KR100895413B1 - A method for preparing porous organic-inorganic hybrid materials, porous organic-inorganic hybrid materials obtained by the method and catalytic uses of the materials - Google Patents
A method for preparing porous organic-inorganic hybrid materials, porous organic-inorganic hybrid materials obtained by the method and catalytic uses of the materials Download PDFInfo
- Publication number
- KR100895413B1 KR100895413B1 KR1020070063881A KR20070063881A KR100895413B1 KR 100895413 B1 KR100895413 B1 KR 100895413B1 KR 1020070063881 A KR1020070063881 A KR 1020070063881A KR 20070063881 A KR20070063881 A KR 20070063881A KR 100895413 B1 KR100895413 B1 KR 100895413B1
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- South Korea
- Prior art keywords
- acid
- inorganic hybrid
- group
- organic
- porous organic
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- 238000000034 method Methods 0.000 title claims description 35
- 239000000463 material Substances 0.000 title abstract description 15
- 230000003197 catalytic effect Effects 0.000 title abstract 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 47
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- 239000002184 metal Substances 0.000 claims description 17
- 150000002894 organic compounds Chemical class 0.000 claims description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 13
- 239000000376 reactant Substances 0.000 claims description 11
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- INBDPOJZYZJUDA-UHFFFAOYSA-N methanedithiol Chemical compound SCS INBDPOJZYZJUDA-UHFFFAOYSA-N 0.000 claims description 8
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- 125000000524 functional group Chemical group 0.000 claims description 3
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 claims description 3
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- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
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- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 125000001841 imino group Chemical group [H]N=* 0.000 claims description 2
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- LVPMIMZXDYBCDF-UHFFFAOYSA-N isocinchomeronic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)N=C1 LVPMIMZXDYBCDF-UHFFFAOYSA-N 0.000 claims description 2
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- 238000002156 mixing Methods 0.000 claims description 2
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- KVQQRFDIKYXJTJ-UHFFFAOYSA-N naphthalene-1,2,3-tricarboxylic acid Chemical compound C1=CC=C2C(C(O)=O)=C(C(O)=O)C(C(=O)O)=CC2=C1 KVQQRFDIKYXJTJ-UHFFFAOYSA-N 0.000 claims description 2
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- 235000006408 oxalic acid Nutrition 0.000 claims description 2
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- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 2
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- 125000003373 pyrazinyl group Chemical group 0.000 claims description 2
- GJAWHXHKYYXBSV-UHFFFAOYSA-N pyridinedicarboxylic acid Natural products OC(=O)C1=CC=CN=C1C(O)=O GJAWHXHKYYXBSV-UHFFFAOYSA-N 0.000 claims description 2
- 229910052702 rhenium Inorganic materials 0.000 claims description 2
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- 239000001384 succinic acid Substances 0.000 claims description 2
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 2
- 229910052715 tantalum Inorganic materials 0.000 claims description 2
- 229910052716 thallium Inorganic materials 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- JSCNZPJYIJBBJI-UHFFFAOYSA-D [V+5].[V+5].[O-]C(=O)c1ccc(cc1)C([O-])=O.[O-]C(=O)c1ccc(cc1)C([O-])=O.[O-]C(=O)c1ccc(cc1)C([O-])=O.[O-]C(=O)c1ccc(cc1)C([O-])=O.[O-]C(=O)c1ccc(cc1)C([O-])=O Chemical compound [V+5].[V+5].[O-]C(=O)c1ccc(cc1)C([O-])=O.[O-]C(=O)c1ccc(cc1)C([O-])=O.[O-]C(=O)c1ccc(cc1)C([O-])=O.[O-]C(=O)c1ccc(cc1)C([O-])=O.[O-]C(=O)c1ccc(cc1)C([O-])=O JSCNZPJYIJBBJI-UHFFFAOYSA-D 0.000 claims 1
- XTWMRBJKMXZQDS-UHFFFAOYSA-N iron;terephthalic acid Chemical compound [Fe].OC(=O)C1=CC=C(C(O)=O)C=C1 XTWMRBJKMXZQDS-UHFFFAOYSA-N 0.000 claims 1
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- 238000000746 purification Methods 0.000 description 6
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 5
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- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 4
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- 238000000635 electron micrograph Methods 0.000 description 3
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- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 description 3
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- 229910017855 NH 4 F Inorganic materials 0.000 description 2
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Classifications
-
- B01J35/60—
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
Abstract
본 발명은 다공성 유무기혼성체 (porous organic inorganic hybrid materials)의 신규 제조방법으로서, 수득되는 다공성 유무기혼성체를 무기염으로 처리하여 정제하는 단계를 포함하며, 특히, 불산을 사용하지 않는 것을 특징으로 하는 제조 방법, 상기 제조 방법에 의하여 제조된 다공성 유무기혼성체 및 이의 촉매적 용도에 관한 것으로서, 상기 다공성 유무기혼성체는 높은 표면적과 분자크기 또는 나노크기의 세공을 갖고 있어 흡착제, 기체 저장, 센서, 멤브레인, 기능성 박막, 촉매 및 촉매 담체 등에 사용될 수 있으며 세공크기보다 작은 게스트 분자를 포집하거나 세공크기를 이용하여 분자들을 분리하는데 사용될 수 있다. The present invention is a novel method for producing a porous organic inorganic hybrid materials, comprising the step of purifying the resulting porous organic inorganic hybrid material with an inorganic salt, in particular, characterized in that it does not use hydrofluoric acid The present invention relates to a manufacturing method, a porous organic-inorganic hybrid prepared by the manufacturing method, and a catalytic use thereof. It may be used in functional thin films, catalysts and catalyst carriers, and may be used to trap guest molecules smaller than the pore size or to separate molecules using pore sizes.
유무기혼성체, 수열합성, 나노입자, 세공물질, 촉매, 마이크로파 합성 Organic-inorganic hybrids, hydrothermal synthesis, nanoparticles, pore materials, catalysts, microwave synthesis
Description
도 1은, 본 발명의 실시예 1의 제조방법에 따라 제조된 다공성 유무기혼성체인 크롬테레프탈레이트의 X-선 결정구조 그래프이다. 1 is an X-ray crystal structure graph of chromium terephthalate, which is a porous organic-inorganic hybrid prepared according to the preparation method of Example 1 of the present invention.
도 2는, 본 발명의 실시예 1의 정제방법에 따라 제조된 다공성 유무기혼성체인 크롬테레프탈레이트의 정제 전후의 X-선 회절 분석 결과를 나타낸 것으로, (a)는 정제전의 결과이고 (b)는 정제후의 결과이다.Figure 2 shows the results of X-ray diffraction analysis before and after the purification of chromium terephthalate, a porous organic-inorganic hybrid prepared according to the purification method of Example 1 of the present invention, (a) is the result before purification (b) Is the result after purification.
도 3은, 본 발명의 실시예 2에 의해 얻어진 다공성 유무기혼성체인 크롬테레프탈레이트에서의 질소 흡착 등온선 결과이다.3 is a nitrogen adsorption isotherm result of chromium terephthalate, which is a porous organic-inorganic hybrid obtained in Example 2 of the present invention.
