KR100816538B1 - Preparation of surface functionalized porous organic-inorganic hybrid materials or mesoporous materials with coordinatively unsaturated metal sites - Google Patents

Abstract

A method for preparing a surface-functionalized porous organic-inorganic hybrid material or mesoporous material is provided to be applicable to an adsorber, a gas storage material, a sensor, a membrane, a functional thin film, a catalyst, a catalyst carrier and the like. A method for preparing a surface-functionalized porous organic-inorganic hybrid material or mesoporous material comprises reaction of porous organic-inorganic hybrid materials having coordinatively unsaturated metal sites with at least one compound selected from silane, an organic metal compound and polyoxometallate. Particularly, the porous organic-inorganic hybrid material is a crystalline polymer compound of a microporous structure, which is formed by combination of a core metal ion thereof with an organic ligand. In the method, the reaction comprises depositing the silane or the organic metal compound onto the porous organic-inorganic hybrid material, or introducing the porous organic-inorganic hybrid material into a solution of the organic metal compound or polyoxometallate.

Description

Preparation of surface functionalized porous organic-inorganic hybrid materials or mesoporous materials with coordinatively unsaturated metal sites

1 shows an XRD pattern of a surface functionalized porous organic-inorganic hybrid, wherein (a) is MIL-101 of Comparative Example 1, (b) is APS-MIL-101 of Example 1, and (c) is Example The XRD pattern of MPTS-MIL-101 of 3 is shown.

Figure 2 shows the infrared spectroscopy spectrum of the surface functionalized porous organic-inorganic hybrid (a) is MIL-101 of Comparative Example 1, (b) is the infrared spectroscopy spectrum of APS-MIL-101 of Example 1.

Figure 3 is a TEM image (a) and EDX elemental analysis (b) results of the surface functionalized porous organic-inorganic hybrid (Pd-APS-MIL-101) prepared in Example 4.

The present invention relates to a nanoporous body having a high surface area, and to a method for selectively functionalizing an organic-inorganic material at a saturated metal site of the nanoporous body, and a surface functionalized nanoporous body prepared therefrom. More specifically, the porous organic-inorganic hybrid materials or metal-organic frameworks or the coordinatively unsaturated metal site (or open metal) of the porous organic-inorganic mesoporous body in the nanopore. Surfaces of porous organic-inorganic hybrids that can optionally be used to functionalize organic-inorganic materials (such as open-metal sites) to be used in adsorbents, gas reservoirs, sensors, membranes, functional thin films, catalysts, and catalyst carriers. Modification methods and surface functionalized porous organic-inorganic hybrids or porous organic-inorganic mesoporous bodies prepared therefrom.

In general, an unsaturated metal site is a coordinable site of a metal in which water or an organic solvent has been removed from an organic-inorganic hybrid or mesoporous body, and means a position at which an organometallic compound can form a covalent bond or a coordinating bond.

The porous organic-inorganic hybrid used in the present invention may be defined as a porous organic-inorganic polymer compound formed by combining a central metal ion with an organic ligand, and includes both organic and inorganic substances in a skeletal structure and has a molecular size or nano size. It means a crystalline compound having a pore structure. Porous organic-inorganic hybrids are termed broadly termed porous coordination polymers (Angew. Chem. Intl. Ed., 43, 2334. 2004). Metal-organic frameworks (Chem. Soc. Rev., 32, 276, 2003). Research into these materials has recently begun to develop anew by incorporating molecular coordination bonds and materials science, which have high surface areas and molecular or nanoscale pores that can be used to adsorbents, gas storage, sensors, membranes, and functionalities. It has been actively researched recently because it can be used only for thin films, catalysts and catalyst carriers.

In addition, the porous organic-inorganic mesoporous body used in the present invention is a regular molecular sieve having a meso-sized pore distribution in the range of 2-50 nm, in which dissimilar metals are substituted to have unsaturated metal sites. Pore size properties have been reported for a wide range of applications as catalyst carriers, catalysts, adsorbents and functional materials (Chem. Rev. 97, 2373, 1997).

The surface functionalization method for giving the applicability of the high surface area porous organic-inorganic mesoporous material is generally a covalent bond between an organometallic compound represented by an organosilane and an already prepared porous pore surface hydroxyl group (-OH). The method of bonding to the surface is mainly used (Curr. Opin. Solid State Mater. Sci. 3,71, 1998, Chem. Lett. 6, 624, 2000). In addition, a method of directly functionalizing a pore surface by mixing an organosilane compound and a mesoporous precursor has been reported (J. Mater. Chem. 16, 1125, 2006).

-Si-OH + R _x M (OR) _4-x (1≤x≤3) → -Si-OM (OR) _3-x R _x + ROH (Scheme 1)

However, a method of selectively functionalizing an unsaturated metal site of an organic-inorganic hybrid having an extremely small amount of hydroxyl groups on the surface or containing only a porous pore unsaturated metal site containing no hydroxyl group or a heterometal-substituted porous organic-inorganic mesoporous body Has not been reported yet.

Accordingly, the present invention proposes a method for selectively functionalizing unsaturated metal sites of porous organic-inorganic hybrids or porous organic-inorganic mesoporous bodies.

Accordingly, in the present invention, in order to solve the above problems, a silane, an organometallic compound or a polyoxometallate is selectively added to an unsaturated metal site which is not a hydroxyl group on the surface of the porous organic-inorganic hybrid or the porous organic-inorganic mesoporous body. It is an object to provide a method for producing a surface functionalized porous organic-inorganic hybrid or porous organic-inorganic mesoporous by combining.

