WO2017209489A1 - Procédé de production de silice mésoporeuse magnétique à l'aide de borohydrure de sodium - Google Patents

Procédé de production de silice mésoporeuse magnétique à l'aide de borohydrure de sodium Download PDF

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Publication number
WO2017209489A1
WO2017209489A1 PCT/KR2017/005639 KR2017005639W WO2017209489A1 WO 2017209489 A1 WO2017209489 A1 WO 2017209489A1 KR 2017005639 W KR2017005639 W KR 2017005639W WO 2017209489 A1 WO2017209489 A1 WO 2017209489A1
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Prior art keywords
mesoporous silica
silica
magnetic
magnetic mesoporous
transition metal
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PCT/KR2017/005639
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English (en)
Korean (ko)
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장정호
이혜선
장서준
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한국세라믹기술원
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Publication of WO2017209489A1 publication Critical patent/WO2017209489A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel

Definitions

  • the present invention relates to a method for producing magnetic mesoporous silica. More specifically, the present invention relates to magnetic mesoporous silica having a uniform pore distribution and excellent magnetism, including reacting mesoporous silica carrying transition metal ions with a reducing agent at a specific temperature.
  • Magnetic nanoparticles are ferromagnetic particles and generally have a size of about 10 nm. Magnetic nanoparticles are widely used in the separation process of biological or chemical substances using magnetic, and have been typically used to diagnose diseases with NMR (nuclear magnetic resonance) increasing reagents and to treat diseases with drug carriers. In addition, magnetic nanocrystals with supermagnetism may be used for magnetothermal treatment of diseases such as tumors. Recently, the functional material is immobilized and used in separation processes such as DNA and proteome. Magnetic nanoparticles have the advantage that functional reuse is possible by immobilizing materials such as enzymes, biological catalysts, as well as increasing efficiency according to time savings. However, there are problems in efficiency reduction due to problems such as aggregation of magnetic nanoparticles and low surface reactivity, and unstable bonding between magnetic nanoparticle surfaces and surface modifying materials in processing a large amount or reducing the time of separation process.
  • magnetic nanoparticles such as metal or iron oxide have been implanted into mesoporous silica.
  • the magnetic nanoparticles are present in the pores to remove pores, thereby reducing the surface area and susceptibility. Let's go.
  • some experiments have suggested a method of mixing magnetic nanoparticles in the wall portion of mesoporous silica, but the magnetic nanoparticles that can be applied thereto are limited.
  • Another method is hard-templating, in which magnetic nanoparticles are deposited after template deposition. And nano-casting method is applied in many ways to make metal oxide which is difficult to make by the conventional method. However, this treatment has a lower magnetization than when using pure metal.
  • the inventors of the present invention while searching for a method for supplementing the problems of the magnetic nanoparticles, when reacting with mesoporous silica and transition metal ions that can control the size of the pores and easy to functionalize the surface and then reduced to sodium borohydride
  • the present invention has been completed by confirming that magnetic mesoporous silica having a uniform pore distribution can be efficiently produced in a short time.
  • the present inventors have confirmed that the pore distribution of the magnetic mesoporous silica can be controlled by controlling the temperature in the reduction step using sodium borohydride, and completed the present invention.
  • An object of the present invention is to provide a magnetic mesoporous silica.
  • mesoporous silica refers to a porous material having a structure in which mesopores of uniform size are regularly arranged and having uniform pores as one of mesoporous molecular sieves, The mesoporous material has pores of 2 nm to 50 nm.
  • reducing agent refers to a substance having a high property of reducing other substances as it is oxidized.
  • the reducing agent is lithium aluminum hydride (LiAlH 4 ), hydrazine (N 2 H 4 H 2 O), sodium borohydride (NaBH 4 ), sodium chloride (NaCl ), it may be selected from sodium hydroxide (NaOH), aqueous ammonia (NH 4 OH), potassium bromide (KBr), and combinations thereof.
  • the reducing agent may be sodium borohydride (NaBH 4 ).
  • the method may further comprise (c) vacuum drying at room temperature after washing the mesoporous silica on which the transition metal ion is supported with alcohol.
  • the transition metal ion may be selected from the group consisting of Co, Fe, Ni, Mn, and combinations thereof.
  • the mesoporous silica may be prepared by hydrothermal synthesis.
  • the hydrothermal synthesis method is:
  • the surfactant is a carboxylate, sulfonate, sulfate ester salt, phosphate ester salt, phosphonate salt, amine salt, quaternary ammonium salt, phosphonium salt, sulfonium salt, fatty acid monoglycerine ester, fatty acid polyglycol ester, fatty acid sorbitan It may be any one or more selected from the group consisting of esters, fatty acid sucrose esters, fatty acid alkanolamides, polyethylene glycol condensed nonionic surfactants, polyethylene glycol-polypropylene glycol copolymers, but is not limited thereto.
  • the silica precursor may be tetraethylorthosilicate (TEOS), tetramethoxysilane (TMOS), or silicon tetrachloride, but is not limited thereto.
  • the magnetic mesoporous silica prepared by the method for producing magnetic mesoporous silica according to the present invention.
  • the magnetic mesoporous silica may have a uniform pore distribution and excellent magnetic properties.
  • the method for producing magnetic mesoporous silica according to the present invention is efficient in a short time when the mesoporous silica and transition metal ions, which can control the pore size and are easy to functionalize the surface, are reacted and reduced with sodium borohydride.
  • Magnetic mesoporous silica having a uniform pore distribution can be produced.
  • the pore distribution of the magnetic mesoporous silica can be easily adjusted by controlling the temperature in the reduction step using sodium borohydride.
  • Figure 1 shows the results of the BET analysis of mesoporous before reduction according to Experimental Example 1.
  • Figure 2 shows the results of the BET analysis of the reduced magnetic mesoporous silica at room temperature according to Experimental Example 1.
  • Figure 3 shows the results of the BET analysis of the magnetic mesoporous silica reduced at 50 °C in Experimental Example 1.
  • Figure 4 shows the results of the BET analysis of the reduced magnetic mesoporous silica at 75 °C in Experimental Example 1.
  • FIG. 5 is a photograph showing the magnetism of the magnetic mesoporous silica prepared according to the embodiment of the present invention.
  • nanoporous silica was first prepared.
  • the nanoporous silica was prepared by mixing Pluronic P123, 2M HCl and secondary distilled water in a weight ratio of 2:60:15.
  • the mixed solution became a transparent solution with stirring.
  • 8.5 g of tetraethyl ortho silica (TEOS) was added and stirred for 8 hours.
  • TEOS tetraethyl ortho silica
  • the solution was administered to a steel press and placed in an oven at 120 ° C. for 8 hours.
  • the solution was cooled to room temperature, washed with water, filtered and dried at room temperature to obtain a powder.
  • the dried powder was calcined at 550 ° C. for 6 hours to produce homogeneous mesoporous silica.
  • FeCl 2 ⁇ H 2 O (Iron (II) chloride tetrahydrate) was dissolved in distilled water to prepare 250 mL of an aqueous solution of iron precursor of 3 M, and 5 g of homogeneous mesoporous silica on the solid powder prepared above was mixed with the iron precursor solution. After stirring for an hour, the iron precursor was supported on mesoporous silica. Then, the mesoporous silica loaded with iron precursor was filtered and stored at -70 ° C for 1 hour and then vacuum dried at room temperature for 12 hours. 1 g of the dried sample and 30 mL of secondary distilled water are placed in a three neck flask, and the temperature is maintained at 50 ° C.
  • the method for producing magnetic mesoporous silica according to the present invention is efficient in a short time when the mesoporous silica and transition metal ions, which can control the pore size and are easy to functionalize the surface, are reacted and reduced with sodium borohydride. Magnetic mesoporous silica having a uniform pore distribution can be produced.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)

