nanoporous material was produced under the same conditions as in Example 1 (Table 10) except that a crystalline layered silicate PLS-1 having a different particle size was used (Run Nos. 17, 18). As shown in FIG. 21, it was confirmed from the powder X-ray diffraction pattern that the product was a high silica nanoporous material APZ-1.

高シリカナノ多孔体ＡＰＺ−２の製造
文献（非特許文献８、９）に基づいて、固相反応合成で得られた結晶性層状ケイ酸塩ＰＬＳ−３に当たるＣＤＯ型ゼオライトの前駆体となる化合物、０．５ｇを１Ｍ塩酸水溶液（和光純薬工業株式会社製）１８ｍｌとともに、ＰＥＦＥテフロン（登録商標）内筒容器を持った内容量２３ｍｌのオートクレーブ（Ｐａｒｒ社製）に加えた。これに、加熱温度１７０℃、加熱時間１８時間の条件で、高温酸処理を施した。次に、オートクレーブから生成物を取り出した後、蒸留水で十分濾過・洗浄し、６０℃で１２時間乾燥させた。 Production of high silica nanoporous material APZ-2 Based on the literature ( Non- patent Documents 8 and 9 ), a compound that is a precursor of CDO-type zeolite corresponding to crystalline layered silicate PLS-3 obtained by solid-phase reaction synthesis, 0.5 g was added together with 18 ml of 1M hydrochloric acid aqueous solution (manufactured by Wako Pure Chemical Industries, Ltd.) to an autoclave (manufactured by Parr) having an inner volume of 23 ml having a PEFE Teflon (registered trademark) inner cylinder container. This was subjected to high-temperature acid treatment under the conditions of a heating temperature of 170 ° C. and a heating time of 18 hours. Next, after removing the product from the autoclave, it was sufficiently filtered and washed with distilled water, and dried at 60 ° C. for 12 hours.

この生成物として、表２に示される回折ピーク位置と相対強度の関係を持ち、図３に代表される粉末Ｘ線回折図形によって示される、高シリカナノ多孔体（ＡＰＺ−２：Ａｔｏｍｉｃ Ｐｉｌｌａｒｅｄ Ｚｅｏｌｉｔｅ−２）が得られた。これは、表１１に示されるＲｕｎ Ｎｏ．１に対応する。更に表１１に示される調製条件（Ｒｕｎ Ｎｏ．２−７）で実施した場合について、生成物の粉末Ｘ線回折パターンを図２２に示す。全てにおいて、生成物が高シリカナノ多孔体ＡＰＺ−２であることが確認された。   As this product, a high silica nanoporous material (APZ-2: Atomic Pillared Zeolite-2, which has a relationship between the diffraction peak position shown in Table 2 and relative intensity and is shown by a powder X-ray diffraction pattern represented in FIG. )was gotten. This is because of the Run No. shown in Table 11. Corresponding to 1. Furthermore, about the case where it implemented on the preparation conditions (Run No.2-7) shown in Table 11, the powder X-ray-diffraction pattern of a product is shown in FIG. In all, it was confirmed that the product was a high silica nanoporous material APZ-2.

高シリカナノ多孔体ＡＰＺ−２の製造
上記実施例５における高シリカナノ多孔体ＡＰＺ−２の調製条件において、添加物テトラメチルアンモニウムヒドロキシド五水和物（ＳＩＧＭＡ−ＡＬＤＲＩＣＨ Ｃｏｒｐ．ＳＩＧＭＡ−ＡＬＤＲＩＣＨ Ｊａｐａｎ Ｋ．Ｋ．社製）及びワコーゲルＱ−６３（和光純薬工業株式会社製）を添加物としてシリカ重量比に対して５％加えた以外は、実施例１と同じ条件（表１２）で高シリカナノ多孔体の製造を行った（Ｒｕｎ Ｎｏ．８、９）。図２３で示されるように、粉末Ｘ線回折パターンから、生成物が高シリカナノ多孔体ＡＰＺ−１であることが確認された。 Production of High Silica Nanoporous Material APZ-2 In the preparation conditions of the high silica nanoporous material APZ-2 in Example 5, the additive tetramethylammonium hydroxide pentahydrate (SIGMA-ALDRICH Corp. SIGMA-ALDRICH Japan K.K. High silica nanoporous material under the same conditions as in Example 1 (Table 12) except that 5% of silica weight ratio was added as an additive to Wako Gel Q-63 (manufactured by Wako Pure Chemical Industries, Ltd.). (Run Nos. 8 and 9). As shown in FIG. 23, it was confirmed from the powder X-ray diffraction pattern that the product was a high silica nanoporous material APZ-1.

高シリカナノ多孔体ＡＰＺ−３の製造
文献（非特許文献１０）に基づいて、固相反応合成で得られた結晶性層状ケイ酸塩ＰＬＳ−４に当たるＣＤＯ型ゼオライトの前駆体となる化合物、０．５１８ｇを１Ｍ塩酸水溶液（和光純薬工業株式会社製）１８ｍｌとともに、ＰＥＦＥテフロン（登録商標）内筒容器を持った内容量２３ｍｌのオートクレーブ（Ｐａｒｒ社製）に加えた。これに、加熱温度１７０℃、加熱時間２４時間の条件で、高温酸処理を施した。次に、オートクレーブから生成物を取り出した後、蒸留水で十分濾過・洗浄し、６０℃で１２時間乾燥させた。 Production of high silica nanoporous material APZ-3 Based on the literature ( Non- Patent Document 10 ), a compound that is a precursor of CDO-type zeolite corresponding to crystalline layered silicate PLS-4 obtained by solid-phase reaction synthesis; 518 g was added together with 18 ml of 1M aqueous hydrochloric acid (manufactured by Wako Pure Chemical Industries, Ltd.) to a 23 ml autoclave (manufactured by Parr) having a PEFE Teflon (registered trademark) inner cylinder container. This was subjected to high-temperature acid treatment under the conditions of a heating temperature of 170 ° C. and a heating time of 24 hours. Next, after removing the product from the autoclave, it was sufficiently filtered and washed with distilled water, and dried at 60 ° C. for 12 hours.

