KR100830840B1 - Precious metal doped organic-inorganic mesoporous materials - Google Patents
Precious metal doped organic-inorganic mesoporous materials Download PDFInfo
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- 239000010970 precious metal Substances 0.000 title claims abstract description 6
- 239000013335 mesoporous material Substances 0.000 title abstract description 8
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 4
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- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
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- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
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- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
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- 229910052767 actinium Chemical class 0.000 description 1
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- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
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- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
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- SNKDQHAHAVFEKZ-UHFFFAOYSA-N triethoxy-(1-triethoxysilylcyclohexa-2,4-dien-1-yl)silane Chemical compound C(C)O[Si](C1(CC=CC=C1)[Si](OCC)(OCC)OCC)(OCC)OCC SNKDQHAHAVFEKZ-UHFFFAOYSA-N 0.000 description 1
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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
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
-
- B01J35/60—
Abstract
본 발명은 유해물질 제거용 다공성 유-무기 메조세공체의 제조 방법에 관한 것으로서, 더욱 상세하게는 메조세공체의 골격 내에 친유성기를 포함하고, 활성금속이 세공체 동공 내에 고분산되어 특정유해 물질을 선택적으로 흡착하여 저온에서 분해시킬 수 있는 귀금속 담지 유-무기 메조세공체 촉매의 제조 방법에 관한 것으로서, a) 금속염과 킬레이트 화합물의 혼합 용액; 실리카 전구체; 및 고분자 계면활성제 혼합물;을 혼합하여 메조구조체를 형성하는 단계; b) 상기 메조구조체로부터 킬레이트제 및 계면활성제를 제거하는 단계;를 포함하는 것을 특징으로 한다. 본 발명에 따른 제조방법에 의하여 제조된 다공성 유-무기 메조세공체는 휘발성 유기 화합물, 니트로소아민류, 폴리사이클릭아로마틱하이드로카본류 등과 같은 증기상 특정유해물질에 대한 제거능력이 우수하며, 담배 유해물질 제거용 촉매, 방독마스크용 필터로 응용가능하다.The present invention relates to a method for preparing a porous organic-inorganic mesoporous body for removing harmful substances, and more particularly, to include a lipophilic group in the backbone of the mesoporous body, and to disperse the active metal in the pore of the pore body so that the specific harmful substance. A method for producing a precious metal-supported organic-inorganic mesoporous catalyst capable of selectively adsorbing and decomposing at low temperature, comprising: a) a mixed solution of a metal salt and a chelate compound; Silica precursors; And a polymer surfactant mixture; to form a meso structure; b) removing the chelating agent and the surfactant from the mesostructures. Porous organic-inorganic mesoporous body prepared by the production method according to the present invention is excellent in the ability to remove the specific vapor harmful substances such as volatile organic compounds, nitrosoamines, polycyclic aromatic hydrocarbons, harmful to tobacco Applicable as a catalyst for removing substances and a filter for gas masks.
유-무기 메조세공체, 저온산화촉매, 하이브리드, 휘발성 유기 화합물, 나이트로소아민류, 귀금속 Organic-inorganic mesoporous materials, low temperature oxidation catalysts, hybrids, volatile organic compounds, nitrosoamines, precious metals
Description
도 1은 본 발명의 실시예 1에 제조된 PdO 담지 다공성 유-무기 메조세공체의 저각 X-선 회절 패턴이며, 1 is a low angle X-ray diffraction pattern of a PdO-supported porous organic-inorganic mesoporous body prepared in Example 1 of the present invention,
도 2는 본 발명의 실시예 1에 제조된 PdO 담지 유-무기 메조세공체(a)와 비교에 1에 의해서 골격구조가 실리카만으로 제조된 메조세공체(b)의 적외선 분광 패턴이고, 2 is an infrared spectral pattern of a mesoporous body (b) whose skeleton structure is made of silica only by 1 compared with the PdO-supported organic-inorganic mesoporous body (a) prepared in Example 1 of the present invention,
도 3은 본 발명의 실시예 1에 제조된 PdO 담지 유-무기 메조세공체(a)와 비교에 1에 의해서 골격구조가 실리카만으로 제조된 메조세공체(b)를 이용한 유해물질 톨루엔의 제거반응 (GHSV=30,000) 결과이며,3 is a removal reaction of the toxins harmful toluene using a mesoporous body (b) having a skeleton structure made only of silica by comparison with the PdO-supported organic-inorganic mesoporous body (a) prepared in Example 1 of the present invention (GHSV = 30,000) result,
도 4는 본 발명의 실시예 1에 제조된 PdO 담지 유-무기 메조세공체(a)와 비교에 1에 의해서 골격구조가 실리카만으로 제조된 메조세공체(b)의 질소흡탈착 등온선이다.4 is a nitrogen adsorption-desorption isotherm of a mesoporous body (b) whose skeleton structure is made of silica only by 1 compared with the PdO-supported organic-inorganic mesoporous body (a) prepared in Example 1 of the present invention.