In addition, it provides a surface functionalized porous organic-inorganic hybrid or porous organic-inorganic mesoporous body prepared by the above production method, which can be used in adsorbents, gas reservoirs, sensors, membranes, functional thin films, catalysts and catalyst carriers. There is another object of the present invention.

In addition, another object of the present invention is a catalyst for acid or base reaction, hydrogenation, dehydrogenation, carbon-carbon bond reaction, or oxidation reaction using the surface functionalized porous organic-inorganic hybrid or porous organic-inorganic mesoporous body To provide a composition.

Surface functionalized porous characterized in that the porous organic-inorganic hybrids or mesoporous bodies having unsaturated metal sites are reacted with at least one selected from silanes (SiH ₄ ), organometallic compounds or polyoxometalates. Process for preparing organic-inorganic hybrids or porous organic-inorganic mesoporous bodies, surface functionalized porous organic-inorganic hybrids or porous organic-inorganic mesoporous bodies prepared from the preparation method thereof, and the surface functionalized porous organic-inorganic It relates to a catalyst composition using a hybrid or porous organic-inorganic mesoporous material.

The present invention is capable of coordinating or covalently binding one or more selected from silanes, organometallic compounds or polyoxometallates to unsaturated metal sites that are not hydroxyl groups on the surface of porous organic-inorganic hybrids or porous organic-inorganic mesoporous bodies. It is characterized by functionalizing a porous organic-inorganic hybrid or a porous organic-inorganic mesoporous body.

The porous organic-inorganic hybrid refers to a crystalline polymer compound having a pore structure formed by combining a central metal ion with an organic ligand, and the porous organic-inorganic mesoporous body has a meso size having an unsaturated metal site by dissimilar metals. It means a molecular sieve having pores of. The porous organic-inorganic mesoporous body is a regular molecular sieve having a pore distribution of about 2 to 50 nm, and the porous organic-inorganic hybrid generally has a molecular size or a pore of several nm.

In addition, the present invention, after functionalizing the surface of the primary porous organic-inorganic hybrid or porous organic-inorganic mesoporous body with at least one selected from silane, organometallic compound or polyoxometalate, precious metal, transition metal or It may further comprise the step of supporting at least one selected from metal oxides thereof.

In addition, the method for producing a surface functionalized porous organic-inorganic hybrid or porous organic-inorganic mesoporous body of the present invention comprises a pretreatment step of removing the water or solvent component bonded to the unsaturated metal site of the porous organic-inorganic hybrid. It may further include.

Hereinafter, the present invention will be described in more detail.

In the present invention, the porous organic-inorganic hybrid is not particularly limited, but may be prepared through a method of heating a reactant mixture containing a metal source, an organic material which may act as a ligand, and a solvent. The heating is not limited to the method, and may be selected and used in an electric heating method, a micro irradiation or a method of irradiating sound waves, but in order to prepare a nano-sized porous organic-inorganic hybrid crystals, the electric heating method or The method using a microwave is more preferable.

The metal material, which is a member of the porous organic-inorganic hybrid, can be any metal and can be Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh , Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, Mg, Ca, Sr, Ba, Sc, Y, Al, Ga, In, Tl, Si, Ge, Sn, Pb, As , Sb, Bi and the like are representative metal materials. Particularly suitable are transition metals that make coordination compounds well. Among the transition metals, chromium, vanadium, iron, nickel, cobalt, copper, titanium, aluminum and manganese are suitable, and chromium, iron, aluminum and vanadium are more suitable. In addition to transition metals, rare earth metals such as lanthanum are possible, as well as typical elements that make up coordination compounds. Among the typical elements, aluminum and silicon are suitable, and among lanthanum metals, cerium and lanthanum are suitable. As the metal source, any compound of the metal may be used as well as the metal itself.

), 아미드기(-CONH₂), 술폰산기(-SO₃H), 술폰산 음이온기(-SO₃ ^-), 메탄디티오산기(-CS₂H), 메탄디티오산 음이온기(-CS₂ ^-), 피리딘기 또는 피라진기 등이 예시될 수 있다. 보다 안정한 유무기혼성체를 유도하기 위해서는 배위할 수 있는 자리가 2개 이상인, 예를 들면 바이덴테이트 또는 트리덴테이트인 유기물이 유리하다. 유기물로는 배위할 자리가 있다면 비피리딘, 피라진 등의 중성 유기물, 테레프탈레이트, 나프탈렌디카복실레이트, 벤젠트리카복실레이트, 글루타레이트, 숙신네이트 등으로 예시될 수 있는 카복실산의 음이온 등의 음이온성 유기물은 물론 양이온 물질도 가능하다. 카복실산 음이온의 경우 예를 들면 테레프탈레이트 같은 방향족 링을 갖는 것 외에 포르메이트 같은 선형의 카복실산의 음이온은 물론이고 시클로헥실디카보네이트와 같이 비방향족 링을 갖는 음이온 등 어느 것이라도 가능하다. 배위할 수 있는 자리를 가진 유기물은 물론이고 잠재적으로 배위할 자리를 가져 반응 조건에서 배위할 수 있게 변화되는 것도 가능하다. 즉, 테레프탈산 같은 유기산을 사용하여도 반응 후에는 테레프탈레이트로 금속 성분과 결합할 수 있다. 사용할 수 있는 유기물의 대표적인 예로는 벤젠디카르복실산, 나프탈렌디카복실산, 벤젠트리카복실산, 나프탈렌트리카복실산, 피리딘디카복실산, 비피리딜디카복실산, 포름산, 옥살산, 말론산, 숙신산, 글루타르산, 헥산다이오익산, 헵탄다이오익산, 또는 시클로헥실디카복실산에서 선택되는 유기산 및 그들의 음이온, 피라진, 비피리딘 등이다. 또한, 하나 이상의 유기물을 혼합하여 사용할 수도 있다.Organics, another member of the porous organic-inorganic hybrid, are also called linkers and can be any organic having coordinating functional groups. Coordinating functional groups are carboxylic acid groups, carboxylic acid anion groups, amino groups (-NH). ₂ ), imino (