この生成物として、表３に示される回折ピーク位置と相対強度の関係を持ち、図５に代表される粉末Ｘ線回折図形によって示される、高シリカナノ多孔体（ＡＰＺ−３：Ａｔｏｍｉｃ Ｐｉｌｌａｒｅｄ Ｚｅｏｌｉｔｅ−３）が得られた。これは、表１３に示されるＲｕｎ Ｎｏ．１に対応する。更に、表１３に示される調製条件（Ｒｕｎ Ｎｏ．２−５）で実施した場合について、生成物の粉末Ｘ線回折パターンを図２４に示す。全てにおいて、生成物が高シリカナノ多孔体ＡＰＺ−２であることが確認された。   As this product, a high silica nanoporous material (APZ-3: Atomic Pillared Zeolite-3, which has a relationship between the diffraction peak position shown in Table 3 and a relative intensity and is shown by a powder X-ray diffraction pattern represented in FIG. )was gotten. This is because of the Run No. shown in Table 13. Corresponding to 1. Furthermore, about the case where it implemented on the preparation conditions (Run No.2-5) shown in Table 13, the powder X-ray-diffraction pattern of a product is shown in FIG. In all, it was confirmed that the product was a high silica nanoporous material APZ-2.

高シリカナノ多孔体ＡＰＺ−４の製造
文献（非特許文献８、９）に基づいて、水熱合成で得られた結晶性層状ケイ酸塩ＰＲＥＦＥＲ、０．５ｇを１Ｍ塩酸水溶液（和光純薬工業株式会社製）１８ｍｌとともに、ＰＥＦＥテフロン（登録商標）内筒容器を持った内容量２３ｍｌのオートクレーブ（Ｐａｒｒ社製）に加えた。これを、加熱温度１７０℃、加熱時間６時間の条件で、高温酸処理を行った。次に、オートクレーブから生成物を取り出した後、蒸留水で十分濾過・洗浄し、６０℃で１２時間乾燥させた。 Production of High Silica Nanoporous Material APZ-4 Based on the literature (Non-patent Documents 8 and 9), 0.5 g of crystalline layered silicate PREFER obtained by hydrothermal synthesis was added to 1M hydrochloric acid aqueous solution (Wako Pure Chemical Industries Ltd.) The product was added to an autoclave (manufactured by Parr) having a capacity of 23 ml with a PEFE Teflon (registered trademark) inner cylinder container. This was subjected to high-temperature acid treatment under the conditions of a heating temperature of 170 ° C. and a heating time of 6 hours. Next, after removing the product from the autoclave, it was sufficiently filtered and washed with distilled water, and dried at 60 ° C. for 12 hours.

この生成物として、表４に示される回折ピーク位置と相対強度の関係を持ち、図７に代表される粉末Ｘ線回折図形によって示される、高シリカナノ多孔体（ＡＰＺ−４：Ａｔｏｍｉｃ Ｐｉｌｌａｒｅｄ Ｚｅｏｌｉｔｅ−４）が得られた。これは、表１４に示されるＲｕｎ Ｎｏ．１に対応する。更に、表１４に示される調製条件（Ｒｕｎ Ｎｏ．２−５）で実施した場合について、生成物の粉末Ｘ線回折パターンを図２５に示す。全てにおいて、生成物が高シリカナノ多孔体ＡＰＺ−２であることが確認された。   As this product, a high silica nanoporous material (APZ-4: Atomic Pillared Zeolite-4, which has a relationship between a diffraction peak position shown in Table 4 and a relative intensity, and is represented by a powder X-ray diffraction pattern represented in FIG. )was gotten. This is the same as the Run No. shown in Table 14. Corresponding to 1. Furthermore, the powder X-ray diffraction pattern of a product is shown in FIG. 25 about the case where it implements on the preparation conditions (Run No. 2-5) shown in Table 14. In all, it was confirmed that the product was a high silica nanoporous material APZ-2.

高シリカナノ多孔体ＡＰＺシリーズの２９Ｓｉ核の固体ＮＭＲによる特性評価
上記実施例１−８記載の高シリカナノ多孔体ＡＰＺ−１、ＡＰＺ−２、ＡＰＺ−３及びＡＰＺ−４が、層間が架橋された新規ナノ多孔体であることの証明は、２９Ｓｉ ＤＤＭＡＳ ＮＭＲ及び粉末ＸＲＤからの構造解析から行った。なお、以下の解析データは、実施例で得られた試料で解析し得たものである。 Characterization of high-silica nanoporous material APZ series 29 Si nuclei by solid-state NMR High-silica nanoporous materials APZ-1, APZ-2, APZ-3 and APZ-4 described in Example 1-8 were cross-linked. Proof that it is a novel nanoporous material was performed from 29 Si DDMAS NMR and structural analysis from powder XRD. The following analysis data was obtained by analyzing the samples obtained in the examples.

２９Ｓｉ ＤＤＭＡＳ ＮＭＲより解析したＳｉ周りのＯの配位環境を図１０に示す。それぞれのスペクトル中には、Ｑ２（−９０．０〜−９１．４ｐｐｍ）、Ｑ３（−１０２．５〜−１０３．６ｐｐｍ）及びＱ４構造に帰属されるピーク（−１１２．４〜−１１３．６ｐｐｍ）が観測された。Ｑ２の強度は、他に比べ非常に小さいことが特徴である。このＱ２は、層間を架橋する化学式ＳｉＯ２（ＯＨ）２で表される四面体部位の存在を表すものである。 FIG. 10 shows the coordination environment of O around Si analyzed by 29 Si DDMAS NMR. In each spectrum, Q2 (−90.0 to −91.4 ppm), Q3 (−102.5 to −103.6 ppm) and a peak attributed to the Q4 structure (−112.4 to −113.6 ppm) ) Was observed. The strength of Q2 is very small compared to the others. This Q2 represents the presence of a tetrahedral portion represented by the chemical formula SiO 2 (OH) 2 that crosslinks the layers.