본 발명은 다공성 유-무기 메조세공체의 제조 방법에 관한 것으로서, 더욱 상세하게는 메조세공체의 골격 내에 친유성기를 포함하고, 활성금속이 세공체 동공 내에 고분산되어 특정유해 물질을 선택적으로 흡착하여 저온에서 분해시킬 수 있는 귀금속 담지 유-무기 메조세공체 촉매의 제조 방법에 관한 것이다.The present invention relates to a method for producing a porous organic-inorganic mesoporous body, and more particularly, to include a lipophilic group in the skeleton of the mesoporous body, and active metal is highly dispersed in the pore body to selectively adsorb specific harmful substances. The present invention relates to a method for preparing a precious metal-supported organic-inorganic mesoporous catalyst which can be decomposed at low temperature.
메조세공체는 대략 1,000 m2/g 의 높은 표면적과 2-50nm 의 메조동공을 갖는 물질로 촉매담체, 촉매, 흡착제 및 기능성 박막 등으로 광범위하게 사용되고 있다. 특히, 메조세공체의 동공 내에 활성금속을 담지함으로서, 촉매 및 유해물질 제거용 흡착제로 사용되고 있다 (한국특허 제 10-0458325). 기존의 메조세공체의 동공 내에 활성금속을 담지시키기 위하여 메조세공체 동공 표면에 유기작용기를 고정시켜 금속을 유기 작용기에 결합시켜 나노분산시키는 방법 (J. Am. Chem. Soc. 2005, 17, 2475), 음파를 이용하여 활성금속을 세공체 내에 분산시키거나 ( Scripta Mater. 2003, 48, 1061), 또는 계면활성제와 활성금속 용액을 에어로졸 형태로 분산시켜 제조하는 방법(Chem. Mater. 2005, 17, 2475) 등이 공지되어 있으나, 대부분의 공지 귀금속 담지지지체들은 메조세공체의 내부구조의 뼈대가 실리카와 산소의(-Si-O-Si-) 의 친수성 무기물로만 구성되어 있을 뿐이다.Mesoporous material is a material having a high surface area of approximately 1,000 m 2 / g and mesopores of 2-50 nm, and is widely used as a catalyst carrier, a catalyst, an adsorbent, and a functional thin film. In particular, by supporting the active metal in the cavity of the mesoporous body, it is used as an adsorbent for removing the catalyst and harmful substances (Korean Patent No. 10-0458325). In order to support the active metal in the pupil of the existing mesoporous body, a method of immobilizing an organic functional group on the surface of the mesoporous pore to bind the metal to the organic functional group to nanodisperse (J. Am. Chem. Soc. 2005, 17, 2475 Or by dispersing the active metal into the pore using sound waves (Scripta Mater. 2003, 48, 1061), or by dispersing the surfactant and active metal solution in the form of an aerosol (Chem. Mater. 2005, 17). , 2475), and the like, but most of the known precious metal carriers are composed only of the hydrophilic inorganic material of silica and oxygen (-Si-O-Si-).
최근 소수성 유-무기 뼈대 구조를 갖는 유-무기 메조세공체가 공지(Chem. Mater. 2005, 17, 6674)되었으나, 소수성 특성을 갖는 유해물질 흡착 및 촉매로서 의 활용에는 한계가 있으며, 따라서 금속이 분산된 소수성의 유-무기 나노세공체에 금속을 직접 고분산 시키는 방법의 개발이 요구되고 있다.Recently, an organic-inorganic mesoporous body having a hydrophobic organic-inorganic skeleton structure has been known (Chem. Mater. 2005, 17, 6674), but there are limitations in the adsorption of harmful substances having hydrophobic properties and utilization as a catalyst, thus dispersing metals. There is a need to develop a method of directly dispersing a metal directly into a hydrophobic organic-inorganic nanoporous body.
한편, 담배연기 성분에는 아세트알데이드, 포름알데히드, 메탄, 톨루엔, 아 세트니트릴등 등과 같은 증기상 물질, 그리고 니코틴이나 타르와 같은 담배 고유의 향을 가지고 있는 다환상 방향족 탄화수소 등의 입자상 물질로 구분할 수 있는데, 이들은 각 성분 군에 따라 제거하거나 감소시키는 방법이 다르다. 지금까지 보고된 방법으로는 입자상 물질들은 섬유상 필터에 의한 여과나 공기희석 방법이 효과적이고, 증기상 물질들은 공기희석이나 확산 흡착방법이 효과적인 것으로 알려져 있다. On the other hand, the tobacco smoke component may be classified into vapor substances such as acetaldehyde, formaldehyde, methane, toluene, acetonitrile and the like, and particulate substances such as polycyclic aromatic hydrocarbons having inherent odor such as nicotine or tar. They can be removed or reduced depending on the group of components. As far as is reported, particulate matters are known to be effective by filtration or air dilution by fibrous filters, and vapor dilution or diffusion adsorption is known to be effective for vaporous materials.