), Amide group (-CONH _2), a sulfonic acid group (-SO ₃ H), a sulfonic acid anion group (-SO ₃ ^-), methane dithiol Osan group (-CS ₂ H), methane dithiol Osan anion group (-CS ₂ ^- ), Pyridine group or pyrazine group and the like can be exemplified. In order to induce a more stable organic-inorganic hybrid, an organic substance having two or more coordinating sites, for example, bidentate or tridentate, is advantageous. As organic materials, if there is a position to coordinate, neutral organic materials such as bipyridine and pyrazine, anionic organic materials such as terephthalate, naphthalenedicarboxylate, benzenetricarboxylate, glutarate, anion of carboxylic acid which can be exemplified by succinate, etc. Of course, cationic materials are also possible. In the case of the carboxylic acid anion, for example, anion of a linear carboxylic acid such as formate as well as an anion having a non-aromatic ring such as cyclohexyl dicarbonate can be used, in addition to having an aromatic ring such as terephthalate. Organics with coordinating sites, as well as potentially coordinating sites, can also be changed to coordinate under reaction conditions. That is, even if an organic acid such as terephthalic acid is used, it can be combined with a metal component with terephthalate after the reaction. Representative examples of organic materials that can be used include benzenedicarboxylic acid, naphthalenedicarboxylic acid, benzenetricarboxylic acid, naphthalenetricarboxylic acid, pyridinedicarboxylic acid, bipyridyldicarboxylic acid, formic acid, oxalic acid, malonic acid, succinic acid, glutaric acid and hexanedioo Organic acids selected from Ixic acid, heptanedioic acid, or cyclohexyldicarboxylic acid and their anions, pyrazine, bipyridine and the like. It is also possible to mix and use one or more organics.

In addition to the metal source and organic matter, an appropriate solvent is required for the synthesis of the organic-inorganic hybrid, and alcohols such as water, methanol, ethanol and propanol, ketones such as acetone and methyl ethyl ketone, and hydrocarbons such as hexane, heptane and octane Substances may be used, or two or more solvents may be mixed and water is most suitable.

Representative examples of porous organic-inorganic hybrids include chromium terephthalate, vanadium terephthalate, iron terephthalate, aluminum terephthalate, and in particular, MIL-100 (Angew. Chem. Int. Ed. 43, 6296, 2004). ), MIL-101 (Science, 309, 2040, 2005) or MOF-500 (Angew. Chem. Int. Ed. 45, 2528, 2006), such as porous organic-inorganic hybrids are most suitable.

The porous organic-inorganic hybrid may have a thin film or membrane form, and the porous organic-inorganic hybrid of the thin film or membrane form may include alumina, silicon, glass, indium tin oxide (ITO), indium zinc oxide (IZO), and heat resistant polymer. The material or the substrate surface-treated with the material may be prepared by immersing the reactant mixture.

In addition, porous organic-inorganic mesoporous bodies having unsaturated metal sites are heterogeneous metal-substituted materials, such as MCM-41, SBA-15, MSU-H, or three-dimensional cubic SBA-16, having a hexagonal structure of pores. SBA-1, FDU-1, MCM-48, etc. are suitable.

Moreover, as a compound which can be bonded to an unsaturated metal site, 1 or more types can be selected and used from a silane, an organometallic compound, or a polyoxo metalate. The organometallic compound may be used by selecting one or more from compounds represented by the following Chemical Formulas 2 to 9, wherein the silane is represented by the following Chemical Formula 1.

[Formula 1]

SiH ₄

[Formula 2]

Si (OR ¹ ) _4-x R _x (1≤x≤3)

[Formula 3]

Si (OR ³ ) _{4- (y + z)} R ² _y Z _z (1≤y + z≤3)

[Formula 4]

Si (OR ⁴ ) _4-a R ⁵ _a Si (1≤a≤3)

[Formula 5]

Z ¹ _b (OR ⁶ ) _3-b Si-A-Si (OR ⁷ ) _3-C Z ² _C (0≤b≤2, 0≤c≤2)

[Formula 6]

R ⁸ _e M ¹ (OR ⁹ ) _4-e (1≤e≤3)

[Formula 7]

R ¹⁰ _g M ² Z ³ _f (OR ¹¹ ) _{4- (f + g)} (1≤f + g≤3)

[Formula 8]

M ³ (OR ¹² ) _h (1≤h≤2)

[Formula 9]

M ⁴ (OR ¹³ ) _i Z ⁴ _j (1≤i + j≤2)