通常、プロトンがその局所構造周りに多く存在する場合は、ＣＰ／ＭＡＳ法により感度を増強させることが可能である。そこで、４つのサンプルについて、２９Ｓｉ ＣＰ／ＭＡＳ ＮＭＲを測定したところ、図１０に示されるように、Ｑ２シグナル及びＱ３シグナルのＱ４シグナルに対する相対強度比が増大することが分かった。ここで、Ｑ２構造は、１個のＳｉのまわりに２個のＳｉ−Ｏが存在し、Ｑ３構造は、１個のＳｉのまわりに３個のＳｉ−Ｏが存在し、Ｑ４構造では、４個のＳｉ−Ｏが存在していることを表す。Ｓｉは４官能性であるため、Ｑ２、Ｑ３構造の残りの官能基は、Ｓｉ−Ｏではなく、ＯがＯ−もしくはＯＨとなっている。 Usually, when many protons exist around the local structure, the sensitivity can be enhanced by the CP / MAS method. Therefore, when 29 Si CP / MAS NMR was measured for the four samples, it was found that the relative intensity ratio of the Q2 signal and the Q3 signal to the Q4 signal increased as shown in FIG. Here, the Q2 structure has two Si-Os around one Si, the Q3 structure has three Si-Os around one Si, and the Q4 structure has four Si-Os. This means that there are Si-O pieces. Since Si is a tetrafunctional, Q2, Q3 remaining functional group of the structure, the Si-O without, O is O - has become or OH.

通常、ゼオライトは、完全に閉じたＳｉ−Ｏネットワークであるので、全てがＱ４構造となる。なお、原料に用いた結晶性層状ケイ酸塩ＰＬＳ−１、ＰＬＳ−３、ＰＬＳ−４及びＰＲＥＦＥＲの、２９Ｓｉ ＤＤＭＡＳ ＮＭＲスペクトルは、Ｑ３及びＱ４の２種類のシグナルだけ観測されることが明らかとなっている（非特許文献１及び２、特許文献６、特許文献７、非特許文献８及び９）。以上のことから、Ｑ２シグナルは、ＳｉＯ２（ＯＨ）２四面体に寄るものであり、Ｑ２及びＱ３構造が観測されたことは、層間が、ＳｉＯ２（ＯＨ）２四面体により部分的に架橋されたことを示唆している。 Normally, zeolite is a completely closed Si—O network, so all have a Q4 structure. In addition, it is clear that the 29 Si DDDMA NMR spectra of the crystalline layered silicates PLS-1, PLS-3, PLS-4 and PREFER used as raw materials are observed only for two types of signals Q3 and Q4. (Non-Patent Documents 1 and 2, Patent Document 6, Patent Document 7, Non-Patent Documents 8 and 9). From the above, the Q2 signal is close to the SiO 2 (OH) 2 tetrahedron, and the observation of the Q2 and Q3 structures is that the interlayer is partially crosslinked by the SiO 2 (OH) 2 tetrahedron. It is suggested that.

高シリカナノ多孔体ＡＰＺシリーズの１３Ｃ核の固体ＮＭＲによる特性評価
上記実施例１−８記載の高シリカナノ多孔体ＡＰＺ−１、ＡＰＺ−２、ＡＰＺ−３及びＡＰＺ−４における、１３Ｃ ＣＰ／ＭＡＳ ＮＭＲスペクトルを図１１に示す。ＰＬＳ−１では、有機構造規程剤にテトラメチアンモニウムが、ＰＬＳ−３では、テトラエチルアンモニウムが、ＰＬＳ−４では、ジエチルジメチルアンモニウムが、そして、ＰＲＥＦＥＲには、４−アミノ−２，２，６，６−テトラメチルピペリジンが、それぞれ結晶内に含まれているが、高温酸処理によって、それらに由来するピークは殆ど観測されていないか、非常に弱いピーク強度しか観測されなかった。このことから、高温酸処理によって、有機構造規程剤は、生成物結晶内から分解又は脱離したと考えられる。 Characterization of 13 C nuclei by solid-state NMR of high silica nanoporous material APZ series 13 C CP / MAS in high silica nanoporous materials APZ-1, APZ-2, APZ-3 and APZ-4 described in Example 1-8 above The NMR spectrum is shown in FIG. In PLS-1, tetramethammonium is used as the organic structural control agent, tetraethylammonium is used in PLS-3, diethyldimethylammonium is used in PLS-4, and 4-amino-2,2,6, is used in PREFER. Although 6-tetramethylpiperidine was contained in each crystal, few peaks were observed due to high-temperature acid treatment, or only very weak peak intensity was observed. From this, it is considered that the organic structural control agent was decomposed or eliminated from the product crystal by the high temperature acid treatment.

高シリカナノ多孔体ＡＰＺシリーズのＴＧ−ＤＴＡ測定による特性評価
上記実施例１−８記載の高シリカナノ多孔体ＡＰＺ−１、ＡＰＺ−２、ＡＰＺ−３及びＡＰＺ−４について、ＴＧ−ＤＴＡ熱測定を行ったところ、図１２に示すように、どれも室温から３００℃にかけて、吸着水の脱離に由来する緩やかな重量減少が観測された。ＡＰＺ−１及びＡＰＺ−２では、２５０−４００℃にかけて、小さな発熱ピークが観測された。 Characterization of high silica nanoporous material APZ series by TG-DTA measurement TG-DTA thermal measurement was performed on high silica nanoporous materials APZ-1, APZ-2, APZ-3 and APZ-4 described in Example 1-8 above. As a result, as shown in FIG. 12, a gradual decrease in weight due to desorption of adsorbed water was observed from room temperature to 300 ° C. In APZ-1 and APZ-2, a small exothermic peak was observed from 250 to 400 ° C.