현재까지 특정유해 물질의 제거촉매로는 미세동공이 발달되어 비표면적이 매우 크고, 비극성 분자에 대한 흡착력이 강하여 배기가스 제거, 냄새제거 및 탈색 효과가 우수한 활성탄이나, 3 내지 10 Å 정도의 세공직경을 갖는 친수성 흡착제로서 나이트로소다이페닐아민(N-Nitrosodiphenylamine), 일산화탄소, 이산화탄소 및 수분흡착특성이 강한 특성을 갖는 제올라이트가 공지되었다 (New J. Chem. 28, 807, 2004, Jiangsu Huagong, 31, 29, 2003). 또한 제올라이트보다 세공크기가 큰 메조세공체SBA-15와 MCM-48을 사용하여 제올라이트 (NaY)보다 나이트로소니코틴(N-nitrosonornicotine) 등의 분해활성이 뛰어나다는 결과를 보고하였다 (Chem. Lett. 32, 338, 2003). To date, the removal catalyst of specific harmful substances is activated carbon, which has a very large specific surface area and a strong adsorptive force to nonpolar molecules, and has excellent effect of removing exhaust gas, removing odors and discoloring, but having a pore diameter of about 3 to 10 Å. As a hydrophilic adsorbent having a nitrosodiphenylamine (N-Nitrosodiphenylamine), carbon monoxide, carbon dioxide and zeolites having strong water adsorption properties are known (New J. Chem. 28, 807, 2004, Jiangsu Huagong, 31, 29 , 2003). In addition, using mesoporous SBA-15 and MCM-48 having a larger pore size than zeolite, it was reported that the decomposing activity of nitrosonornicotine and the like was superior to that of zeolite (NaY) (Chem. Lett. 32, 338, 2003).
하지만, 상기에 기술한 특정유해물질제거 촉매중에서 활성탄은 물질 자체가 산소가 존재시 CO2로 분해하는 문제가 있기 때문에 산화촉매로서의 적용에 무리가 있다. 또한 제올라이트 물질은 세공크기가 제한적이고, 활성금속인 귀금속 물질을 세공내에 나노분산시키기가 매우 어렵다. 그리고 단순 메조세공체의 경우 세공크기는 충분하지만, 표면에 친수성 하이드록실작용기가 매우 많은 친수성 물질이기 때 문에 금속의 분산 및 담배 유해물질의 대부분이 친유성 물질을 흡착 제거하기는 한계가 있다.However, in the above-described specific harmful substance removal catalyst, activated carbon is unsuitable for use as an oxidation catalyst because the substance itself decomposes into CO 2 in the presence of oxygen. In addition, zeolite materials have a limited pore size, and it is very difficult to nanodisperse precious metal materials, which are active metals, in pores. In the case of the simple mesoporous body, the pore size is sufficient, but since the hydrophilic material has a large number of hydrophilic hydroxyl functional groups on the surface, most of the metal dispersion and the harmful substances of tobacco have a limitation in adsorbing and removing the lipophilic material.
다공성 물질 이외에도 벤젠, 톨루엔, 자이렌, 폴리사이크릭 불포화탄화수소 (PAHs), 일산화탄소등의 비 다공성 유해물질 제거 촉매로는 삼원촉매인 Pd/Rh/CeO2/Al2O3 이 사용된 예가 보고되었다 (Appl. Catal. B: Environmental 48 (2004) 25). 그 외에도 저온 산화 촉매로서 CuO-CeO2 나노컴포짓 물질이 일산화탄소, 산화질소, 탄화수소 등을 제거할 수 있는 담배 필터용 촉매물질로 보고되었다 (미국특허 공개번호 20041100633). 또한 담배를 둘러쌓고 있는 담배지 등에 Zr, Mn, 또는 Zn 등의 알루미나에 희토류원소가 포함된 복합체를 제화하여 특정 유해물질 제거용 촉매물질에 대해 보고하였다(Fr2841438). 하지만, 상기에 기술한 유해물질 제거 촉매물질은 표면적인 상대적으로 적으며, 고도로 조절된 나노입자를 제외하고는 높은 온도에서 특정유해물질을 제거해야하는 문제점이 있다. In addition to the porous material, a three-way catalyst, Pd / Rh / CeO 2 / Al 2 O 3, has been reported as a catalyst for removing non-porous harmful substances such as benzene, toluene, xylene, polycyclic unsaturated hydrocarbons (PAHs), and carbon monoxide. (Appl. Catal. B: Environmental 48 (2004) 25). In addition, CuO-CeO 2 nanocomposite material as a low temperature oxidation catalyst has been reported as a catalyst material for tobacco filters that can remove carbon monoxide, nitrogen oxides, hydrocarbons, etc. (US Patent Publication No. 20041100633). In addition, a complex containing rare earth elements in alumina, such as Zr, Mn, or Zn, was produced on tobacco papers surrounding cigarettes, and a catalyst material for removing specific harmful substances was reported (Fr2841438). However, the above-described harmful substance removal catalyst material has a relatively small surface area, and there is a problem of removing specific harmful substances at high temperature except for highly controlled nanoparticles.