Wherein A is a C ₁ to C ₂₀ alkylene or aralkylene group, with or without unsaturated hydrocarbons, Z ¹ to Z ⁴ are independently selected from halogen elements, and M ¹ and M ² are independently At least one element selected from the group consisting of transition metals, lanthanum series and actinium series metals, M ³ and M ⁴ are independently at least one element selected from alkaline earth metals or alkali metals, and R, R ¹ to R ¹³ are Independently selected from halogen, vinyl group (-C = CH), amino group (-NH ₂ ), imino group (-NHR ¹⁴ ), mercapto group (-SH), hydroxy group (-OH) or carboxylic acid group (-COOH) C ₁ to C ₂₀ alkyl group, alkenyl group or alkynyl group, or a vinyl group (-C = CH) or an amino group (-NH). ₂ ), from the imino group (-NHR ¹⁴ ), mercapto group (-SH), hydroxy group (-OH) or carboxylic acid group (-COOH) R ¹⁴ is a C ₁ to C ₁₀ alkyl group, alkenyl group or alkynyl group which is optionally substituted with a halogen element, an amino group, a mercapto group or a hydroxy group.

Among the organometallic compounds, an organosilane-containing compound is mainly used, and specific examples thereof include a silylating agent, a silane coupling agent, a silane polymer, or a mixture thereof.

Among the surface functionalizing materials, the organosilane compounds of Formulas 2 to 5 are not only easy to bond to unsaturated metal sites of porous organic-inorganic hybrids or porous organic-inorganic mesoporous bodies, but also stably exist after bonding, and more preferably, the organic silane compounds Among the silane compounds, when having an alkoxy group and on the other side having an alkyl, alkenyl, or alkynyl group having a functional group selected from an amino group or a mercapto group, it forms a stable bond with the porous organic-inorganic hybrid or the porous organic-inorganic mesoporous body. At the same time, the activity as a catalyst is high, which is more preferable.

In addition, polyoxometalates such as [AlO ₄ Al1 ₂ (OH) ₂₄ (H ₂ O) ₁₂ ] ⁷⁺ cation and [PW ₁₂ O ₄₀ ] ^4- anion may be used as the surface functionalizing material. As an anion of the Keggin structure in the late compound [(XM ₁₂ O ₄₀ ) ^{n −} , n = 1 to 10; X = P, Si, H, Ga, Ge, V, Cr, Me or Fe; At least one of M = W, Mo, and Co], as an anion of the Lindqvist structure [(M ₆ O ₁₉ ) ^{n −} , n = 1 to 10; As the anion of Evans structure (Anderson-Evans structure) [( M x (OH) 6 M 6 O 18) n - - M = W, Mo, Ta, V or W], Anderson, n = 1 ~ 10; M _x = Cr, Ni, Fe, Mn; M = Mo, W] or _{[(M 4 (H 2 O} ) 4 (P 2 W 15 O 56) 2) n -, n = 1 ~ 10; M = one or more transition metals or transition metal clusters selected from Cu, Zn, Ni, Mn, or the like, or (P ₂ W ₁₅ O ₅₆ ) ₂ or the like as a material of a Dawson-Wells structure. have.

In addition, when functionalizing a porous organic-inorganic hybrid or a porous organic-inorganic mesoporous body by selecting two or more kinds of silanes, organometallic compounds or polyoxometalates, two or more kinds of substances may be mixed and used sequentially. It is also possible to use a method of first functionalizing one substance and then functionalizing another substance later. Preferably, after the first reaction with the organometallic compound, the second reaction with the polyoxo metalate to prepare a porous organic-inorganic hybrid or porous organic-inorganic mesoporous surface functionalized with two or more materials. In particular, this method has an advantage of suppressing the dissolution of the metal when the active material is secondly supported on the functional group.

More preferably, the pretreatment step of removing the water or the solvent component bonded to the unsaturated metal site is performed before the surface functionalization of the porous organic-inorganic hybrid or porous organic-inorganic mesoporous body. The pretreatment may be any method as long as it can remove water or solvent components without causing deformation of the porous organic-inorganic hybrid or the porous organic-inorganic mesoporous body, and more specifically, at a temperature of 100 ° C. or higher under reduced pressure. It is preferable to heat 2 hours or more, and it is more preferable to heat 4 hours or more at the temperature of 150 degreeC or more.

Embodiments of the method for producing a surface functionalized porous organic-inorganic porous body or porous organic-inorganic mesoporous body according to the present invention include (a) a porous organic-inorganic mesoporous substituted with a porous organic-inorganic hybrid or a dissimilar metal. Removing organic solvents such as water (H ₂ O) or alcohols coordinated to unsaturated metal sites on the surface of the sieve, (b) dissolving the organometallic compounds or polyoxometalates in organic solvents such as toluene. Adding a pre-treated porous organic-inorganic pore or porous organic-inorganic mesoporous body to a reflux reaction in an organometallic compound solution or a polyoxometallate solution to functionalize it, and (c) the porous functionalized organometallic compound. And purifying the organic-inorganic pore or porous organic-inorganic mesoporous body.

In addition, when surface-functionalizing a porous organic-inorganic hybrid or porous organic-inorganic mesoporous body using highly volatile silane or organometallic compound, the gaseous silane or organometallic compound may be porous by a method such as chemical vapor deposition. The organic-inorganic hybrid or mesoporous may be contacted to selectively bind to the unsaturated metal sites of the porous organic-inorganic hybrid or mesoporous.