도 4는, 본 발명의 실시예 3(a) 및 비교예 2(b)에 의해 얻어진 다공성 유무기혼성체인 크롬테레프탈레이트의 전자현미경 사진이다.4 is an electron micrograph of chromium terephthalate which is a porous organic-inorganic hybrid obtained in Example 3 (a) and Comparative Example 2 (b) of the present invention.
도 5는, 본 발명의 실시예 9에 의해 얻어진 다공성 유무기혼성체인 프리델-크래프트 벤질화반응 결과이다.5 is a result of Friedel-Craft benzylation reaction of the porous organic-inorganic hybrid obtained in Example 9 of the present invention.
본 발명은 다공성 유무기혼성체의 제조 방법 및 상기 유무기혼성체의 촉매응용에 관한 것으로, 보다 상세하게는, 수득되는 다공성 유무기혼성체를 무기염으로 처리하여 정제하는 단계를 포함하며, 또한, 종래기술에서 질산과 불산의 혼합용액을 사용하여만 제조가 가능했던 다공성 유무기세공체를, 불산을 사용하지 않고 다공성 유무기혼성체를 제조하는 신규 제조방법 및 상기 제조방법에 의하여 수득되는 다공성 유무기혼성체의 불균일 촉매로서의 응용에 관한 것이다. The present invention relates to a method for preparing a porous organic-inorganic hybrid and a catalyst application of the organic-inorganic hybrid, and more particularly, comprising the step of purifying the porous organic-inorganic hybrid obtained by treating with an inorganic salt, and also, the prior art A novel preparation method for producing a porous organic-inorganic hybrid which was only possible using a mixed solution of nitric acid and hydrofluoric acid, and a porous organic-inorganic hybrid obtained by the method It relates to an application as a heterogeneous catalyst.
본 발명에 따라 제조되는 다공성 유무기혼성체는 중심금속 이온이 유기 리간드와 결합하여 형성된 다공성 유무기 고분자 화합물로 정의될 수 있으며, 골격구조내에 유기물과 무기물을 모두 포함하고 분자크기 또는 나노크기의 세공구조를 갖는 결정성 화합물을 의미한다. 다공성 유무기혼성체는 광범위한 의미의 용어로서 일반적으로 다공성 배위고분자 (porous coordination polymers)라고도 하며 [Angew. Chem. Intl. Ed., 43, 2334. 2004], 금속-유기 골격체 (metal-organic frameworks)라고도 한다[Chem. Soc. Rev., 32, 276, 2003]. 이러한 물질에 대한 연구는 분자배위결합과 재료과학의 접목에 의해 최근에 새롭게 발전하기 시작하였으며, 이 물질들은 고표면적과 분자크기 또는 나노크기의 세공을 갖고 있어 흡착제, 기체 저장, 센서, 멤브레인, 기능성 박막, 촉매 및 촉매 담체 등에 사용될 뿐만 아니라, 세공크기보다 작은 게스트 분자를 포집하거나 세공을 이용하여 분자들의 크기에 따라 분자들을 분리하는데 사용될 수 있기 때문에 최근에 활발히 연구되어 왔다. 이러한 물질들은 여러 가지 방법으로 제조되었으며, 대표적으로 실온 근처에서 용매확산(solvent diffusion)을 이용하거나 물을 용매로 사용하여 고온에서 반응시키는 수열 합성(hydrothermal synthesis) 또는 유기 용매를 사용하는 용매열 합성(solvothermal synthesis) 방법을 통해 제조되었다 [Microporous Mesoporous Mater., 73, 15, 2004; Accounts of Chemical Research, 38, 217, 2005]. The porous organic-inorganic hybrid prepared according to 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 include both organic and inorganic substances in a skeletal structure and have a molecular or nano-sized pore structure. It means a crystalline compound having a. Porous organic-inorganic hybrids are termed broadly and generally referred to as porous coordination polymers [Angew. Chem. Intl. Ed., 43, 2334. 2004], also known as metal-organic frameworks [Chem. Soc. Rev., 32, 276, 2003]. Research on these materials has recently begun to develop anew by the incorporation of molecular coordination bonds and materials science. These materials have high surface areas and molecular or nanoscale pores that can be used for adsorbents, gas storage, sensors, membranes, and functionalities. In addition to being used in thin films, catalysts and catalyst carriers, etc., they have been actively studied recently because they can be used to trap guest molecules smaller than pore size or to separate molecules according to the size of molecules using pores. These materials have been prepared in a number of ways, typically hydrothermal synthesis using solvent diffusion at room temperature or using water as a solvent, or hydrothermal synthesis using organic solvents ( solvothermal synthesis) method [Microporous Mesoporous Mater., 73, 15, 2004; Accounts of Chemical Research, 38, 217, 2005].
특히 수열합성에 의한 다공성 유무기혼성체 합성의 경우, 일반적으로 결정의 형성 속도를 조절하기 위해서 질산과 불산 등의 복합산을 사용하였다. 상기 수열합성에 의하여 제조된 대표적인 다공성 유무기혼성체로는 화학식이 Cr3O(H2O)2F[C6H3-(CO2)3]2·nH2O (n~14.5)인 MIL-100 (Cr) 과, Cr3F(H2O)2O[C6H4(CO2)2]3·nH2O (n~25) 인 MIL-101 (Cr) 등이 보고되었다 [Science 23, 2040, 2005;Accounts of Chemical Research, 38, 217, 2005]. 그러나, 상기 종래 공정에서와 같이 불산을 사용한 경우, 다공성 유무기혼성체의 실제적 응용단계인 스케일 업 공정 적용시 합성용 반응기의 사용에 제한이 심각하며, 폐기물 처리비용도 상대적으로 높다. 또한 기존의 유무기혼성 세공체의 합성에서는 유기 리간드의 세공내 존재로 인하여 유무기혼성체의 결정성이 우수함에도 불구하고 표면적 또는 세공부피가 낮은 문제점이 있었다. 특히, Cr 이외의 금속이 치환된 금속-유기 골격구조의 유무기혼성체는 아직 보고되지 않았다. In particular, in the case of the synthesis of porous organic-inorganic hybrids by hydrothermal synthesis, complex acids such as nitric acid and hydrofluoric acid were generally used to control the rate of crystal formation. Representative porous organic-inorganic hybrid prepared by the hydrothermal synthesis as the formula Cr 3 O (H 2 O) 2 F [C 6 H 3- (CO 2 ) 3 ] 2 · nH 2 O (n ~ 14.5) MIL -100 (Cr) and MIL-101 (Cr) with Cr 3 F (H 2 O) 2 O [C 6 H 4 (CO 2 ) 2 ] 3 nH 2 O (n-25) have been reported [ Science 23, 2040, 2005; Accounts of Chemical Research, 38, 217, 2005]. However, when the hydrofluoric acid is used as in the conventional process, the use of the synthesis reactor is severely limited when applying the scale-up process, which is a practical application step of the porous organic-inorganic hybrid, and the waste disposal cost is relatively high. In addition, in the synthesis of the existing organic-inorganic hybrid pore, despite the excellent crystallinity of the organic-inorganic hybrid due to the presence of the organic ligand in the pore there is a problem of low surface area or pore volume. In particular, organic-inorganic hybrids of metal-organic frameworks substituted with metals other than Cr have not yet been reported.