이에 따라 본 발명에서는 상기와 같은 문제점을 해결하기 위해서, 유-무기 메조세공체 하이브리드 물질을 제조하는데 있어, 킬레이트제를 동시에 첨가하여 저 농도의 금속 물질을 담지하여 촉매 제조비를 절감할 수 있었다. 특히, 킬레이트 분자를 사용하면 팔라듐 등의 귀금속 물질을 고분산 시킬 수 있으며, 에틸렌, 페닐렌, 비닐렌 등과 같은 유기물 사슬을 가지는 메조 유-무기 실리카를 원료로 사용하 여 무기-유기 메조세공체를 제조하여 표면의 친유성을 도입함으로서 유해물질제거 효율을 증가시킬 수 있는 다공성 유-무기 메조세공체의 제조방법을 제공하는데 그 목적이 있다.Accordingly, in the present invention, in order to solve the above problems, in the preparation of the organic-inorganic mesoporous hybrid material, the chelating agent can be added at the same time to support the low concentration metal material to reduce the catalyst manufacturing cost. In particular, the use of chelate molecules can highly disperse noble metals such as palladium, and use inorganic-organic mesoporous materials by using meso-organic silica having organic chains such as ethylene, phenylene and vinylene as raw materials. The purpose of the present invention is to provide a method for preparing a porous organic-inorganic mesoporous body which can increase the efficiency of removing harmful substances by introducing lipophilic properties of the surface.
또한 친유성기를 메조세공체의 구조 내에 포함하여 표면 친유성기가 조절되어 친유성 특정유해물질을 쉽게 흡착할 수 있으며, 활성금속 물질을 다공성 메조세공체의 동공 내에 고분산 시킬 수 있는 제조 방법을 제공하는 것이다.In addition, by including a lipophilic group in the structure of the mesoporous body, the surface lipophilic group is controlled to easily adsorb lipophilic specific harmful substances, and provides a manufacturing method capable of highly dispersing the active metal material in the pupil of the porous mesoporous body. It is.
본 발명은 킬레이트 분자를 이용하여 팔라듐 등의 활성물질을 무-유기 사슬을 포함한 메조세공체에 고분산 시켜 유해물질 제거능이 뛰어난 다공성 유-무기 메조세공체의 제조방법에 관한 것이다. The present invention relates to a method for producing a porous organic-inorganic mesoporous body having excellent ability to remove harmful substances by highly dispersing an active substance such as palladium to a mesoporous body including an organic chain using a chelate molecule.
본 발명에 따른 다공성 유-무기 메조세공체의 제조방법은 Method for producing a porous organic-inorganic mesoporous body according to the present invention
a) 금속염과 킬레이트 화합물의 혼합 용액; 실리카 전구체; 및 계면활성제 혼합물;을 혼합하여 메조구조체를 형성하는 단계;a) a mixed solution of a metal salt and a chelate compound; Silica precursors; And a surfactant mixture; to form a meso structure;
b) 상기 메조구조체로부터 킬레이트제 및 고분자 계면활성제를 제거하는 단계;b) removing the chelating agent and the polymeric surfactant from the mesostructures;
를 포함하는 것을 특징으로 한다.Characterized in that it comprises a.
본 발명에 따른 다공성 유-무기 메조세공체의 제조방법에 사용되는 금속염은 1종 이상의 귀금속염 또는 알칼리 토금속, 알칼리 금속, 전이금속, 란탄 계열및 악티늄 계열 금속의 염으로부터 선택되며, 구체적으로는 팔라듐(Pd)염, 백금(Pt)염, 금(Au)염이 예시될 수 있다.The metal salt used in the method for producing a porous organic-inorganic mesoporous body according to the present invention is selected from one or more precious metal salts or salts of alkaline earth metals, alkali metals, transition metals, lanthanides and actinium-based metals, specifically palladium (Pd) salt, platinum (Pt) salt, gold (Au) salt can be illustrated.
본 발명에 따른 다공성 유-무기 메조세공체는 제조된 메조세공체에 대하여 금속이 0.1 내지 20 중량% 담지된 것이 비람직하다.The porous organic-inorganic mesoporous material according to the present invention is preferably supported by 0.1 to 20% by weight of the metal with respect to the prepared mesoporous material.
본 발명에 따른 제조방법에서 사용되는 킬레이트제는 폴리에틸렌 글리콜, 폴리프로필렌 글리콜 또는 에틸렌 글리콜, 또는 그 혼합물인 것을 특징으로 하며, 메조구조 형성을 위한 계면활성제는 이온성 계면활성제, 양쪽성 고분자 계면활성제 및 플로닉(Pluronic) 중에서 선택하여 사용할 수 있으며, 상기 이온성 계면활성제는 CnH2n +1N(CH3)3X와 CnH2n +1N(C2H5)3X 계열(이때, n = 8 ~ 22의 정수, X = Cl, Br, I 또는 F등의 할로겐 원자), 양쪽성 고분자 계면활성제는 CnH2n +1(OCH2CH2)xOH 계열(이때, n = 12 ~ 23의 정수, x = 0 ~ 100의 정수), 플로닉(Pluronic)은 (EO)x(PO)y(EO)x 계열(이때, 20 < x < 120, 20 < y < 120)을 사용할 수 있으며, 이들 계면활성제는 상기 혼합용액에 100 중량부에 대하여 1 내지 10 중량부 사용한다. 특히, 바람직한 고분자 계면활성제로는 Ethylene Oxide/Propylene Oxide Block Copolymer인 Pluronic P123(분자량 5750, BASF 사), Pluronic F127(분자량 12600, BASF 사)이다.The chelating agent used in the production method according to the invention is characterized in that the polyethylene glycol, polypropylene glycol or ethylene glycol, or a mixture thereof, the surfactant for forming the meso structure is an ionic surfactant, amphoteric polymer surfactant and Pionic (Pluronic) can be selected and used, the ionic surfactant is C n H 2n + 1 N (CH 3 ) 3X and C n H 2n + 1 N (C 2 H 5 ) 3X series (where n = An integer from 8 to 22, X = Cl, Br, I or F halogen atoms), amphoteric polymeric surfactants are C n H 2n +1 (OCH 2 CH 2 ) x OH series (where n = 12 to 23) , An integer of x = 0 to 100), and Pluronic can use (EO) x (PO) y (EO) x series (where 20 <x <120, 20 <y <120), These surfactants are used in the mixed solution in an amount of 1 to 10 parts by weight based on 100 parts by weight. Particularly preferred polymer surfactants are Pluronic P123 (molecular weight 5750, BASF) and Pluronic F127 (molecular weight 12600, BASF) which are Ethylene Oxide / Propylene Oxide Block Copolymer.