しかし、これらは、約２ｗｔ％未満の重量減少でしかなく、他の２つでは、発熱ピークは観測されなかった。これは、用いた４種の層状ケイ酸塩の本来の熱重量減少（約１５−２３％）に比べると少なく、また、顕著な発熱ピークを示していないことから、有機構造規程剤の脱離・燃焼も非常に少ないことを意味している。これは、１３Ｃ ＣＰ／ＭＡＳ ＮＭＲの結果ともつじつまが良く合っている。 However, these were only less than about 2 wt% weight loss, and no exothermic peak was observed in the other two. This is less than the original thermogravimetric loss (about 15-23%) of the four layered silicates used, and does not show a significant exothermic peak.・ It means that there is very little combustion. This is in good agreement with the 13 C CP / MAS NMR results.

高シリカナノ多孔体ＡＰＺシリーズの走査型電子顕微鏡（ＳＥＭ）による特性評価
上記実施例１−８記載の高シリカナノ多孔体ＡＰＺ−１、ＡＰＺ−２、ＡＰＺ−３及びＡＰＺ−４について、ＳＥＭ観察を行ったところ、図１３に示されるように、ＡＰＺ−１からＡＰＺ−３までは、サブミクロンレベルの板状の結晶が凝集していて、高温酸処理前の層状ケイ酸塩のモルフォロジーと大きな差はなかった。また、もともと大きな結晶サイズを有したＰＲＥＦＥＲから得られるＡＰＺ−４では、結晶表面に小さな多数の付着物が観測された。 Characteristic Evaluation of High Silica Nanoporous Material APZ Series by Scanning Electron Microscope (SEM) SEM observation was performed on high silica nanoporous materials APZ-1, APZ-2, APZ-3 and APZ-4 described in Example 1-8. As shown in FIG. 13, from APZ-1 to APZ-3, submicron level plate-like crystals are agglomerated, and there is a big difference from the morphology of layered silicate before high-temperature acid treatment. There wasn't. In APZ-4 obtained from PREFER having a large crystal size, many small deposits were observed on the crystal surface.

高シリカナノ多孔体ＡＰＺシリーズの粉末Ｘ線回折による構造評価
上記実施例１−８記載の高シリカナノ多孔体ＡＰＺ−１、ＡＰＺ−２、ＡＰＺ−３及びＡＰＺ−４について、粉末ＸＲＤデータに基づくリートベルト法による結晶構造精密化から、図２、図４、図６及び図８に示される概念構造に類似した結晶構造モデルを得た。これによって、ＳｉＯ２（ＯＨ）２四面体が、層間に架橋した構造を形成していることが明らかとなった。このときの結晶学データを表１５に示す。 Structure evaluation by powder X-ray diffraction of high silica nanoporous material APZ series For high silica nanoporous materials APZ-1, APZ-2, APZ-3 and APZ-4 described in Example 1-8, Rietveld based on powder XRD data From the refinement of the crystal structure by the method, a crystal structure model similar to the conceptual structure shown in FIGS. 2, 4, 6 and 8 was obtained. As a result, it became clear that the SiO 2 (OH) 2 tetrahedron formed a crosslinked structure between layers. The crystallographic data at this time is shown in Table 15.

高シリカナノ多孔体ＡＰＺシリーズのガス吸着測定及び水蒸気吸着測定による細孔構造・特性評価
上記実施例１−３、５−８記載の高シリカナノ多孔体ＡＰＺ−１、ＡＰＺ−２、ＡＰＺ−３及びＡＰＺ−４について、細孔構造を持ったナノ多孔体であることの証明は、このナノ多孔体の窒素ガスの等温吸着性から行った。加熱温度４００℃、２４時間の真空脱気による前処理を行った後、測定した吸着等温曲線を図１４に示す。本発明で得られた新規ナノ多孔体ＡＰＺは、気体の吸着性能が高いことを示し、ＢＥＴ比表面積と細孔容積及び、ＮＬＤＦＴ（非線形密度汎関数法）による解析から見積もられたミクロ細孔径は、表１６のように与えられた。 High silica nanoporous material APZ series pore structure / characteristic evaluation by gas adsorption measurement and water vapor adsorption measurement High silica nanoporous material APZ-1, APZ-2, APZ-3 and APZ described in Examples 1-3 and 5-8 above For -4, the nanoporous body having a pore structure was proved from the isothermal adsorption property of nitrogen gas of the nanoporous body. FIG. 14 shows a measured adsorption isotherm after pretreatment by vacuum degassing at a heating temperature of 400 ° C. for 24 hours. The novel nanoporous material APZ obtained in the present invention shows high gas adsorption performance, and the micropore diameter estimated from the BET specific surface area, pore volume, and analysis by NLDFT (nonlinear density functional theory) Are given in Table 16.

ＳＥＭ観察の結果と併せて、相対圧の大きな領域（Ｐ／Ｐ０≒１）での吸着量の増加が著しいことから、外表面による吸着が非常に大きいことが理解される。また、結晶サイズが小さいものほどその傾向が強いことが示された。更に、ＡＰＺ−１では、吸着・脱着にヒステリシスが見られることから、メソ孔程度の空隙ができていることを意味し、層状骨格が一部剥離したためにできたものと考えられる。更に、ＡＰＺ−１から、ＡＰＺ−４は、架橋部位に孤立シラノール基（水酸基）を持つことから、親水性の特徴を有する。これは、水蒸気吸着を行うことで明らかとなった。図１５に示されるように、結晶１ｇあたり最大で０．２−０．３５ｇの高い水吸着能を示すことが分かった。このときのＢＥＴ比表面積は、表１７で与えられる。 Together with the results of SEM observation, it is understood that the adsorption by the outer surface is very large since the amount of adsorption in the region where the relative pressure is large (P / P 0 ≈1) is remarkable. It was also shown that the smaller the crystal size, the stronger the tendency. Furthermore, in APZ-1, since hysteresis is observed in adsorption / desorption, it means that voids of about mesopores are formed, and it is considered that the layered skeleton was partially peeled off. Furthermore, APZ-1 to APZ-4 have hydrophilic characteristics because they have an isolated silanol group (hydroxyl group) at the cross-linked site. This became clear by performing water vapor adsorption. As shown in FIG. 15, it was found that a maximum water adsorption capacity of 0.2 to 0.35 g per 1 g of crystals was exhibited. The BET specific surface area at this time is given in Table 17.