In addition, the method for producing a surface functionalized porous organic-inorganic hybrid or porous organic-inorganic mesoporous body according to the present invention may include a silane, an organometallic compound, or a polyoxometallate in order to impart a catalyst, a sensor, and other applications. The surface-functionalized porous organic-inorganic hybrid or mesoporous body may be immobilized by supporting at least one selected from noble metals, transition metals, rare earth elements or oxides thereof. As the noble metal, a single or complex metal such as Pd, Au, Pt, Ru, etc. may generally be used. In addition, as the transition metal, Ti, Zr, V, Fe, Ni, Nb, W, Mo, Ta, Mn and the like may be preferably used. In addition, as the rare earth element, an element of lanthanide can be used.

The method of fixing one or more selected from the noble metals, transition metals, rare earth elements or oxides thereof may be carried out by conventional methods, and reducing compounds containing noble metals, transition metals or rare earth elements with a reducing agent in solution. After that, a method of supporting in a reduced state or supporting a compound in a non-reduced state may be used, and may be supported in the form of a metal oxide combined with oxygen.

The present invention provides a surface functionalized porous organic-inorganic hybrid or porous organic-inorganic mesoporous body prepared by the above method, and the present invention also provides the surface-functionalized porous organic-inorganic hybrid or porous organic- It provides a catalyst composition for acid or base reaction or inorganic, dehydrogenation or carbon-carbon bond reaction using an inorganic mesoporous body, or a catalyst composition for oxidation reaction using oxygen, air and hydrogen peroxide. The catalyst composition for hydrogenation, dehydrogenation, or carbon-carbon bond reaction or catalyst composition for oxidation reaction is primarily a silane, organometallic compound or poly in the surface functionalized porous organic-inorganic hybrid or porous organic-inorganic mesoporous body. It is suitable to use porous organic-inorganic mesoporous bodies or porous organic-inorganic mesoporous bodies which are surface functionalized with oxometalate and are secondarily supported with at least one selected from noble metals, transition metals or metal oxides thereof.

The catalyst composition according to the present invention is a composition containing a surface functionalized porous organic-inorganic hybrid or porous organic-inorganic mesoporous body prepared by the above method, and the surface functionalized porous organic-inorganic hybrid or porous oil. Inorganic mesoporous body may be used alone, or may be used in combination with other catalyst components, or may be prepared by mixing the surface functionalized porous organic-inorganic hybrid or porous organic-inorganic mesoporous body with the base material. And coating the surface functionalized porous organic-inorganic hybrid or porous organic-inorganic mesoporous body on the substrate.

Hereinafter, the present invention is described in more detail in the following non-limiting examples.

Comparative Example 1 Preparation of Porous Organic-Inorganic Hybrid (MIL-101)

Prepared by the previously reported method of porous organic-inorganic hybrid MIL-101 having a pore size of 1 nm or more (Science, 309, 2040, 2005). In the preparation method, Cr (NO ₃ ) _{3 ·} 9H ₂ O, HF aqueous solution and 1,4-benzenedicarboxylic acid (BDCA) were added to a Teflon reactor, distilled water was added thereto, and the final molar ratio of the reactant was Cr: HF: BDCA: H ₂ O = 1: 1: 1: 275. The reaction mixture was maintained in an oven at 220 ° C. for 8 hours to react, cooled to room temperature, centrifuged, washed with distilled water, and dried to obtain an organic-inorganic hybrid MIL-101. The X-ray diffraction morphology of the solids was in good agreement with the reported previous studies (Science 2005, 309, 2040). The XRD pattern of the obtained crystal is shown in FIG. 1A.

Example 1 APS-MIL-101 Functionalized with Amino Group

1 g of MIL-101 prepared in Comparative Example 1 was pretreated for 12 hours in a 200 ° C. vacuum oven to dehydrate water coordinated to an unsaturated metal site. 1 g of the dehydrated MIL-101 is added to 50 ml of toluene solution containing 5.7 ml of 3-aminopropyltriethoxysilane (APS). The solution was refluxed at 110 ° C. for 12 hours to prepare a porous organic-inorganic hybrid having an ethoxy functional group coordinated at an unsaturated metal site. From the X-ray diffraction pattern before and after supporting APS, it was found that a material having the same structure as that of MIL-101 having a pure change in the structure of the porous organic-inorganic hybrid was obtained (FIG. 1B). Of APS was coordinated is an amino group (-NH ₂₎ and ethyl group in the APS - it was found that the presence in 2800 -3000cm ^-1 and 3200-3400 cm ^-1 by infrared spectroscopy, APS (-CH ₂ CH ₂₎ The -OH group (3550-3650 cm ^-1 ) of the porous organic-inorganic hybrid before and after the coordination of Al showed little change, indicating that APS selectively reacted with unsaturated metal sites (FIG. 2).

Example 2 APS-MIL-100 Functionalized with Amino Group

Cr metal is used as a precursor of Cr and 1,3,5-benzenetricarboxylic acid (H3BTC) is added to the organic-structure support as distilled water, and the final molar ratio of the reactants is Cr: HF: H3BTC: H ₂ O = 1.4: 2.8 Except for 1: 1: 373, the same procedure as in Comparative Example 1 was carried out to obtain a porous organic-inorganic hybrid MIL-100. The X-ray diffraction morphology of the solids was found to be in good agreement with the reported previous studies (Angew. Chem. Int. Ed. 43, 6296, 2004).

In addition, functionalizing 3-aminopropyltriethoxysilane (APS) on the surface of MIL-100 by the same method as in Example 1 except using MIL-100 instead of MIL-101 I could make it.