또한 유-무기 실리카전구체는 특정유해물질의 흡착력을 증가시키기 위해서 사용되는 것으로 유-무기 실란의 실리콘과 실리콘 사이에 유기기능기로 결합된 유-무기 실란을 포함하는 것이 바람직하며, 구체적으로는 1,2-비스트리에톡시실릴에 탄, 1,4-비스트리에톡시실릴벤젠 또는 트리에톡시비닐실란, 1,3,-비스트리에톡시실릴벤젠, 4,4-비스트리에톡시실릴벤젠, 1,4-비스트리에톡시실릴바이페닐 또는 그 혼합물일 수 있다.In addition, the organic-inorganic silica precursor is used to increase the adsorption power of specific harmful substances, and it is preferable to include an organic-inorganic silane bonded to an organic functional group between silicon of the organic-inorganic silane and specifically, 1, 2-bistriethoxysilylethane, 1,4-bistriethoxysilylbenzene or triethoxyvinylsilane, 1,3, -bistriethoxysilylbenzene, 4,4-bistriethoxysilylbenzene, 1,4- Bistriethoxysilylbiphenyl or mixtures thereof.
본 발명에 따른 다공성 유-무기 메조세공체의 제조방법을 상세히 설명하면 다음과 같다.Referring to the method of manufacturing a porous organic-inorganic mesoporous body according to the present invention in detail.
a) 단계의 메조구조체는 구체적으로는 (1) 금속염을 킬레이트 화합물이 녹아 있는 산 용액에 녹인 후, (2) 상기 용액을 한 시간 동안 교반한 후 구조지지체인 계면활성제를 넣고 녹을 때까지 교반하고. (3) 실리카 전구체를 상기의 (1)과 (2)에 형성된 용액에 넣고 교반함으로서 제조되며, 특히 40 내지 70℃에서 10 내지 40 시간 숙성한 후에 10 내지 30 시간 동안 수열반응에 의하여 효과적으로 제조된다.Specifically, the meso structure of step a) is (1) a metal salt is dissolved in an acid solution in which a chelating compound is dissolved, and (2) the solution is stirred for one hour, and then a surfactant is added to the structural support until it is dissolved. . (3) Prepared by stirring the silica precursor into the solution formed in the above (1) and (2), especially after aging for 10 to 40 hours at 40 to 70 ℃, it is effectively prepared by hydrothermal reaction for 10 to 30 hours .
b) 단계는 메조구조체로부터 유기주형물질을 제거하는 단계로서 용매추출법 또는 소성법이 바람직하며, 구체적으로는 상기 a) 단계 후 실온에서 물, 에탄올, 아세톤 등으로 충분히 세척하여 얻어진 분말을 에탄올/HCl 용액에 넣고 구조지시시약을 제거한 후 300 내지 500℃에서 3 내지 8시간 동안 소성함으로서 효과적으로 친유성의 다공성 유-무기 메조세공체를 제조할 수 있다. b) step is a step of removing the organic template material from the meso structure is preferably a solvent extraction method or a calcination method, specifically after the step a) is a powder obtained by washing sufficiently with water, ethanol, acetone, etc. at room temperature ethanol / HCl The lipophilic porous organic-inorganic mesoporous body can be effectively prepared by sintering at 300-500 ° C. for 3 to 8 hours after removing the structural indicator reagent.
본 발명에 따른 제조방법에 있어서, 반응물의 몰 비는 구체적으로는 실리카 전구체 : 고분자 계면활성제 : 염산 : 킬레이트 화합물 : 금속염의 몰비가 1:0.02~0.05:1.2:0.005~ 0.01:0.004~0.002:210 인 것이 바람직하다.In the production method according to the present invention, the molar ratio of the reactant specifically includes a molar ratio of silica precursor: polymer surfactant: hydrochloric acid: chelate compound: metal salt in the range of 1: 0.02 to 0.05: 1.2: 0.005 to 0.01: 0.004 to 0.002: 210. Is preferably.
한편 금속산화물이 분산된 다공성 유-무기 메조세공체를 200 내지 400℃의 온도에서 수소 분위기 하에서 환원하여 금속이 분산된 다공성 유-무기 메조세공체를 제조할 수 있다.Meanwhile, the porous organic-inorganic mesoporous body in which the metal oxide is dispersed may be reduced under a hydrogen atmosphere at a temperature of 200 to 400 ° C. to prepare the porous organic-inorganic mesoporous body in which the metal is dispersed.