高シリカナノ多孔体ＡＰＺ−１のガス吸着測定及び水蒸気吸着測定による細孔構造・特性評価
上記実施例４記載の高シリカナノ多孔体ＡＰＺ−１（表１０記載のＲｕｎ Ｎｏ．１７、１８）は、用いた結晶性層状ケイ酸塩ＰＬＳ−１の結晶サイズやモルフォロジーを大きく変化させたものを用いている。これによる吸着特性の違いを調べるために、窒素ガス吸着及び水蒸気吸着を行い、図１６に示される等温曲線を得た。大きな結晶を使って調製したＡＰＺ−１では、窒素ガス吸着測定からは、吸着と脱着に大きなヒステリシスが観測された。ＮＬＤＦＴ解析から細孔分布を見積もったところ、９．０Åのミクロ孔以外に、１．８ｎｍ付近と５．３ｎｍ付近にメソ孔があることが示唆された。一方、水蒸気吸着等温曲線からは、２つのサンプルとも基本的な同じ傾向を示した。しかし、相対圧の大きな領域（Ｐ／Ｐ０≒１）での吸着量の増加は、高密度凝集結晶の方が顕著であることから、結晶サイズが小さいことによる粒子間空隙への吸着が支配的であると考えられる。 Evaluation of pore structure and properties by gas adsorption measurement and water vapor adsorption measurement of high silica nanoporous material APZ-1 High silica nanoporous material APZ-1 described in Example 4 above (Run Nos. 17 and 18 described in Table 10) The crystallized layered silicate PLS-1 having a greatly changed crystal size and morphology is used. In order to investigate the difference in the adsorption characteristics, nitrogen gas adsorption and water vapor adsorption were performed to obtain an isothermal curve shown in FIG. In APZ-1 prepared using large crystals, a large hysteresis was observed in adsorption and desorption from nitrogen gas adsorption measurement. When the pore distribution was estimated from the NLDFT analysis, it was suggested that there were mesopores in the vicinity of 1.8 nm and 5.3 nm in addition to the 9.0 mm micropores. On the other hand, from the water vapor adsorption isotherm, the two samples showed the same basic tendency. However, the increase in the amount of adsorption in the region where the relative pressure is large (P / P 0 ≈1) is more noticeable in the high-density agglomerated crystal, and the adsorption to the interparticle void due to the small crystal size is dominant. It is considered to be appropriate.

高シリカナノ多孔体ＡＰＺシリーズの耐熱性の評価
上記実施例１−８記載の高シリカナノ多孔体ＡＰＺ−１、ＡＰＺ−２、ＡＰＺ−３及びＡＰＺ−４の耐熱性について検討した。電気炉を用いて、２Ｌ／ｍｉｎの空気流通下で、１℃／ｍｉｎの昇温速度にて６０℃から６００℃まで昇温し、２時間保持の熱処理（焼成）を行ったときのＡＰＺ−１の構造変化を示す、粉末ＸＲＤパターンを図１７に示す。６００℃の焼成後も、やや結晶性が低下するものの、ＡＰＺ−１の構造が保持されていることが分かった。この他、ＡＰＺ−２からＡＰＺ−４においても、図１８に示すように、６００℃の焼成後も構造が保たれていることを確認した。また、吸着測定において、４００℃の前処理後でも、高いガス吸着能を示しており、結晶性の低下が僅かであることから、６００℃以上の耐熱性を有していると言える。 Evaluation of heat resistance of high silica nanoporous material APZ series The heat resistance of high silica nanoporous materials APZ-1, APZ-2, APZ-3 and APZ-4 described in Example 1-8 was examined. APZ- when the temperature was raised from 60 ° C. to 600 ° C. at a rate of 1 ° C./min using an electric furnace at an air flow rate of 2 L / min and heat treatment (firing) was held for 2 hours. A powder XRD pattern showing the structural change of 1 is shown in FIG. Even after baking at 600 ° C., it was found that the structure of APZ-1 was maintained, although the crystallinity was slightly lowered. In addition, in APZ-2 to APZ-4, as shown in FIG. 18, it was confirmed that the structure was maintained after baking at 600 ° C. Further, in the adsorption measurement, even after the pretreatment at 400 ° C., the high gas adsorption ability is exhibited and the crystallinity is slightly lowered, so that it can be said that the heat resistance is 600 ° C. or higher.

以上詳述したように、本発明は、結晶性層状ケイ酸塩の高温酸処理による高シリカナノ多孔体の製造方法及びその高シリカナノ多孔体に係るものであり、本発明により、結晶性層状ケイ酸塩の高温酸処理により、迅速に、親水性を有する高シリカナノ多孔体を製造し、提供することができる。本発明の新規ナノ多孔体ＡＰＺシリーズは、既知・既存のケイ素５員環構造からなるシリカ含有量が高い結晶性層状ケイ酸塩を母体とし、例えば、親水性分離剤、吸着剤、金属担持用固体、形状選択性固体触媒、イオン交換剤、クロマトグラフィー充填剤材料及び化学反応場など、広範な用途に利用可能である。また、本発明のナノ多孔体は、高シリカ型に特徴的な耐熱性と耐薬品性の性質を持ちながらも、高い結晶性や高親水性及び高いガス吸着能を示す。本発明のＡＰＺシリーズの合成は、既存の結晶性層状ケイ酸塩をその合成条件に近い温度条件で短時間酸処理するだけでナノ多孔体ＡＰＺが得られることが大きな特徴である。本発明は、既存の高シリカ型ゼオライトと性質を異にする新規結晶性高シリカナノ多孔体の製造技術として高い優位性を有するものである。   As described above in detail, the present invention relates to a method for producing a high silica nanoporous material by high-temperature acid treatment of a crystalline layered silicate and the high silica nanoporous material. By high-temperature acid treatment of the salt, a high-silica nanoporous material having hydrophilicity can be rapidly produced and provided. The novel nanoporous material APZ series of the present invention is based on a known and existing crystalline layered silicate having a high silica content and consisting of a 5-membered silicon ring structure. For example, a hydrophilic separator, an adsorbent, and a metal support It can be used for a wide range of applications such as solids, shape selective solid catalysts, ion exchangers, chromatographic filler materials and chemical reaction fields. In addition, the nanoporous material of the present invention exhibits high crystallinity, high hydrophilicity, and high gas adsorption ability while having the heat resistance and chemical resistance properties characteristic of the high silica type. The synthesis of the APZ series of the present invention is characterized in that the nanoporous material APZ can be obtained simply by acid-treating an existing crystalline layered silicate under a temperature condition close to the synthesis condition. The present invention is highly advantageous as a technique for producing a novel crystalline high-silica nanoporous material having properties different from those of existing high-silica zeolite.