이에, 상기 종래기술의 문제점을 해결하기 위하여, 본 발명자들은, 다공성 유무기혼성체를 제조함에 있어서, 수득되는 다공성 유무기혼성체를 무기염으로 처리하여 정제하는 단계를 포함하며, 불산을 전혀 사용하지 않는 신규 제조공정을 통하여 상대적으로 작은 입자 크기를 갖는 다공성 유무기혼성 나노세공체의 제조 및 정제 방법을 개발하고자 하였다. 또한 본 발명자들은 상기 신규 제조 방법에 의하여 수득되는 다공성 유무기혼성체를 포함하는 촉매로서, 산화환원반응 등에 높은 활성을 갖는 불균일 촉매를 개발하고자 하였다. 나아가 본 발명자들은 신속 및 연속제조 공정으로 마이크로파 조사에 의한 다공성 유무기혼성체 제조방법을 개발하고자 하였다.Thus, in order to solve the problems of the prior art, the present inventors, in the preparation of a porous organic-inorganic hybrid, comprising the step of purifying the resulting porous organic-inorganic hybrid with an inorganic salt, do not use any hydrofluoric acid Through the new manufacturing process, a method for preparing and purifying porous organic-inorganic hybrid nanoporous bodies having a relatively small particle size was developed. In addition, the inventors of the present invention have attempted to develop a heterogeneous catalyst having high activity as a catalyst including a porous organic-inorganic hybrid obtained by the novel production method. Furthermore, the present inventors have attempted to develop a porous organic-inorganic hybrid production method by microwave irradiation in a rapid and continuous manufacturing process.
따라서, 본 발명은, 상기 종래기술의 문제점을 해결하기 위하여, 다공성 유무기혼성체를 제조함에 있어서, 수득되는 다공성 유무기혼성체를 무기염으로 처리하여 정제하는 단계를 포함하며, 불산을 전혀 사용하지 않는 신규 제조공정에 의하여 환경 친화적 방법에 의하여 다공성 유무기혼성체를 제조하고, 정제하는 방법 및, 상기 방법에 의하여 제조된 다공성 유무기혼성체의 촉매로서 용도를 제공하는 것을 목적으로 한다. 또한, 본 발명은, 마이크로파 조사에 의하여 신속 및 연속제조 공정으로 다공성 유무기혼성체를 제조하는 방법을 제공하는 것을 목적으로 한다.Accordingly, the present invention, in order to solve the problems of the prior art, in the preparation of a porous organic-inorganic hybrid, comprising the step of purifying the obtained inorganic organic-inorganic hybrid with an inorganic salt, does not use any hydrofluoric acid It is an object of the present invention to provide a method for preparing and purifying a porous organic-inorganic hybrid by an environmentally friendly method by a novel manufacturing process, and to use it as a catalyst for the porous organic-inorganic hybrid prepared by the method. In addition, an object of the present invention is to provide a method for producing a porous organic-inorganic hybrid in a rapid and continuous manufacturing process by microwave irradiation.
본 발명은, 다공성 유무기혼성체의 효율적인 제조 방법에 관한 것으로서, 다 공성 유무기혼성체의 표면적을 증가시키기 위한 정제 방법을 포함하는 것을 특징으로 하며, 특히 수열합성 시 불산을 사용하지 않고 나노 크기의 입경을 갖는 다공성 유무기혼성체를 제조하는 것을 특징으로 한다. 또한, 본 발명은 상기 신규 제조방법에 의하여 수득되는 다공성 유무기혼성체를 산화반응용 촉매로서 사용하는 것을 특징으로 하는 용도에 관한 것이다.The present invention relates to an efficient method for producing a porous organic-inorganic hybrid, characterized in that it comprises a purification method for increasing the surface area of the porous organic-inorganic hybrid, particularly in the case of hydrothermal synthesis without using hydrofluoric acid It characterized in that the porous organic-inorganic hybrid having a. The present invention also relates to the use of a porous organic-inorganic hybrid obtained by the novel production method as an oxidation reaction catalyst.
즉, 본 발명은, 하기 단계를 포함하는, 다공성 유무기혼성체의 제조방법에 관한 것이다:That is, the present invention relates to a method for preparing a porous organic-inorganic hybrid, comprising the following steps:
1) 금속전구체, 리간드로 작용할 수 있는 유기 화합물 및 용매를 혼합하여 반응물 혼합액을 제조하는 단계; 1) preparing a reactant mixture by mixing a metal precursor, an organic compound that can act as a ligand, and a solvent;
2) 상기 반응물 혼합액을 전기가열 또는 마이크로파를 조사하여 100 ℃이상으로 가열하는 단계; 및2) heating the reactant mixture to 100 ° C. or more by electric heating or microwave irradiation; And
3) 상기 단계2)에서 수득되는 다공성 유무기혼성체를 무기염으로 처리하여 정제하는 단계.3) Purifying the porous organic-inorganic hybrid obtained in step 2) by treating with an inorganic salt.
본 발명에 따른 상기 제조방법에 의해 제조되는 다공성 유무기혼성체는 나노입자로서 수득될 수 있으며 상기 나노입자의 크기는 약 450nm 이하이다. 또한, 본 발명에 따른 상기 제조방법에 의해 제조되는 다공성 유무기혼성체는 분말상이거나, 박막 또는 멤브레인 형태일 수 있다. Porous organic-inorganic hybrids prepared by the method according to the present invention can be obtained as nanoparticles and the size of the nanoparticles is about 450 nm or less. In addition, the porous organic-inorganic hybrid prepared by the manufacturing method according to the present invention may be in the form of a powder, thin film or membrane.
나노입자, 박막 또는 멤브레인 형태의 다공성 유무기혼성체는, 상기 반응물 혼합액에 기판을 침지한 후 전기 가열 및 마이크로파를 조사하여 가열하는 방법으로 용이하게 제조할 수 있다.Porous organic-inorganic hybrids in the form of nanoparticles, thin films or membranes can be easily prepared by immersing the substrate in the reactant mixture and heating by irradiating with electric heating and microwaves.
이하 본 발명을 보다 상세히 설명한다.Hereinafter, the present invention will be described in more detail.
본 발명의 다공성 유무기혼성체의 제조방법은, 다공성 나노세공체의 제조를 위한 수열합성에서 불산을 사용하지 않고 나노 크기의 입경을 갖는 유무기혼성체를 제조하고, 또한, 다공성 유무기혼성체의 표면적을 증가시키기 위한 정제방법으로서 일반적으로 사용되는 용매 이외에 염화암모늄 또는 불화칼륨 등의 무기염을 사용하여 처리함으로써 유무기혼성체의 세공 내 불순물을 정제하는 과정을 포함하는 것을 특징으로 한다. 또한 상기 다공성 유무기혼성체가 산화 반응용 촉매로서 응용되는 용도를 갖는 것을 특징으로 한다.In the method for preparing a porous organic-inorganic hybrid of the present invention, an organic-inorganic hybrid having a particle size of nano size without hydrofluoric acid is prepared in the hydrothermal synthesis for the production of a porous nanoporous body, and the surface area of the porous organic-inorganic hybrid is further reduced. As a purification method for increasing, in addition to the solvent generally used, a process for purifying impurities in the pores of the organic-inorganic hybrid by treating with an inorganic salt such as ammonium chloride or potassium fluoride is characterized in that it comprises. In addition, the porous organic-inorganic hybrid is characterized in that it has a use that is applied as a catalyst for oxidation reaction.