Example 3 Preparation of MIL-101 Incorporated with Thiol Group

Example 1 except that mercaptopropyltriethoxylsilane (MPTS) is functionalized at the unsaturated metal configuration of MIL-101 instead of 3-aminopropyltriethoxysilane (APS) To proceed in the same manner as to prepare a MIL-101 introduced with a thiol group. From the X-ray diffraction pattern, it can be seen that an organic-inorganic hybrid having a thiol group functionalized without the same structural change as in Example 1 was obtained (FIG. 1C). IR analysis showed that the -SH group was functionalized in the porous organic-inorganic hybrid MIL-101.

Example 4 Preparation of Pd-APS-MIL-101 Supported with Palladium

In order to carry out vacuum pretreatment of 1 g of APS-MIL-101 prepared in Example 1 at 150 ° C. and to carry 1 wt% Pd with the organic-inorganic hybrid (APS-MIL-101), 0.016 g of PdCl _{2 was added} to ethanol. Disperse in 30 ml solution. 0.9 g of NaBH ₄ as a reducing agent was added to the mixture to prepare Pd-APS-MIL-101 loaded with Pd. XRD analysis showed that the crystal structure was maintained even with NaBH ₄ , a strong reducing agent. It was confirmed by TEM / EDX analysis that the particles of Pd were distributed in the MIL-101 pores (FIG. 3).

Example 5 Preparation of Au-MPTS-MIL-101 Supported with Gold

Except for using HAuCl ₄ instead of PdCl ₂ was prepared in the same manner as in Example 4 to prepare Au-MPTS-MIL-101 loaded with 1% by weight of Au. XRD analysis showed that the crystal structure was maintained even with NaBH ₄ , a strong reducing agent.

Example 6 Preparation of PWA-NH3-MIL-101 Supported Heteropolyanion

0.5 g APS-MIL-101 prepared in Example 1 was prepared using PWA (10 ml of 0.01 MH ₃ PW ₁₂ O _40. 12H ₂ O, MWPW = 2882) and stirred at room temperature for 12 hours to prepare a PWA-NH ₃ -MIL-101 organic-inorganic hybrid in which the heteropolyanion was supported by NH ₃ ⁺ -MIL-101 cation by ion bonding. . ICP elemental analysis confirmed that the PWA was loaded by 50% by weight.

Example 7 APS-MIL-101 Functionalized with Amino Group

In Comparative Example 1, HF was removed and synthesized at 200 ° C. for 16 hours to prepare MIL-101 having F removed therein, and then the surface of the organic-inorganic hybrid was modified with APS under the same conditions as in Example 1 to obtain APS- ( MIL-101 with F removed) was prepared.

Example 8 Preparation of APS-MIL-101 Functionalized with Amino Group (Adjustment of Pretreatment Conditions)

Similar to Example 4, an organic-inorganic hybrid APS-MIL-101 was prepared, but functionalization was performed using MIL-101 at 150 ° C. as a pretreatment condition. Compared with the prepared APS-MIL-101 it was confirmed that the specific surface area is slightly reduced. In contrast, it was confirmed that the catalytic activity in the base catalyst reaction was inferior. This is interpreted to prevent the pores of the porous organic-inorganic hybrid by reacting the water remaining in the unsaturated metal site on the surface of the porous organic-inorganic hybrid and the alkoxy group of the APS (Table 1).

Example 9 APS-SBA-15 Functionalized with Amino and Base Catalysis

SBA-15, a hexagonal silica mesoporous body, was prepared by a method known in the literature (J. Phys. Chem. 106, 255, 2002). The calcined silica SBA-15 was confirmed to be the same as the XRD form reported in the literature. Similarly to Example 1, a functional group of amino groups was prepared, but the mesoporous SBA-15, which was not a porous organic-inorganic hybrid, was used for the functionalized support. The reaction resulted in lower catalytic reactivity than APS-MIL-101 at the same reaction time. This can be explained by the fact that the Free -NH ₂ group of APS-MIL-101 was activated relative to APS-SBA-15 (Table 1).

<Example 10>

Benzaldehyde (BZA), which is a basic catalysis, using a porous organic-inorganic hybrid (APS-MIL-101) containing aminosilane functional groups obtained in Examples 1, 8 and 9 and having an alkoxy group coordinated thereto , 10 mmol) and ethyl cyanoacetate (ECA) were used as a reactant to conduct a Knoevenagel condensation reaction to form ethyl trans -a-cyanocinnamate. The reaction results are shown in Table 1. As shown in Table 1, the reaction result was superior to APS-MIL-101 of Example 8 or APS-SBA-15 of Example 9, which was surface treated by pretreatment at 150 ° C, and showed superior activity as a superior base catalyst. there was.

Table 1 Comparison of catalytic activity of Knoevenagel condensation reactions

<Example 11>

CC bond formation reaction to form trans-stilbene from iodobenzene and styrene using Pd-supported Pd-APS-MIL-101 obtained in Example 4 ) Was performed. As a result of the reaction, Pd-APS-SBA-15 was found to have two or more times higher activity.