본 발명에 따른 제조방법에 의하여 제조된 다공성 유-무기 메조세공체의 벽이 무정형 유-무기 실리카, 제올라이트 USY, ZSM-5 제올라이트, MCM-22 또는 β-제올라이트인 미세세공체를 가지게 된다.The wall of the porous organic-inorganic mesoporous body prepared by the manufacturing method according to the present invention has a microporous body which is amorphous organic-inorganic silica, zeolite USY, ZSM-5 zeolite, MCM-22 or β-zeolite.
본 발명에 따른 제조방법에 의하여 제조된 다공성 유-무기 메조세공체의 구조안정성을 검증하기 위해서 400℃에서 6시간 동안 소성한 후 제조된 유-무기 메조세공체의 SAXS 측정결과 도 1에서 알 수 있는 바와 같이 동공의 규칙성이 매우 뛰어난 나노세공체임을 확인할 수 있었으며, IR 분석을 실시한 결과 프로필렌의 스트레칭 및 벤딩 특성 진동모드가 1400 cm-1 와 2800-3000 cm-1에서 관측되었으며, 이는 메조세공체의 벽이 유기프로필렌기로와 실리콘으로 연결되었다는 것을 의미한다. 또한, 도 2에서 알 수 있는 바와 같이 본 발명에 따른 다공성 유-무기 메조세공체와 단순 실리카만 존재하는 메조세공체 사이의 표면 하이드록실 그룹의 세기(~1600cm-1) 차이가 3배 이상 났으며, 이는 본 발명에 따라 제조된 다공성 유-무기 메조세공체가 종래의 실리카 메조세공체에 비해서 표면이 3배 정도 친유성을 띄는 것을 확인하였다. SAXS measurement results of the prepared organic-inorganic mesoporous body after firing at 400 ℃ for 6 hours to verify the structural stability of the porous organic-inorganic mesoporous body prepared by the manufacturing method according to the present invention As can be seen, it was confirmed that the nanoporous body was very excellent in the regularity of the pupil, and the IR analysis showed that the stretching and bending characteristic vibration modes of propylene were observed at 1400 cm -1 and 2800-3000 cm -1 . It means that the wall of the sieve is connected to the organic propylene group and the silicon. In addition, as can be seen in Figure 2 the difference between the strength of the surface hydroxyl group (~ 1600cm -1 ) between the porous organic-inorganic mesoporous body and the mesoporous body in which only simple silica is present was more than three times In addition, it was confirmed that the porous organic-inorganic mesoporous body prepared according to the present invention exhibited about three times lipophilic surface compared to the conventional silica mesoporous body.
제조된 촉매의 특정유해 물질 제거능을 검증하기 위해, 본 발명에 따른 제조방법에 의하여 제조된 다공성 유-무기 메조세공체 분말 1g을 실리카 샌드와 1:1로 섞은 후 quartz 반응기에 넣은 후 담배의 기체상 특정유해 물질중의 하나인 톨루엔에 대한 저온산화 반응을 수행한 결과 단순 실리카 벽을 갖고 있는 메조세공체에 비해서 50℃ 이하의 저온 및 공간속도 500-30,000/h 사이에서도 톨루엔이 물과 이산화탄소로 완전 산화됨을 확인하였다. In order to verify the ability of removing the specific harmful substances of the prepared catalyst, 1 g of porous organic-inorganic mesoporous powder prepared by the preparation method according to the present invention was mixed 1: 1 with silica sand and placed in a quartz reactor, followed by As a result of the low temperature oxidation reaction of toluene, one of the phase-specific harmful substances, toluene was converted into water and carbon dioxide even at a low temperature below 50 ° C and a space velocity of 500-30,000 / h, compared to mesoporous body having a simple silica wall. It was confirmed to be completely oxidized.
이상에서 설명한 바와 같은 본 발명은 다음의 실시예에 의거하여 상세히 설명하겠는 바, 본 발명이 다음의 실시예에 의해 한정되는 것은 아니다. The present invention as described above will be described in detail based on the following examples, but the present invention is not limited by the following examples.
[실시예 1] 에틸렌기를 구조 내에 갖는 PdO 담지 다공성 유-무기 메조세공체의 제조Example 1 Preparation of PdO Supported Porous Organic-Inorganic Mesoporous Body Having Ethylene Group in Structure
물 116.5g과 35% 염산 2.92 ml의 염산 수용액에 0.033g 의 PdCl2를 녹인 후, 상기의 PdCl2 수용액에 평균 분자량 3,400을 가지는 폴리에틸렌글리콜(PEG) 0.49g을 넣어 1시간 동안 교반한다. 계면활성제 P123((EO)x(PO)y(EO)x x=20, y=70, MW=5600, BASF사) 2.65g을 넣은 후 녹을 때까지 교반한 후, 상기 혼합용액에 1,2-비스트리에톡시시릴에탄(BTEE) 10.9 ml을 가하고 1시간 교반한 후, 상기 혼합물을 폴리프로필렌재질의 반응기에서 60℃에서 24시간 동안 숙성을 시킨 후 100℃에서 24시간 수열반응을 시켜 메조구조체를 제조하였다. After dissolving 0.033 g of PdCl 2 in 116.5 g of water and 2.92 ml of hydrochloric acid in 35% hydrochloric acid, 0.49 g of polyethylene glycol (PEG) having an average molecular weight of 3,400 was added to the PdCl 2 aqueous solution and stirred for 1 hour. 2.65 g of surfactant P123 ((EO) x (PO) y (EO) xx = 20, y = 70, MW = 5600, BASF) was added thereto, stirred until it dissolved, and then mixed with 1,2- After adding 10.9 ml of bistriethoxysilylethane (BTEE) and stirring for 1 hour, the mixture was aged at 60 ° C. for 24 hours in a polypropylene reactor, followed by hydrothermal reaction at 100 ° C. for 24 hours to prepare a meso structure. It was.