본 발명의 제조방법에 있어서, 다공성 유무기혼성체의 하나의 구성원소인 금속 물질은 어떠한 금속이라도 가능하며, 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, Ga, In, Tl, Si, Ge, Sn, Pb, As, Sb, Bi 등이 대표적인 금속 물질이다. 특히 배위화합물을 잘 만드는 전이금속이 적당하다. 전이금속 중에서 크롬, 바나듐, 철, 니켈, 코발트, 구리, 티타늄 및 망간 등이 적당하며 크롬 및 철이 가장 적당하다. 전이금속 외에도 배위화합물을 만드는 전형원소는 물론 란타늄 같은 금속도 가능하다. 전형원소 중에는 알루미늄 및 실리콘이 적당하며 란타늄 금속 중에는 세륨, 란타늄이 적당하다. 금속원으로는 금속 자체는 물론이고 금속의 어떠한 화합물도 사용할 수 있다. In the production method of the present invention, the metal material which is one member of the porous organic-inorganic hybrid may be any metal, and 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, 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 and manganese are suitable, and chromium and iron are most suitable. In addition to transition metals, metals such as lanthanum may be used as well as typical elements for making 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.
유무기혼성체의 또 하나의 구성원소인 리간드로서 작용할 수 있는 유기 화합물은 링커 (linker)라고도 하며 배위할 수 있는 작용기를 가진 어떠한 유기 화합물도 가능하며, 배위할 수 있는 작용기는 카르복실산기, 카르복실산 음이온기, 아미노기(-NH2), 이미노기(
금속 성분과 유기 화합물 외에 유무기혼성체의 합성에는 적당한 용매가 필요하며 물, 메탄올, 에탄올, 프로판올 등의 알콜류, 아세톤, 메틸에틸케톤 등의 케톤 류, 헥산, 헵탄, 옥탄 등의 탄화수소류 등 어떠한 물질도 사용 가능하며 두 가지 이상의 용매를 섞어 사용할 수도 있으며 물이 가장 적합하다. In addition to metal components and organic compounds, suitable solvents are required for the synthesis of organic-inorganic hybrids. Alcohols such as water, methanol, ethanol and propanol, ketones such as acetone and methyl ethyl ketone, and hydrocarbons such as hexane, heptane and octane Also available is a mixture of two or more solvents, water is the best choice.
유무기혼성 나노세공체의 결정 성장속도를 조절하기 위하여, 종래에는 질산, 염산, 불산 중에서 불산 등을 포함한 복합산을 산을 사용하는 것이 일반적인 제조방법 이었다 [Science 23, 2040, 2005; Accounts of Chemical Research, 38, 217, 2005]. 그러나, 불산을 사용하는 공정에서는 테이프론 이외의 반응기를 사용하는데 제한이 있었다. 현재까지의 유무기혼성 나노세공체의 결정성장 속도는 핵형성 속도가 늦은 반면 결정성장 속도는 상대적으로 빠른 것으로 알려져 있다. 따라서 불산이 포함된 반응물에서는 금속이온과 불소 이온 간의 강한 결합특성으로 인하여 상대적으로 핵형성 속도가 늦어 결정 크기가 작은 나노세공체을 얻을 수 없었다. In order to control the crystal growth rate of the organic-inorganic hybrid nanoporous body, it was conventionally a method for producing a complex acid including hydrofluoric acid, such as nitric acid, hydrochloric acid, hydrofluoric acid [Science 23, 2040, 2005; Accounts of Chemical Research, 38, 217, 2005]. However, there was a limitation in using a reactor other than taperon in the process using hydrofluoric acid. The crystal growth rate of organic-inorganic hybrid nanoporous bodies has been known to be slow in nucleation, while the crystal growth rate is relatively fast. Therefore, in the reaction product containing hydrofluoric acid, due to the strong binding property between the metal ion and the fluorine ion, the rate of nucleation was relatively low, and thus the nanoporous body having small crystal size could not be obtained.
그러나, 본 발명의 다공성 유무기혼성체의 제조방법에서는, 불산의 사용으로 인한 종래기술의 상기 문제점을 해결하기 위하여, 다공성 유무기혼성체의 제조를 위하여 불산을 제외한 무기산을 사용하는 것을 특징으로 하며, 이에, 본 발명의 상기 제조방법에 의하여 불산을 전혀 사용하지 않고 상대적으로 작은 입자 크기를 갖 는 다공성 유무기혼성 나노세공체를 제조할 수 있다. However, in the method for producing a porous organic-inorganic hybrid of the present invention, in order to solve the above problems of the prior art due to the use of hydrofluoric acid, it is characterized in that the use of inorganic acids except for hydrofluoric acid for the production of a porous organic-inorganic hybrid, By using the preparation method of the present invention, a porous organic-inorganic hybrid nanoporous body having a relatively small particle size can be prepared without using hydrofluoric acid at all.
또한, 본 발명에 의하여 제조된 다공성 유무기혼성체의 세공 내에 존재하는 금속 또는 유기 리간드를 제거하기 위하여 종래에는 용매를 사용하여 불순물을 제거하였다. 그러나 상기의 경우에는 세공 내에 킬레이션 된 유기 또는 무기물 불순물을 제거하는데 한계가 있었다. 이에 비교하여, 본 발명의 제조방법에서는 무기염, 특히, NH+ 4, 알칼리 금속 및 알칼리토 금속으로 이루어진 군에서 선택되는 1가 또는 2가의 양이온과, 할로겐 음이온, 탄산 이온 (CO3 2-), 질산 이온 및 황산 이온으로 이루어진 군에서 선택되는 1가 또는 2가의 음이온으로 이루어진 무기염을 사용하여 다공성 유무기혼성체를 처리함으로써 유무기혼성 나노세공체의 세공내 불순물을 효율적으로 제거할 수 있으며, 이로써 높은 표면적을 갖는 유무기혼성 나노세공체을 얻을 수 있다. 상기 무기염은 2가 양이온으로서 Ca2+ 또는 Mg2+과 1가 음이온으로서 F-, I- 또는 Br-으로 이루어진 것, 또는 1가 양이온과 2가 음이온으로 이루어진 것, 또는 NH4F, KF, KI 및 KBr 로 이루어진 군에서 선택되는 하나 이상인 것을 사용할 수 있으며, 특히 염화암모늄 또는 불화칼륨 등의 무기염을 사용할 수 있다.In addition, in order to remove the metal or organic ligand present in the pores of the porous organic-inorganic hybrid prepared by the present invention, impurities were conventionally removed using a solvent. However, in the above case, there was a limit in removing the organic or inorganic impurities chelated in the pores. In comparison, in the preparation method of the present invention, monovalent or divalent cations selected from the group consisting of inorganic salts, in particular NH + 4 , alkali metals and alkaline earth metals, halogen anions and carbonate ions (CO 3 2- ) Inorganic salts composed of monovalent or divalent anions selected from the group consisting of nitrate ions and sulfate ions can be used to efficiently remove impurities in the pores of the organic-inorganic hybrid nanoporous body by treating the porous organic-inorganic hybrid. Thereby, an organic-inorganic hybrid nanoporous body having a high surface area can be obtained. The inorganic salt is composed of Ca 2+ or Mg 2+ as a divalent cation and F − , I − or Br − as a monovalent anion, or a monovalent cation and a divalent anion, or NH 4 F, KF , One or more selected from the group consisting of KI and KBr may be used. In particular, inorganic salts such as ammonium chloride or potassium fluoride may be used.