Abstract

La présente invention concerne un procédé destiné à la production de silice mésoporeuse magnétique. Plus spécifiquement, la présente invention concerne une silice mésoporeuse magnétique ayant une distribution de pores uniforme et un excellent magnétisme, la silice étant obtenue par réaction de silice mésoporeuse, ayant des ions de métaux de transition déposés dans celle-ci, avec un agent réducteur, à une température spécifique.
PCT/KR2017/005639 2016-05-30 2017-05-30 Procédé de production de silice mésoporeuse magnétique à l'aide de borohydrure de sodium WO2017209489A1 (fr)

Applications Claiming Priority (2)

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KR10-2016-0066161 2016-05-30
KR20160066161 2016-05-30

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WO2017209489A1 true WO2017209489A1 (fr) 2017-12-07

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019172845A1 (fr) * 2018-03-05 2019-09-12 Agency For Science, Technology And Research Matériau composite et son procédé de préparation

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20100128128A (ko) * 2009-05-27 2010-12-07 한국세라믹기술원 전이금속염을 이용한 메조포러스실리카 나노입자의 제조방법
KR20110064934A (ko) * 2009-12-09 2011-06-15 한국세라믹기술원 자성을 가지는 멀티모달 나노다공성 실리카 및 그 제조 방법
JP2012081391A (ja) * 2010-10-08 2012-04-26 Univ Of Miyazaki 触媒微粒子、カーボン担持触媒微粒子及び燃料電池触媒、並びに当該触媒微粒子及び当該カーボン担持触媒微粒子の製造方法
KR20130140341A (ko) * 2012-06-14 2013-12-24 한국세라믹기술원 세균 세포벽과 강한 표면결합을 위한 자성 메조다공성 실리카의 제조방법및 이를 이용한 고효율 세균의 분리 및 검출 방법

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20100128128A (ko) * 2009-05-27 2010-12-07 한국세라믹기술원 전이금속염을 이용한 메조포러스실리카 나노입자의 제조방법
KR20110064934A (ko) * 2009-12-09 2011-06-15 한국세라믹기술원 자성을 가지는 멀티모달 나노다공성 실리카 및 그 제조 방법
JP2012081391A (ja) * 2010-10-08 2012-04-26 Univ Of Miyazaki 触媒微粒子、カーボン担持触媒微粒子及び燃料電池触媒、並びに当該触媒微粒子及び当該カーボン担持触媒微粒子の製造方法
KR20130140341A (ko) * 2012-06-14 2013-12-24 한국세라믹기술원 세균 세포벽과 강한 표면결합을 위한 자성 메조다공성 실리카의 제조방법및 이를 이용한 고효율 세균의 분리 및 검출 방법

Non-Patent Citations (1)

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Title
KIM, HYUM-JONG ET AL.: "Synthesis and Characterization of Mesoporous Fe/Si02 for Magnetic Drug Targeting", JOURNAL OF MATERIALS CHEMISTRY, vol. 16, 13 February 2006 (2006-02-13), pages 1617 - 1621, XP055445734 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019172845A1 (fr) * 2018-03-05 2019-09-12 Agency For Science, Technology And Research Matériau composite et son procédé de préparation
US20200398246A1 (en) * 2018-03-05 2020-12-24 Agency For Science, Technology And Research Composite material and a method for preparing the same

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