１Ｍ塩酸水溶液中にて加熱温度１７０℃で加熱して得られた新規ナノ多孔体ＡＰＺ−１の粉末Ｘ線回折パターンを示す。The powder X-ray diffraction pattern of the novel nanoporous material APZ-1 obtained by heating at a heating temperature of 170 ° C. in a 1 M hydrochloric acid aqueous solution is shown. １Ｍ塩酸水溶液中にて加熱温度１７０℃で加熱して得られた新規ナノ多孔体ＡＰＺ−１の結晶構造の概略を表す図である。（上）はｃ軸から見た図、（下）はｂ軸から見た図をそれぞれ表す。矢印で示される部位１と部位２は等確率で分布し、局部的にはどちらか片方だけ存在する。It is a figure showing the outline of the crystal structure of novel nanoporous material APZ-1 obtained by heating at a heating temperature of 170 ° C. in a 1M hydrochloric acid aqueous solution. (Upper) is a view seen from the c-axis, and (Lower) is a view seen from the b-axis. The part 1 and the part 2 indicated by the arrows are distributed with equal probability, and only one of them exists locally. １Ｍ塩酸水溶液中にて加熱温度１７０℃で加熱して得られた新規ナノ多孔体ＡＰＺ−２の粉末Ｘ線回折パターンを示す。The powder X-ray diffraction pattern of the novel nanoporous material APZ-2 obtained by heating at a heating temperature of 170 ° C. in a 1M hydrochloric acid aqueous solution is shown. １Ｍ塩酸水溶液中にて加熱温度１７０℃で加熱して得られた新規ナノ多孔体ＡＰＺ−２の結晶構造の概略を表す図である。（上）はｂ軸から見た図、（下）はａ軸から見た図をそれぞれ表す。It is a figure showing the outline of the crystal structure of novel nanoporous material APZ-2 obtained by heating at a heating temperature of 170 ° C. in a 1M hydrochloric acid aqueous solution. (Upper) shows a view from the b-axis, and (Lower) shows a view from the a-axis. １Ｍ塩酸水溶液中にて加熱温度１７０℃で加熱して得られた新規ナノ多孔体ＡＰＺ−３の粉末Ｘ線回折パターンを示す。The powder X-ray diffraction pattern of the novel nanoporous material APZ-3 obtained by heating at a heating temperature of 170 ° C. in a 1M hydrochloric acid aqueous solution is shown. １Ｍ塩酸水溶液中にて加熱温度１７０℃で加熱して得られた新規ナノ多孔体ＡＰＺ−３の結晶構造の概略を表す図である。（上）はｃ軸から見た図、（下）はｂ軸から見た図をそれぞれ表す。矢印で示される部位１と部位２は等確率で分布し、局部的にはどちらか片方だけ存在する。It is a figure showing the outline of the crystal structure of novel nanoporous material APZ-3 obtained by heating at a heating temperature of 170 ° C. in a 1M hydrochloric acid aqueous solution. (Upper) is a view seen from the c-axis, and (Lower) is a view seen from the b-axis. The part 1 and the part 2 indicated by the arrows are distributed with equal probability, and only one of them exists locally. １Ｍ塩酸水溶液中にて加熱温度１７０℃で加熱して得られた新規ナノ多孔体ＡＰＺ−４の粉末Ｘ線回折パターンを示す。The powder X-ray diffraction pattern of the novel nanoporous material APZ-4 obtained by heating at a heating temperature of 170 ° C. in a 1M hydrochloric acid aqueous solution is shown. １Ｍ塩酸水溶液中にて加熱温度１７０℃で加熱して得られた新規ナノ多孔体ＡＰＺ−４の結晶構造の概略を表す図である。（上）はｂ軸から見た図、（下）はａ軸から見た図をそれぞれ表す。It is a figure showing the outline of the crystal structure of the novel nanoporous material APZ-4 obtained by heating at a heating temperature of 170 ° C. in a 1M hydrochloric acid aqueous solution. (Upper) shows a view from the b-axis, and (Lower) shows a view from the a-axis. 結晶性層状ケイ酸塩使って、（１）層間の脱水重縮合によるゼオライト化、（２）層間にＳｉＯ４四面体を架橋剤として導入（シリル化）することによる親水性高シリカナノ多孔体の構築を示したイメージ図である。