본 발명에 있어서 무기염으로 처리한 후의 유무기혼성 나노세공체의 질소 흡착량이 200 ml/g 정도 증가함을 표면적 측정을 통하여 확인할 수 있었다. In the present invention, it was confirmed through surface area measurement that the nitrogen adsorption amount of the organic-inorganic hybrid nanoporous body after treatment with the inorganic salt increased by about 200 ml / g.
본 발명에 있어서 다공성 유무기혼성체의 제조 시 반응 온도는 실제적으로 제한되지는 않으나 100 ℃ 이상이 적당하며 100℃ 이상 250℃ 이하의 온도가 바람직하고, 150℃ 이상 220℃ 이하의 온도가 더욱 바람직하다. 반응 온도가 너무 낮으면 반응 속도가 느려 효과적이지 못하고, 반응 온도가 너무 높으면 세공이 없는 물질이 얻어지기 쉽고 반응 속도가 너무 빨라 불순물이 혼입되기 쉽다. 또한, 반응기 내부 압력이 높아져 반응기의 구성이 비경제적이다. 반응기 압력은 실제적으로 한계가 없으나 반응온도에서의 반응물의 자동 압력 (autogeneous pressure)에서 합성하는 것이 간편하다. 또한, 질소, 헬륨 같은 불활성 기체를 추가하여 고압에서 반응을 수행할 수도 있다.In the present invention, the reaction temperature during the preparation of the porous organic-inorganic hybrid is not practically limited, but is preferably at least 100 ° C, preferably at least 100 ° C and at most 250 ° C, more preferably at least 150 ° C and at most 220 ° C. . If the reaction temperature is too low, the reaction rate is slow and ineffective, and if the reaction temperature is too high, a substance free of pores is easily obtained, and the reaction rate is too fast, and impurities are easily mixed. In addition, the internal pressure of the reactor is increased, which makes the construction of the reactor uneconomical. The reactor pressure is practically unlimited but it is easy to synthesize at the autogeneous pressure of the reactants at the reaction temperature. In addition, an inert gas such as nitrogen or helium may be added to carry out the reaction at a high pressure.
반응은 전기히팅 방식의 수열합성법 이외에도 마이크로파 조사에 의한 회분식 또는 연속식 방식에 의한 수열합성도 가능하다. 또한 유무기혼성체 멤브레인 또는 박막은 상기 1) 단계에서 반응물 혼합액에 기판을 침지한 후 마이크로파를 조사하여 가열하는 방법으로 제조할 수 있다.In addition to the hydrothermal synthesis method of the electric heating method, the reaction may be hydrothermally synthesized by a batch or continuous method by microwave irradiation. In addition, the organic-inorganic hybrid membrane or thin film may be prepared by immersing the substrate in the reactant mixture in step 1) and heating by irradiating microwaves.
본 발명의 상기 제조방법에 의하여, 특히, 불소를 함유하지 않으며, 화학식: Cr3OH(H2O)2O[C6H4(CO2)2]3·nH2O (n~25) 또는 화학식: Fe3O(H2O)2OH[C6H3-(CO2)3]2·nH2O (n~14.5) 을 갖는 신규 다공성 유무기혼성체가 수득될 수 있다.According to the above production method of the present invention, in particular, it does not contain fluorine, and the formula: Cr 3 OH (H 2 O) 2 O [C 6 H 4 (CO 2 ) 2 ] 3 nH 2 O (n ~ 25) Or a novel porous organic-inorganic hybrid having the formula: Fe 3 O (H 2 O) 2 OH [C 6 H 3- (CO 2 ) 3 ] 2 nH 2 O (n-14.5).
또한, 본 발명의 제조 방법에 의하여 수득되는 다공성 유무기혼성체는 산화반응용 촉매 또는 산촉매로서 사용될 수 있다. 본 발명의 제조 방법에 의하여 수득되는 다공성 유무기혼성체가 산화반응용 촉매로서 사용되는 경우, 설폭시화 (sulfoxidation) 반응, 에폭시화(epoxidation) 반응, 포스핀산화반응 또는 프리델-크래프트 벤질화 (Fridel-Crafts benzylation) 반응 등의 산화반응에 있어서 활성을 갖는다. 본 발명의 제조 방법에 의하여 수득되는 다공성 유무기혼성체가 산촉매로 사용되는 경우 알킬화(alkylation) 반응, 에스테르화 반응(esterfication) 또는 베크만 재배열반응（Beckman rearrangement) 등의 산촉매 반응에 대한 활성을 갖는다.In addition, the porous organic-inorganic hybrid obtained by the production method of the present invention can be used as a catalyst or oxidation catalyst for oxidation reaction. When the porous organic-inorganic hybrid obtained by the production method of the present invention is used as a catalyst for oxidation reaction, sulfoxidation reaction, epoxidation reaction, phosphine oxidation reaction or Friedel-craft benzylation (Fridel) It is active in oxidation reactions such as -crafts benzylation. When the porous organic-inorganic hybrid obtained by the production method of the present invention is used as an acid catalyst, it has an activity against an acid catalyst reaction such as alkylation reaction, esterification reaction or Beckman rearrangement.
이하, 아래의 비제한적 실시예에서 본 발명을 보다 자세하게 설명한다. Hereinafter, the present invention is described in more detail in the following non-limiting examples.