<Example 12> A porous organic-inorganic hybrid MIL-101 thin film functionalized with an amino group

Cr (NO ₃ ) _{3 ·} 9H ₂ O, HF aqueous solution and 1,4-benzenedicarboxylic acid (BDCA) were added to the Teflon reactor, and distilled water was added thereto, and the final molar ratio of the reactant was Cr: HF: BDCA: H ₂ O = 1: 1: 1: 275. The Teflon reactor containing the alumina substrate-containing reactant was mounted in a vertically aligned alumina substrate in a solution, mounted in a microwave reactor (CEM, Model Mars-5), and heated to 180 ° C. over 3 minutes by irradiation with microwaves. Thereafter, the mixture was kept at 180 ° C. for 30 minutes to react, cooled to room temperature, washed with distilled water, and dried to obtain an organic-inorganic hybrid, MIL-101. The X-ray diffraction pattern of the thin film was in good agreement with the results of conventional powder synthesis studies (Science 2005, 309, 2040) obtained by synthesis in an electric oven at 220 ° C for 10 hours. The MIL-101 thin film is fixed vertically at a distance to the bottom of a reflux reactor in which 50 ml of toluene solution containing 1 ml of 3-aminopropyltriethoxysilane (APS) is dissolved. The solution was refluxed at 110 ° C. for 12 hours to prepare a porous organic-inorganic hybrid thin film in which an ethoxy functional group was coordinated at an unsaturated metal site.

As described above, according to the present invention, surface functionalization is performed on unsaturated metal sites of porous organic-inorganic hybrids and mesoporous bodies, so that the surface of the hybrids in which a small amount or no hydroxy group is present on the surface can be functionalized. I could confirm that. The method was found to be very fast and highly selective in terms of kinetics compared to the method of functionalizing an organic-inorganic compound on the surface hydroxy group of the pore body.

 In particular, such surface functionalized porous organic-inorganic hybrids or porous organic-inorganic mesoporous bodies can be utilized in the production of catalysts, catalyst carriers, adsorbents, gas storage, ion exchange and nano-reactors and nanomaterials, in particular the presence of surface functionalized porous bodies The hybrid or porous organic-inorganic mesoporous nanoparticles can be used as sensors, photoelectric materials and medical materials as well as catalysts having excellent activity.

Claims (19)

A method for producing a surface functionalized porous organic-inorganic hybrid, characterized by reacting a porous organic-inorganic hybrid having an unsaturated metal site with at least one compound selected from silane, organometallic compound or polyoxometalate. The method of claim 1, The porous organic-inorganic hybrid is a method of producing a surface functionalized porous organic-inorganic hybrid, characterized in that the crystalline polymer compound of the pore structure formed by combining the central metal ion with the organic ligand. The method of claim 1, The reaction is characterized by depositing a silane or organometallic compound on the surface of the porous organic-inorganic hybrid, or by reacting the organic metal-organic compound or the polyoxometallate solution by adding a porous organic-inorganic hybrid Method for producing a porous organic-inorganic hybrid. The method of claim 1, The porous organic-inorganic hybrid is a method of producing a surface functionalized porous organic-inorganic hybrid, characterized in that the removal of water or solvent components bonded to unsaturated metal sites. The method of claim 1, The organometallic compound is a method for producing a surface functionalized porous organic-inorganic hybrid, characterized in that at least one selected from the compounds represented by the formula 2 to 9. [Formula 2] Si (OR ¹ ) _4-x R _x (1≤x≤3) [Formula 3] Si (OR ³ ) _{4- (y + z)} R ² _y Z _z (1≤y + z≤3) [Formula 4] Si (OR ⁴ ) _4-a R ⁵ _a Si (1≤a≤3) [Formula 5] Z ¹ _b (OR ⁶ ) _3-b Si-A-Si (OR ⁷ ) _3-C Z ² _C (0≤b≤2, 0≤c≤2) [Formula 6] R ⁸ _e M ¹ (OR ⁹ ) _4-e (1≤e≤3) [Formula 7] R ¹⁰ _g M ² Z ³ _f (OR ¹¹ ) _{4- (f + g)} (1≤f + g≤3) [Formula 8] M ³ (OR ¹² ) _h (1≤h≤2) [Formula 9] M ⁴ (OR ¹³ ) _i Z ⁴ _j (1≤i + j≤2) Wherein A is a C ₁ to C ₂₀ alkylene or aralkylene group, with or without unsaturated hydrocarbons, Z ¹ to Z ⁴ are independently selected from halogen elements, and M ¹ and M ² are independently At least one element selected from the group consisting of transition metals, lanthanum series and actinium series metals, M ³ and M ⁴ are independently at least one element selected from alkaline earth metals or alkali metals, and R, R ¹ to R ¹³ are Independently selected from halogen element, vinyl group (-C = CH), amino group (-NH ₂ ), imino group (-NHR ¹⁴ ), mercapto group (-SH), hydroxy group (-OH) or carboxylic acid group (COOH) One or more substituted or unsubstituted C ₁ ~ C ₂₀ Alkyl, alkenyl or alkynyl or vinyl group (-C = CH), amino group (-NH ₂ ) , Imino group (-NHR ¹⁴ ), mercapto group (-SH), hydroxyl group (-OH) or carboxylic acid group (COOH) R ¹⁴ is a C ₁ to C ₁₀ alkyl group, alkenyl group or alkynyl group which is unsubstituted or substituted with a halogen element, an amino group, a mercapto group or a hydroxy group. The method of claim 1, A method for producing a surface functionalized porous organic-inorganic hybrid, wherein the porous organic-inorganic hybrid having an unsaturated metal site is first reacted with an organometallic compound and then secondly reacted with polyoxometalate. The method of claim 1, The porous organic-inorganic hybrid is a method for producing a surface functionalized porous organic-inorganic hybrid, characterized in that prepared by heating a reactant mixture comprising a metal source (organic) and a solvent that can act as a ligand. The method of claim 7, wherein Metal precursors are Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn At least one metal selected from Cd, Hg, Mg, Ca, Sr, Ba, Sc, Y, Al, Ga, In, Tl, Si, Ge, Sn, Pb, As, Sb, Bi, or a metal compound thereof. Method for producing a surface functionalized porous organic-inorganic hybrid to. The method of claim 7, wherein Organics that can act as ligands include carboxylic acid groups, carboxylic acid anion groups, amino groups (-NH ₂ ), and imino groups (