Using crystalline layered silicate, (1) Zeolite formation by dehydration polycondensation between layers, (2) Construction of hydrophilic high silica nanoporous material by introducing SiO 4 tetrahedron as a crosslinking agent between layers (silylation) It is the image figure which showed. ＡＰＺ−１、ＡＰＺ−２、ＡＰＺ−３及びＡＰＺ−４の２９Ｓｉ ＭＡＳ ＮＭＲスペクトルを示す。The 29 Si MAS NMR spectra of APZ-1, APZ-2, APZ-3 and APZ-4 are shown. ＡＰＺ−１、ＡＰＺ−２、ＡＰＺ−３及びＡＰＺ−４の１３Ｃ ＣＰ／ＭＡＳ ＮＭＲスペクトル 13 C CP / MAS NMR spectra of APZ-1, APZ-2, APZ-3 and APZ-4 ＡＰＺ−１、ＡＰＺ−２、ＡＰＺ−３及びＡＰＺ−４のＴＧ−ＤＴＡカーブを示す。The TG-DTA curves of APZ-1, APZ-2, APZ-3 and APZ-4 are shown. ＡＰＺ−１、ＡＰＺ−２、ＡＰＺ−３及びＡＰＺ−４のＳＥＭ像である。It is a SEM image of APZ-1, APZ-2, APZ-3, and APZ-4. ＡＰＺ−１、ＡＰＺ−２、ＡＰＺ−３及びＡＰＺ−４の窒素ガス吸着等温曲線である。It is a nitrogen gas adsorption isotherm of APZ-1, APZ-2, APZ-3 and APZ-4. ＡＰＺ−１、ＡＰＺ−２、ＡＰＺ−３及びＡＰＺ−４の水蒸気吸着等温曲線である。It is a water vapor adsorption isotherm of APZ-1, APZ-2, APZ-3 and APZ-4. 表１０記載のＲｕｎ Ｎｏ１８で示される条件で調製したＡＰＺ−１の窒素ガス吸着等温曲線、Ｒｕｎ Ｎｏ １７、１８の水蒸気吸着等温曲線及びＲｕｎ Ｎｏ１８の細孔分布と細孔容積を表すカーブである。It is a curve showing the nitrogen gas adsorption isotherm of APZ-1 prepared on the conditions shown by Run No18 of Table 10, the water vapor adsorption isotherm of Run No17, 18, and the pore distribution and pore volume of Run No18. ＡＰＺ−１の６０℃から６００℃までの各温度で焼成した後の粉末Ｘ線回折パターンを示す。参考として、結晶性層状ケイ酸塩ＰＬＳ−１を最下部に併記してある。The powder X-ray-diffraction pattern after baking at each temperature from 60 degreeC to 600 degreeC of APZ-1 is shown. For reference, the crystalline layered silicate PLS-1 is shown at the bottom. ＡＰＺ−２、ＡＰＺ−３、ＡＰＺ−４の６００℃で焼成した後の粉末Ｘ線回折パターンを示す。参考として、結晶性層状ケイ酸塩ＰＬＳ−３、ＰＬＳ−４、ＰＲＥＦＥＲをそれぞれ最下部に併記してある。The powder X-ray-diffraction pattern after baking at 600 degreeC of APZ-2, APZ-3, APZ-4 is shown. For reference, the crystalline layered silicates PLS-3, PLS-4, and PREFER are shown at the bottom. 表８記載のＲｕｎ Ｎｏ１〜６で示される条件で調製したＡＰＺ−１の粉末Ｘ線回折パターンを示す。The powder X-ray-diffraction pattern of APZ-1 prepared on the conditions shown by Run No1-6 of Table 8 is shown. 表８記載のＲｕｎ Ｎｏ７〜１４で示される条件で調製したＡＰＺ−１の粉末Ｘ線回折パターンを示す。The powder X-ray-diffraction pattern of APZ-1 prepared on condition shown by Run No7-14 of Table 8 is shown. 表９及び表１０記載のＲｕｎ Ｎｏ１５〜１８で示される条件で調製したＡＰＺ−１の粉末Ｘ線回折パターンを示す。The powder X-ray-diffraction pattern of APZ-1 prepared on the conditions shown by Run No15-18 of Table 9 and Table 10 is shown. 表１１記載のＲｕｎ Ｎｏ１〜７で示される条件で調製したＡＰＺ−２の粉末Ｘ線回折パターンを示す。The powder X-ray-diffraction pattern of APZ-2 prepared on the conditions shown by Run No1-7 of Table 11 is shown. 表１１記載のＲｕｎ Ｎｏ１〜７で示される条件で調製したＡＰＺ−２の粉末Ｘ線回折パターンを示す。The powder X-ray-diffraction pattern of APZ-2 prepared on the conditions shown by Run No1-7 of Table 11 is shown. 表１３記載のＲｕｎ Ｎｏ１〜５で示される条件で調製したＡＰＺ−３の粉末Ｘ線回折パターンを示す。The powder X-ray-diffraction pattern of APZ-3 prepared on the conditions shown by Run No1-5 of Table 13 is shown. 表１３記載のＲｕｎ Ｎｏ１〜３で示される条件で調製したＡＰＺ−４の粉末Ｘ線回折パターンを示す。The powder X-ray-diffraction pattern of APZ-4 prepared on the conditions shown by Run No1-3 of Table 13 is shown.