실시예Example
실시예 1 (Cr-BDCA-1) Example 1 (Cr-BDCA-1)
테프론 반응기에 Cr(NO3)3·9H2O, 및 1,4-벤젠디카복실산 (BDCA)을 첨가한 후 증류수를 첨가하여 반응물의 최종 몰비가 Cr:BDCA:H2O=1:1:272가 되도록 하였다. 상기 반응물을 함유한 테프론 반응기를 전기오븐에 넣고 210 ℃에서 11시간 반응을 시킨 후 실온으로 냉각 후 원심 분리, 증류수를 이용한 세척, 건조하여 다공성 유무기혼성체로서 크롬테레프탈레이트(Cr-BDCA)를 얻었다. 제조된 Cr-BDCA의 X-선 회절 분석 결과 2θ값이 대략 3.3, 5.2, 5.9, 8.5 및 9.1에서 특징적인 회절 피크를 가지는 것으로 나타났고, 이로부터 입방정의 결정성을 갖는 크롬테레프탈레이트가 얻어진 것을 알 수 있었다 (도 1). 본 실시예에서 얻어진 크롬테레프탈레이트 결정의 XRD 패턴은 문헌 값과 일치하는 것을 확인하였다[Science 23, 2040, 2005]. 이로써 반응물에 불산(HF)을 사용하지 않는 환경친화형 공정에 의해서도 매우 효과적으로 다공성 유무기혼성체가 얻어짐을 알 수 있었다. ICP분석 결과 상기 수득된 다공성 유무기혼성체 크롬테레프탈레이트는 F이 포함되지 않은 것으로서 그 구조는 MIL-101과 동일하나 구조 내에 F이 포함되지 않는 것으로서 화학식: Cr3OH(H2O)2O[C6H4(CO2)2]3·nH2O (n~25) 로 나타낼 수 있는 물질임을 확인되었다.Cr (NO 3 ) 3 .9H 2 O, and 1,4-benzenedicarboxylic acid (BDCA) were added to the Teflon reactor, followed by distilled water to add a final molar ratio of Cr: BDCA: H 2 O = 1: 1: 272 was made. The Teflon reactor containing the reactants was placed in an electric oven, and reacted at 210 ° C. for 11 hours. After cooling to room temperature, centrifugation, washing with distilled water, and drying were performed to obtain chromium terephthalate (Cr-BDCA) as a porous organic-inorganic hybrid. . X-ray diffraction analysis of the prepared Cr-BDCA showed that the 2θ values had characteristic diffraction peaks at approximately 3.3, 5.2, 5.9, 8.5 and 9.1, from which chromium terephthalate having a cubic crystallinity was obtained. It could be seen (Figure 1). It was confirmed that the XRD pattern of the chromium terephthalate crystals obtained in this example is consistent with the literature values [Science 23, 2040, 2005]. As a result, it was found that a porous organic-inorganic hybrid was obtained very effectively by an environmentally friendly process that does not use hydrofluoric acid (HF). As a result of ICP analysis, the obtained porous organic-inorganic hybrid chromium terephthalate does not contain F and its structure is the same as that of MIL-101, but F is not included in the structure: Cr 3 OH (H 2 O) 2 O [ C 6 H 4 (CO 2 ) 2 ] 3 · nH 2 O (n ~ 25) It was confirmed that the material can be represented.
실시예 2 (Cr-BDCA-2) Example 2 (Cr-BDCA-2)
실시예 1에서 제조된 다공성 유무기혼성체 1g를 1M 농도 NH4F 50ml에 넣고, 70℃ 온도에서 교반하여 세공체의 세공 내에 존재하는 불순물을 제거함으로써 표면적이 향상된 유무기혼성체를 제조하였다. X-선 회절 스펙트럼(도 2)으로부터 암모늄플로라이드 처리 후에 결정성에 손상 없이 유지됨을 확인 할 수 있었다. 또한, 상기 암모늄플로라이드 처리 전, 후의 다공성 유무기혼성체의 질소 흡착 측정결과로부터, 암모늄플로라이드 처리에 의하여 표면적이 700 m2/g (불화암모늄 처리 전 3373 m2/g → 처리 후 4074 m2/g) 증가하고, P/Po=0.5에서의 흡착량이 200 ml/g (불화암모늄 처리 전 1050 ml/g → 처리 후 1250 ml/g) 증가하는 특성을 갖는 유무기혼성체가 얻어짐을 알 수 있었다 (도 3). 1 g of the porous organic-inorganic hybrid prepared in Example 1 was placed in 50 ml of 1 M concentration NH 4 F, and stirred at a temperature of 70 ° C. to remove impurities present in the pores of the pores, thereby preparing an organic-inorganic hybrid having improved surface area. From the X-ray diffraction spectrum (Fig. 2) it can be confirmed that after ammonium fluoride treatment is maintained without damage to crystallinity. In addition, from the measurement results of nitrogen adsorption of the porous organic-inorganic hybrid before and after the ammonium fluoride treatment, the surface area was 700 m 2 / g (3373 m 2 / g before the ammonium fluoride treatment → 4074 m 2 after the ammonium fluoride treatment) / g) increased and the adsorption amount at P / Po = 0.5 was 200 ml / g (1050 ml / g before ammonium fluoride treatment 1250 ml / g after treatment) was found to be obtained an organic-inorganic hybrid (FIG. 3).
실시예 3 : 마이크로파 조사에 의한 다공성 유무기 혼성체(Fe-BTCA-1)의 제조Example 3: Preparation of porous organic-inorganic hybrid (Fe-BTCA-1) by microwave irradiation
테프론 반응기에 금속 철 1 mmol, 1M HNO3 60ml 및 1,3,5-벤젠트리카르복시산(BTCA) 7 mmol을 첨가한 후 증류수를 가하였고, 반응물의 최종 몰비는 Fe:HNO3:BTCA:H2O=1:0.6:0.7:278 이었다. 상기 반응물을 실온에서 500rpm으로 20분간 교반하여 균일한 반응물이 되도록 하였다. 상기 전처리된 반응물을 함유한 테프론 반응기를 마이크로파 반응기 (CEM사, 모델 Mars-5)에 장착하고 마이크로파(2.54 ㎓)를 조사하여 200℃로 승온 시킨 후 200 ℃에서 2분 동안 유지하여 결정화 반응을 수행한 후 실온으로 냉각, 원심 분리, 세척(증류수) 및 건조하여 다공성 유무기 혼성체(Fe-BTCA)를 얻었다. X-선 회절 스펙트럼의 형태가 문헌상 [Bulletin of Korean Chemical Society vol.26, p.880 (2005)]의 결정구조인 Cr-MIL-100구조와 유사함을 보여주었다. ICP분석 결과 얻어진 다공성 유무기혼성체 크롬테레프탈레이트는 F이 포함되지 않은 것으로서 그의 구조는 MIL-100과 동일하나 구조 내에 F이 포함되지 않으며 화학식: Fe3O(H2O)2OH[C6H3-(CO2)3]2·nH2O (n~14.5)로 나타낼 수 있는 물질임이 확인되었다. 전자현미경 분석결과 입자 크기가 200~500 nm 이하로 매우 작아졌음을 알 수 있었다 (도 4a).1 mmol of metal iron, 60 ml of 1M HNO 3 and 7 mmol of 1,3,5-benzenetricarboxylic acid (BTCA) were added to the Teflon reactor, followed by distilled water, and the final molar ratio of the reactants was Fe: HNO 3 : BTCA: H 2. O = 1: 0.6: 0.7: 278. The reaction was stirred at 500 rpm at room temperature for 20 minutes to ensure a uniform reaction. The Teflon reactor containing the pretreated reactant was mounted in a microwave reactor (CEM Co., Model Mars-5) and irradiated with microwave (2.54 mW) to raise the temperature to 200 ° C., and then maintained at 200 ° C. for 2 minutes to perform a crystallization reaction. After cooling to room temperature, centrifugation, washing (distilled water) and drying, a porous organic-inorganic hybrid (Fe-BTCA) was obtained. The morphology of the X-ray diffraction spectrum was shown to be similar to that of Cr-MIL-100, the crystal structure of Bulletin of Korean Chemical Society vol. 26, p. 880 (2005). The porous organic-inorganic hybrid chromium terephthalate obtained as a result of ICP analysis does not contain F and its structure is the same as that of MIL-100, but does not contain F in the structure: Fe 3 O (H 2 O) 2 OH [C 6 H 3- (CO 2 ) 3 ] 2. NH 2 O (n ~ 14.5) was identified as a substance. Electron microscopic analysis showed that the particle size was very small (200 ~ 500 nm or less) (Fig. 4a).