), Amide group (-CONH _2), a sulfonic acid group (-SO ₃ H), a sulfonic acid anion group (-SO ₃ ^-), methane dithiol Osan group (-CS ₂ H), methane dithiol Osan anion group (-CS ₂ ^- ), A compound having at least one functional group selected from a pyridine group or a pyrazine group, or a mixture thereof, the method for producing a surface functionalized porous organic-inorganic hybrid. The method of claim 9, The compound having the carboxylic acid group is benzenedicarboxylic acid, naphthalenedicarboxylic acid, benzenetricarboxylic acid, naphthalene tricarboxylic acid, pyridinedicarboxylic acid, bipyridyldicarboxylic acid, formic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, hexanedioic acid, heptanedio A method for producing a surface functionalized porous organic-inorganic hybrid, characterized in that it is selected from Ikic acid, or cyclohexyldicarboxylic acid. The method of claim 1, A method for producing a surface functionalized porous organic-inorganic hybrid further comprising supporting at least one selected from a noble metal, a transition metal or a metal oxide thereof in the surface functionalized porous organic-inorganic hybrid. The method of claim 1, Method for producing a surface functionalized porous organic-inorganic hybrid, characterized in that the porous organic-inorganic hybrid is chromium terephthalate, iron terephthalate or vanadium terephthalate, aluminum terephthalate. The method of claim 12, Method for producing a surface functionalized porous organic-inorganic hybrid, characterized in that the porous organic-inorganic hybrid having a MIL-101 or MIL-100 structure. The method of claim 12, The porous organic-inorganic hybrid is a method of producing a surface functionalized porous organic-inorganic hybrid, characterized in that the iron terephthalate of the MOF-500 structure. The method of claim 7, wherein Method for producing a surface functionalized porous organic-inorganic hybrid, characterized in that the porous organic-inorganic hybrid has a thin film or membrane form. The method of claim 15, The porous organic-inorganic hybrid in the form of a thin film or membrane may be immersed in a reactant mixture by alumina, silicon, glass, indium tin oxide (ITO), indium zinc oxide (IZO), a heat resistant polymer material, or a surface treated with the material. Method for producing a surface functionalized porous organic-inorganic hybrid, characterized in that for producing. Surface functionalization characterized in that a silane, at least one compound selected from an organometallic compound selected from the following Chemical Formulas 2 to 9 or polyoxometalate is bonded to an unsaturated metal site of a porous organic-inorganic hybrid having an unsaturated metal site Porous organic-inorganic hybrids. [Formula 2] Si (OR ¹ ) _4-x R _x (1≤x≤3) [Formula 3] Si (OR ³ ) _{4- (y + z)} R ² _y Z _z (1≤y + z≤3) [Formula 4] Si (OR ⁴ ) _4-a R ⁵ _a Si (1≤a≤3) [Formula 5] Z ¹ _b (OR ⁶ ) _3-b Si-A-Si (OR ⁷ ) _3-C Z ² _C (0≤b≤2, 0≤c≤2) [Formula 6] R ⁸ _e M ¹ (OR ⁹ ) _4-e (1≤e≤3) [Formula 7] R ¹⁰ _g M ² Z ³ _f (OR ¹¹ ) _{4- (f + g)} (1≤f + g≤3) [Formula 8] M ³ (OR ¹² ) _h (1≤h≤2) [Formula 9] M ⁴ (OR ¹³ ) _i Z ⁴ _j (1≤i + j≤2) Wherein A is a C ₁ to C ₂₀ alkylene or aralkylene group, with or without unsaturated hydrocarbons, Z ¹ to Z ⁴ are independently selected from halogen elements, and M ¹ and M ² are independently At least one element selected from the group consisting of transition metals, lanthanum series and actinium series metals, M ³ and M ⁴ are independently at least one element selected from alkaline earth metals or alkali metals, and R, R ¹ to R ¹³ are Independently selected from halogen element, vinyl group (-C = CH), amino group (-NH ₂ ), imino group (-NHR ¹⁴ ), mercapto group (-SH), hydroxy group (-OH) or carboxylic acid group (COOH) One or more substituted or unsubstituted C ₁ ~ C ₂₀ Alkyl, alkenyl or alkynyl or vinyl group (-C = CH), amino group (-NH ₂ ) , Imino group (-NHR ¹⁴ ), mercapto group (-SH), hydroxyl group (-OH) or carboxylic acid group (COOH) R ¹⁴ is a C ₁ to C ₁₀ alkyl group, alkenyl group or alkynyl group which is unsubstituted or substituted with a halogen element, an amino group, a mercapto group or a hydroxy group. A catalyst composition for acid or base reaction using the surface functionalized porous organic-inorganic hybrid according to claim 17. A catalyst composition for hydrogenation, dehydrogenation, carbon-carbon coupling, or oxidation using oxygen, air or hydrogen peroxide using the surface functionalized porous organic-inorganic hybrid according to claim 17.

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