상기에 제조된 메조구조체의 동공 내에 존재하는 계면활성제와 폴리에틸렌글리콜 유기물을 제거하기 위해서 에탄올 150ml에 35% 염산 3ml를 섞은 용액에 상기 메조구조체를 넣고 6시간 동안 상온에서 교반하고, 400℃에서 6시간 동안 소성하여 PdO 담지 다공성 유-무기 메조세공체를 제조하였다.In order to remove the surfactant and polyethylene glycol organic material present in the cavity of the prepared meso structure, the meso structure was added to a solution of 3 ml of 35% hydrochloric acid in 150 ml of ethanol and stirred at room temperature for 6 hours, and then stirred at 400 ° C. for 6 hours. It was calcined during to prepare a PdO-supported porous organic-inorganic mesoporous body.
[실시예 2] 벤젠기를 구조 내에 갖는 PdO 담지 다공성 유-무기 메조세공체 촉매 제조Example 2 Preparation of PdO Supported Porous Organic-Inorganic Mesoporous Catalyst Having Benzene in the Structure
상기 실시예 1에서 사용된 에틸렌을 가지는 실리카 전구체 대신 벤젠을 구조 내에 가지는 실리카 전구체를 사용하여 동일한 비율로 PdO가 담지된 유-무기 메조세공체 하이브리드 물질을 제조하였다.An organic-inorganic mesoporous hybrid material in which PdO was supported in the same ratio was prepared using a silica precursor having benzene in the structure instead of the silica precursor having ethylene used in Example 1.
[실시예 3] 비닐기를 구조 내에 갖는 Pd금속 담지 다공성 유-무기 메조세공체 촉매 제조Example 3 Preparation of Pd Metal Supported Porous Organic-Inorganic Mesoporous Catalyst Having a Vinyl Group in the Structure
상기 실시예 1에서 제조된 PdO담지 유-무기 메조세공체를 300℃에서 수소환원하여 Pd이 담지된 유-무기 메조세공체를 제조하였다. Pd-supported organic-inorganic mesoporous bodies prepared in Example 1 were hydrogen-reduced at 300 ° C. to prepare Pd-supported organic-inorganic mesoporous bodies.
[실시예 4] 에틸렌기를 구조 내에 갖는 AuO 담지 다공성 유-무기 메조세공체 촉매 제조Example 4 Preparation of AuO Supported Porous Organic-Inorganic Mesoporous Catalyst Having Ethylene Group in Structure
상기 실시예 1에서, 귀금속 전구체로서 PdCl2 대신에 동일한 양의 HAuCl4을 사용하여 Au가 담지된 다공성 유-무기 메조세공체를 제조하였다.In Example 1, Au-supported porous organic-inorganic mesoporous body was prepared using the same amount of HAuCl 4 as a noble metal precursor instead of PdCl 2 .
[실시예 5] 벤젠기를 구조 내에 갖는 Au 담지 다공성 유-무기 메조세공체 촉매 제조[Example 5] Preparation of Au-supported porous organic-inorganic mesoporous catalyst having a benzene group in its structure
상기 실시예 2에서 귀금속 전구체로서 사용된 PdCl2 대신에 동일한 양의 HAuCl4을 사용하여 Au가 담지된 다공성 유-무기 메조세공체를 제조하였다. Instead of PdCl 2 used as the noble metal precursor in Example 2, an Au-supported porous organic-inorganic mesoporous body was prepared using the same amount of HAuCl 4 .
[실시예 6] 비닐기를 구조 내에 갖는 Pt 담지 다공성 유-무기 메조세공체 촉매 제조[Example 6] Preparation of Pt-supported porous organic-inorganic mesoporous catalyst having a vinyl group in its structure
상기 실시예 3에서 귀금속 전구체로서 사용된 PdCl2 대신에 동일한 양의 H2PtCl6 을 사용하여 Pt가 담지된 다공성 유-무기 메조세공체를 제조하였다.Pt-supported porous organic-inorganic mesoporous bodies were prepared using the same amount of H 2 PtCl 6 instead of PdCl 2 used as the noble metal precursor in Example 3.