실시예 4: 전기 가열에 의한 다공성 유무기 혼성체(Fe-BTCA-2)의 제조Example 4: Preparation of porous organic-inorganic hybrid (Fe-BTCA-2) by electric heating
상기 실시예 3 과 동일한 방법으로 다공성 유무기 혼성체를 제조하였으나, 열원으로 마이크로파를 조사하는 대신에 일반적인 전기히팅방식을 이용한 전기가열방식으로 6시간 동안 가열하여 유무기혼성체를 제조하였다. 제조된 유무기 혼성체의 결정구조는 XRD 분석 결과 피크의 상대적인 세기는 다르지만 실시예 3 과 동일한 위치에서 회절패턴이 얻어짐을 확인하였다. 전자현미경으로 분석결과 입자의 사이즈가 2-5 μm로 상대적으로 큰 결정을 얻을 수 있었다. A porous organic-inorganic hybrid was prepared in the same manner as in Example 3, but instead of irradiating microwaves with a heat source, an organic-inorganic hybrid was prepared by heating for 6 hours by an electric heating method using a general electric heating method. As a result of XRD analysis, the crystal structure of the prepared organic-inorganic hybrid was different, but the diffraction pattern was obtained at the same position as in Example 3. As a result of analysis by electron microscopy, particles of 2-5 μm in size were obtained.
실시예 5 (Cr-BDCA-3) Example 5 (Cr-BDCA-3)
실시예 1에서 전기히팅 방식이 아닌 마이크로파 조사에 의한 히팅방식을 사용하는 것을 제외하고는 실시예 1과 동일한 방법으로 유무기혼성체를 제조하였다. 단, 2.5GHz 진동수의 마이크로파 반응장치를 이용하고, 반응온도 210℃, 반응시간 40분 동안 유지하여 유무기혼성체를 제조하였다. X-선 회절스펙트럼 분석결과 실시예 1과 동일한 구조의 물질이 얻어짐을 알 수 있었다. An organic-inorganic hybrid was prepared in the same manner as in Example 1 except for using the heating method by microwave irradiation instead of the electric heating method. However, using a microwave reactor of 2.5GHz frequency, the organic-inorganic hybrid was prepared by maintaining the reaction temperature of 210 ℃,
실시예 6 (Fe-BDCA-3)Example 6 (Fe-BDCA-3)
실시예 1과 동일하게 진행하되 Cr(NO3)3·9H2O 대신에 Fe를 사용하여 유무기혼성체를 제조하였다. X-선 회절 형태로부터 실시예 1과 동일한 구조의 물질이 얻어짐을 알 수 있었다.Proceed in the same manner as in Example 1, but instead of Cr (NO 3 ) 3 · 9H 2 O was used to prepare an organic-inorganic hybrid. From the X-ray diffraction pattern, it was found that a material having the same structure as in Example 1 was obtained.
실시예 7 (V-BDCA-1)Example 7 (V-BDCA-1)
실시에 1에서 Cr(NO3)3·9H2O를 사용하는 대신에 VCl3를 사용하는 것을 제외하고는 실시예 1와 동일한 방법으로 유무기혼성체를 제조하였다. X-선 회절 스펙트럼으로부터 실시예 1과 동일한 구조의 물질이 얻어졌고, 전자 현미경 사진으로부터 50-80 nm 정도의 균일한 입경 특성을 갖는 유무기혼성체가 얻어짐을 알 수 있었다.An organic-inorganic hybrid was prepared in the same manner as in Example 1, except that VCl 3 was used instead of Cr (NO 3 ) 3 .9H 2 O in Example 1. From the X-ray diffraction spectrum, a material having the same structure as in Example 1 was obtained, and it was found from the electron micrograph that an organic-inorganic hybrid having a uniform particle size characteristic of about 50-80 nm was obtained.
실시예 8 (Cr-BDCA-1-박막)Example 8 (Cr-BDCA-1-Thin Film)
테프론 반응기에 Cr(NO3)3·9H2O, 및 1,4-벤젠디카복실산 (BDCA)을 첨가한 후 증류수를 첨가하여 반응물의 최종 몰비를 Cr:BDCA:H2O=1:1:275가 되도록 하였다. 상기 용액에 알루미나 기판을 수직으로 정렬시켜 알루미나 기판-함유 반응물을 함유한 테프론 반응기를 마이크로파 반응기 (CEM사, 모델 Mars-5)에 장착하고 2.45 GHz의 마이크로파를 조사하여 3분에 걸쳐 210 ℃로 승온시켰다. 그 후 210 ℃에서 30분 유지하여 반응을 시킨 후 실온으로 냉각 후 원심 분리, 증류수를 이용한 세척, 건조하여 유무기혼성체로서 Cr-BDCA를 수득하였다. 박막의 X-선 회절 스펙트럼은 실시예 1의 결과와 일치하였다. 수득된 유무기혼성체 박막의 결정의 전자현미경 사진은 도 4에 나타나 있으며 매우 균일한 입자로 코팅된 Cr-BDCA/알루미나 박막을 보여 주고 있다. 이로써, 본 발명이 제조방법이, 마이크로파 조사를 이용함으로써 유무기혼성체 박막을 직접 제조할 수 있는 매우 효과적인 방법임을 확인 할 수 있었다.Cr (NO 3 ) 3 .9H 2 O, and 1,4-benzenedicarboxylic acid (BDCA) were added to the Teflon reactor, followed by distilled water to add a final molar ratio of Cr: BDCA: H 2 O = 1: 1: 275 was made. Teflon reactor containing alumina substrate-containing reactants was vertically aligned with the alumina substrate in the solution, mounted in a microwave reactor (CEM, Model Mars-5), and heated to 210 ° C. over 3 minutes by irradiating microwave at 2.45 GHz. I was. Thereafter, the mixture was held at 210 ° C. for 30 minutes to react, cooled to room temperature, centrifuged, washed with distilled water, and dried to obtain Cr-BDCA as an organic-inorganic hybrid. The X-ray diffraction spectrum of the thin film was consistent with the result of Example 1. Electron micrographs of the crystals of the obtained organic-inorganic hybrid thin film are shown in FIG. 4 and show Cr-BDCA / alumina thin films coated with very uniform particles. As a result, it could be confirmed that the present invention is a very effective method for directly producing an organic-inorganic hybrid thin film by using microwave irradiation.