Claims (14)

隣接する層状骨格構造がＳｉＯ４四面体部位で架橋されたことで、層間にミクロ孔が形成された構造を有し、親水性を有し、架橋部位が、化学式Ｏ２Ｓｉ（ＯＨ）２で表される局所構造であり、かつその耐熱性が少なくとも６００℃以上であり、表１に示される回折ピーク位置と相対強度の関係を有する、ことを特徴とする高シリカナノ多孔体ＡＰＺ−１。
Adjacent layered skeletal structure is cross-linked at the SiO 4 tetrahedral site, resulting in a structure in which micropores are formed between the layers, hydrophilic, and the cross-linked site is represented by the chemical formula O 2 Si (OH) 2 . A high-silica nanoporous material APZ-1 having a local structure expressed and having a heat resistance of at least 600 ° C. and having a relationship between a diffraction peak position shown in Table 1 and a relative intensity.
窒素ガス吸着から細孔径８．６Åのミクロ孔及びＳＢＥＴ＝２５０ｍ２／ｇの比表面積を有する、請求項１記載の高シリカナノ多孔体ＡＰＺ−１。 The high silica nanoporous material APZ-1 according to claim 1, which has micropores having a pore diameter of 8.6 mm and a specific surface area of S BET = 250 m 2 / g from nitrogen gas adsorption. 水蒸気吸着からＳＢＥＴ＝１９０ｍ２／ｇの比表面積を有する、請求項１記載の高シリカナノ多孔体ＡＰＺ−１。 The high silica nanoporous material APZ-1 according to claim 1, which has a specific surface area of S BET = 190 m 2 / g from water vapor adsorption. 隣接する層状骨格構造がＳｉＯ４四面体部位で架橋されたことで、層間にミクロ孔が形成された構造を有し、親水性を有し、架橋部位が、化学式Ｏ２Ｓｉ（ＯＨ）２で表される局所構造であり、かつその耐熱性が少なくとも６００℃以上であり、表２に示される回折ピーク位置と相対強度の関係を有する、ことを特徴とする高シリカナノ多孔体ＡＰＺ−２。
Adjacent layered skeletal structure is cross-linked at the SiO 4 tetrahedral site, resulting in a structure in which micropores are formed between the layers, hydrophilic, and the cross-linked site is represented by the chemical formula O 2 Si (OH) 2 . A high-silica nanoporous material APZ-2 which has a local structure represented and has a heat resistance of at least 600 ° C. or more and a relationship between a diffraction peak position and a relative intensity shown in Table 2.
窒素ガス吸着から細孔径８．６Åのミクロ孔及びＳＢＥＴ＝５１０ｍ２／ｇの比表面積を有する、請求項４記載の高シリカナノ多孔体ＡＰＺ−２。 The high silica nanoporous material APZ-2 according to claim 4, which has a micropore having a pore diameter of 8.6 mm and a specific surface area of S BET = 510 m 2 / g from nitrogen gas adsorption. 水蒸気吸着からＳＢＥＴ＝１２０ｍ２／ｇの比表面積を有する、請求項４記載の高シリカナノ多孔体ＡＰＺ−２。 The high silica nanoporous material APZ-2 according to claim 4, which has a specific surface area of S BET = 120 m 2 / g from water vapor adsorption. 隣接する層状骨格構造がＳｉＯ４四面体部位で架橋されたことで、層間にミクロ孔が形成された構造を有し、親水性を有し、架橋部位が、化学式Ｏ２Ｓｉ（ＯＨ）２で表される局所構造であり、かつその耐熱性が少なくとも６００℃以上であり、表３に示される回折ピーク位置と相対強度の関係を有する、ことを特徴とする高シリカナノ多孔体ＡＰＺ−３。
Adjacent layered skeletal structure is cross-linked at the SiO 4 tetrahedral site, resulting in a structure in which micropores are formed between the layers, hydrophilic, and the cross-linked site is represented by the chemical formula O 2 Si (OH) 2 . A high-silica nanoporous material APZ-3, which has a local structure represented, has a heat resistance of at least 600 ° C., and has a relationship between a diffraction peak position and a relative intensity shown in Table 3.
アルゴンガス吸着から細孔径９．０Åのミクロ孔及びＳＢＥＴ＝３４０ｍ２／ｇの比表面積を有する、請求項７記載の高シリカナノ多孔体ＡＰＺ−３。 The high silica nanoporous material APZ-3 according to claim 7, which has a micropore having a pore diameter of 9.0 mm and a specific surface area of S BET = 340 m 2 / g from argon gas adsorption. 水蒸気吸着からＳＢＥＴ＝１２０ｍ２／ｇの比表面積を示し、親水性である、請求項７記載の高シリカナノ多孔体ＡＰＺ−３。 The high silica nanoporous material APZ-3 according to claim 7, which exhibits a specific surface area of S BET = 120 m 2 / g from water vapor adsorption and is hydrophilic. 隣接する層状骨格構造がＳｉＯ４四面体部位で架橋されたことで、層間にミクロ孔が形成された構造を有し、親水性を有し、架橋部位が、化学式Ｏ２Ｓｉ（ＯＨ）２で表される局所構造であり、かつその耐熱性が少なくとも６００℃以上であり、表４に示される回折ピーク位置と相対強度の関係を有する、ことを特徴とする高シリカナノ多孔体ＡＰＺ−４。
Adjacent layered skeletal structure is cross-linked at the SiO 4 tetrahedral site, resulting in a structure in which micropores are formed between the layers, hydrophilic, and the cross-linked site is represented by the chemical formula O 2 Si (OH) 2 . A high-silica nanoporous material APZ-4, which is represented by a local structure, has a heat resistance of at least 600 ° C. and has a relationship between a diffraction peak position shown in Table 4 and a relative intensity.
窒素ガス吸着から細孔径９．０Åのミクロ孔及びＳＢＥＴ＝３３０ｍ２／ｇの比表面積を有する、請求項１０記載の高シリカナノ多孔体ＡＰＺ−４。 The high silica nanoporous material APZ-4 according to claim 10 , which has a micropore having a pore diameter of 9.0 mm and a specific surface area of S BET = 330 m 2 / g from nitrogen gas adsorption. 水蒸気吸着からＳＢＥＴ＝１６０ｍ２／ｇの比表面積を有する、請求項１０記載の高シリカナノ多孔体ＡＰＺ−４。 The high silica nanoporous material APZ-4 according to claim 10, which has a specific surface area of S BET = 160 m 2 / g from water vapor adsorption. 請求項１から１２のいずれか一項に記載の高シリカナノ多孔体を製造する方法であって、結晶性層状ケイ酸塩ＰＬＳ−１、ＰＬＳ−３、ＰＬＳ−４、又はＰＲＥＦＥＲを高温酸処理することを特徴とする高シリカナノ多孔体の製造方法。   A method for producing the high silica nanoporous material according to any one of claims 1 to 12, wherein the crystalline layered silicate PLS-1, PLS-3, PLS-4, or PREFER is subjected to high-temperature acid treatment. A method for producing a high silica nanoporous material. 上記結晶性層状ケイ酸塩を、塩酸又は硝酸水溶液中で、加熱温度１６０−１８０℃、加熱時間１−２４時間の条件で高温酸処理する、請求項１３記載の高シリカナノ多孔体の製造方法。   The method for producing a high silica nanoporous material according to claim 13, wherein the crystalline layered silicate is subjected to high-temperature acid treatment in a hydrochloric acid or nitric acid aqueous solution under the conditions of a heating temperature of 160 to 180 ° C and a heating time of 1 to 24 hours.
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