[실시예 7] 다공성 유-무기 메조세공체를 이용한 특정 유해물질제거 Example 7 Removal of Specific Hazardous Substances Using Porous Organic-Inorganic Mesoporous Materials
상기 제조된 PdO 담지 유-무기 메조세공체 1g을 곱게 빻은 후 2mm mesh 체를 이용하여 약 0.5~1mm의 크기로 거른 후, 걸러진 촉매 0.5g과 실리카 샌드 0.5g을 섞은 후 quartz 반응기에 넣고 기상 특정유해물질인 톨루엔에 대한 산화반응을 테스트하였다. 사용된 특정 유해물질의 농도는 700ppm, 공간속도는 30,000/h 조건에서 산화반응을 테스트하였다. 실시예 1에 제조된 다공성 유-무기 혼성 메조세공체의 산화반응 결과를 도 3에 도시하였다. After finely grinding 1 g of the prepared PdO-supported organic-inorganic mesoporous material, and filtering it to a size of about 0.5 to 1 mm using a 2 mm mesh sieve, 0.5 g of the filtered catalyst and 0.5 g of silica sand were mixed and placed in a quartz reactor. Oxidation reaction to toluene, a harmful substance, was tested. Oxidation reactions were tested at specific concentrations of 700 ppm and space velocity of 30,000 / h. The oxidation result of the porous organic-inorganic hybrid mesoporous body prepared in Example 1 is shown in FIG. 3.
[비교예 1] Pd 담지 유-무기 메조세공체와 메조세공체 실리카의 유해물질 분해 [Comparative Example 1] Degradation of Hazardous Substances in Pd-supported Organic-Inorganic Mesopores and Mesoporous Silicas
실시예 1에서 실리카 전구체로서 1,2-bis(triethoxylsiyl)ethane(BTEE) 대신에 유기물이 담지 되어 있지 않은 테트라에톡실란(TEOS)을 사용하여 팔라듐이 담지 된 메조세공체를 제조하였다. In Example 1, instead of 1,2-bis (triethoxylsiyl) ethane (BTEE) as a silica precursor, tetraethoxysilane (TEOS) without organic material was used to prepare palladium-containing mesoporous body.
도 2에서 알 수 있는 바와 같이 실시예 1에서 제조된 다공성 유-무기 메조세공체와 단순 실리카만 존재하는 비교예 1의 메조세공체 사이의 표면 하이드록실 그룹의 세기(~1600cm-1) 차이가 3배 이상 났으며, 이는 본 발명에 따라 제조된 다공성 유-무기 메조세공체가 종래의 실리카 메조세공체에 비해서 표면이 3배 정도 친유성을 갖는다는 것을 의미한다.As can be seen in Figure 2 the difference between the intensity of the surface hydroxyl group (~ 1600cm -1 ) between the porous organic-inorganic mesoporous body prepared in Example 1 and the mesoporous body of Comparative Example 1 in which only simple silica is present It is more than three times, which means that the porous organic-inorganic mesoporous body prepared according to the present invention has about three times more lipophilic surface than the conventional silica mesoporous body.
또한 실시예 1에서 제조된 다공성 유-무기 메조세공체와 비교예 1의 메조세공체의 산화반응성을 테스트 한 결과 도 3에서 알 수 있는 바와 같이 실시예 1의 메조세공체가 상대적으로 높은 온도에서 특정유해 물질이 분해됨을 확인할 수 있었으며, 또한, 도 4에 도시된 바와 같이 실시예 1의 메조세공체의 질소흡착 등온선으로부터, 동공구조가 1차원 육방정계에서 3차원 정방정계로 바뀌었다는 것을 확인 할 수 있었다. In addition, as a result of testing the oxidation reactivity of the porous organic-inorganic mesoporous body prepared in Example 1 and the mesoporous body of Comparative Example 1 as shown in Figure 3, the mesoporous body of Example 1 was identified at a relatively high temperature As shown in FIG. 4, the nitrogenous adsorption isotherm of the mesoporous body of Example 1 showed that the pupil structure was changed from one-dimensional hexagonal system to three-dimensional tetragonal system as shown in FIG. 4. there was.
이상에서 설명한 바와 같이, 본 발명에 따른 제조방법은 단순 친유기가 없는 메조세공체와 킬레이팅제가 없이 제조되는 종래의 유-무기 하이브리드 메조세공체 제조방법에 비해서 금속의 분산이 용이하고, 상대적으로 경제적이며, 제조된 메조세공체는 낮은 온도에서 특정유해물질의 제거 능력이 우수한 장점이 있고, 따라서 본 발명에 따른 제조방법에 의해서 제조된 다공성 유-무기 하이브리드 메조세공체는 촉매, 촉매 담체, 흡착제, 및 나노 물질 제조에 활용될 수 있고 특히 나노 입자는 활성이 우수한 촉매는 물론 센서, 광전 재료 및 의료용 재료로 사용될 수 있다.As described above, the manufacturing method according to the present invention is easier to disperse metals and relatively economical as compared to the conventional organic-inorganic hybrid mesoporous body manufacturing method prepared without the simple lipophilic mesoporous body and the chelating agent. The prepared mesoporous body has an advantage of excellent ability to remove specific harmful substances at low temperatures, and thus the porous organic-inorganic hybrid mesoporous body prepared by the preparation method according to the present invention is a catalyst, a catalyst carrier, an adsorbent, And nanoparticles, in particular nanoparticles can be used as sensors, photovoltaic materials and medical materials as well as catalysts with excellent activity.
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