실시예 9 (Fe-BTCA-1 촉매반응) Example 9 (Fe-BTCA-1 Catalysis)
본 발명의 제조방법에 의하여 수득되는 유무기혼성 나노세공체를 프리델-크래프트 벤질화반응의 촉매로서 사용하기 위하여, 실시예 4에서 얻어진 유무기혼성 나노세공체 Fe-BTCA 0.1g 을 벤젠(7.8ml)과 벤질클로라이드(1.3 ml)와 혼합하여, 70 ℃에서 프리델-크래프트 벤질화반응을 수행하였다. 그 결과, 상기 본 발명의 유무기혼성 나노세공체는 촉매로서 상기 반응에서 10분 이내에 반응이 100% 전환되도록 하는 매우 높은 활성을 갖고 있음을 확인하였다 (도 5). In order to use the organic-inorganic hybrid nanoporous body obtained by the production method of the present invention as a catalyst for Friedel-Craft benzylation, 0.1 g of the organic-inorganic hybrid nanoporous Fe-BTCA obtained in Example 4 was added to benzene (7.8 ml). ) And benzyl chloride (1.3 ml), and Friedel-Craft benzylation was carried out at 70 ℃. As a result, it was confirmed that the organic-inorganic hybrid nanoporous material of the present invention has a very high activity such that the reaction is 100% converted within 10 minutes in the reaction as a catalyst (FIG. 5).
실시예 10 (Fe-BTCA -1촉매반응) Example 10 (Fe-BTCA-1 Catalysis)
실시예 4에서 얻어진 유무기혼성체 Fe-BTCA 0.1g을 촉매로서 사용하여 티오애니졸 (thioanisole)과 과산화수소을 상온에서 반응시킨 결과 상기 Fe-BTCA가 전화율 88%, 선택도 100%의 매우 높은 산화촉매 활성를 갖고 있음을 확인하였다. When thioanisole and hydrogen peroxide were reacted at room temperature using 0.1 g of the organic-inorganic hybrid Fe-BTCA obtained in Example 4, the Fe-BTCA exhibited very high oxidation catalyst activity of 88% conversion and 100% selectivity. It confirmed that it has.
비교예 1 (Cr-BDCA-4) Comparative Example 1 (Cr-BDCA-4)
실시예 1에 따른 제조방법에 있어서 반응 혼합물 조제 시 불산을 사용하여 다공성 유무기혼성 나노세공체를 제조하였다. 반응 혼합물의 최종 몰비는 Cr:HF:BDCA:H2O=1:1:1:272가 되도록 하였다. 제조된 다공성 유무기혼성 나노세공체의 표면적 분석결과 P/Po=0.5에서 흡착량이 1044 ml/g, BET 3439 m2/g 인 유무기 혼성체가 얻어짐을 알 수 있었다.In the preparation method according to Example 1, a porous organic-inorganic hybrid nanoporous body was prepared using hydrofluoric acid when preparing a reaction mixture. The final molar ratio of the reaction mixture was such that Cr: HF: BDCA: H 2 O = 1: 1: 1: 272. As a result of surface area analysis of the prepared porous organic-inorganic nanoporous material, it can be seen that an organic-inorganic hybrid having an adsorption amount of 1044 ml / g and BET 3439 m 2 / g was obtained at P / Po = 0.5.
비교예 2 (Fe-BTCA)Comparative Example 2 (Fe-BTCA)
실시예 3에 따른 제조방법에 있어서 반응 혼합물 조제 시 불산을 사용하여 다공성 유무기혼성 나노세공체를 제조하였다. 반응 혼합물의 최종 몰비는 Fe:HF:HNO3:BTCA:H2O=1:1:0.6:0.7:278 가 되도록 하였다. 제조된 유무기혼성체의 X-선 회절 분석 결과, 실시예 3과 동일한 결정성을 갖는 유무기혼성체가 얻어지는 대신에 결정 크기 매우 큰 (~ 10 μm) 물질이 얻어짐을 알 수 있었다 (도 4b).In the preparation method according to Example 3, a porous organic-inorganic hybrid nanoporous body was prepared using hydrofluoric acid when preparing the reaction mixture. The final molar ratio of the reaction mixture was such that Fe: HF: HNO 3 : BTCA: H 2 O = 1: 1: 0.6: 0.7: 278. As a result of X-ray diffraction analysis of the prepared organic-inorganic hybrid, it was found that instead of obtaining an organic-inorganic hybrid having the same crystallinity as in Example 3, a very large crystal size (˜10 μm) was obtained (FIG. 4B).
상기 실시예 및 비교예의 결과로부터, 불산을 사용하는 종래 공정과 비교히여, 불산을 포함하지 않는 본 발명의 제조방법에 의하여 동일한 결정성을 갖는 다공성 유무기혼성 나노세공체룰 제조할 수 있음을 확인하였으며, 특히 암모늄염 및 불화칼륨 등의 무기염으로 처리할 경우에 표면적이 10% 이상 증가됨을 확인할 수 있었다. 또한 본 발명의 제조방법에 따라 제조된 다공성 유무기혼성 나노세공체가 촉매로서 활성이 매우 높음을 확인하였다. From the results of the above examples and comparative examples, it was confirmed that compared to the conventional process using hydrofluoric acid, porous organic-inorganic hybrid nanoporous body having the same crystallinity can be prepared by the production method of the present invention does not contain hydrofluoric acid. , Especially when treated with inorganic salts such as ammonium salt and potassium fluoride was confirmed that the surface area increased by more than 10%. In addition, it was confirmed that the porous organic-inorganic hybrid nanoporous body prepared according to the preparation method of the present invention has very high activity as a catalyst.
상기한 바와 같이, 본 발명의 신규 제조방법에 따라서 제조된 다공성 유무기혼성체는 수열합성 시 불산을 사용하지 않음에도 불구하고 높은 결정성을 갖는 나노세공체이며, 특히 무기염으로 처리함으로써 상기 유무기혼성 나노세공체의 세공 내 불순물을 제거하여 정제함으로써 그 표면적을 증가시킬 수 있다. 또한 본 발명의 제조방법에 따라서 제조된 다공성 유무기혼성 나노세공체를 선택적 산화반응용 촉매 또는 산 촉매로서 사용할 수 있다. 이러한 유무기혼성체는 기타 촉매, 촉매 담체, 흡착제, 기체 저장, 이온교환 및 나노 반응기 및 나노 물질 제조에 활용될 수 있고 특히 상기 유무기혼성체의 나노 입자는 우수한 활성을 갖는 촉매, 센서, 광전 재료 및 의료용 재료로서 사용될 수 있다.As described above, the porous organic-inorganic hybrid prepared according to the novel production method of the present invention is a nanoporous body having high crystallinity even though hydrofluoric acid is not used in hydrothermal synthesis, and in particular, the organic-inorganic The surface area can be increased by removing and purifying impurities in the pores of the hybrid nanoporous body. In addition, the porous organic-inorganic hybrid nanoporous body prepared according to the production method of the present invention can be used as a catalyst for selective oxidation or acid catalyst. Such organic / inorganic hybrids can be utilized in other catalysts, catalyst carriers, adsorbents, gas storage, ion exchange and nanoreactors and nanomaterials production, in particular the nanoparticles of the organic / inorganic hybrids have catalysts, sensors, photoelectric materials and It can be used as a medical material.
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