WO2011108649A1 - 多孔質シリカの製造方法および多孔質シリカ - Google Patents
多孔質シリカの製造方法および多孔質シリカ Download PDFInfo
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- WO2011108649A1 WO2011108649A1 PCT/JP2011/054928 JP2011054928W WO2011108649A1 WO 2011108649 A1 WO2011108649 A1 WO 2011108649A1 JP 2011054928 W JP2011054928 W JP 2011054928W WO 2011108649 A1 WO2011108649 A1 WO 2011108649A1
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- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
- C01B37/02—Crystalline silica-polymorphs, e.g. silicalites dealuminated aluminosilicate zeolites
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- 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
- C01B33/16—Preparation of silica xerogels
- C01B33/163—Preparation of silica xerogels by hydrolysis of organosilicon compounds, e.g. ethyl orthosilicate
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- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
- C04B38/0051—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof characterised by the pore size, pore shape or kind of porosity
- C04B38/0054—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof characterised by the pore size, pore shape or kind of porosity the pores being microsized or nanosized
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- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
- C04B38/009—Porous or hollow ceramic granular materials, e.g. microballoons
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- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
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Definitions
- the present invention is a technique effective when applied to a method for producing porous silica and porous silica.
- Mesoporous silica is a porous body having hexagonal close packed cylinder-type pores, and has a uniform pore diameter of 2 to 10 nm in average pore diameter.
- This substance can be prepared by dissolving, hydrolyzing alkoxysilane, sodium silicate aqueous solution, kanemite, silica fine particles, etc., which are silica sources in water or alcohol, and using surfactant rod-like micelles formed in water as a template. Synthesized in the presence of a base catalyst.
- Patent Document 2 proposes a method for avoiding these problems by reducing the amount of water added as a solvent, and at the same time obtaining a concentrated precursor solution suitable for application and immersion on various substrates. Yes.
- a cationic surfactant cannot be used under this reaction condition.
- Mesoporous silica is expected to be used as an adsorbent for removing harmful volatile organic substances.
- the target component When used for processing exhaust gas, which is a typical application, the target component must be adsorbed from the flowing gas, so that a strong adsorbing power is required.
- the adsorbent preferably has a pore diameter of 1 to 1.5 times the molecular diameter. Since many volatile organic substances have a molecular diameter of 1 nm or less, the adsorbent preferably has pores of about 0.5 to 1 nm. In order to synthesize mesoporous silica having pores in this range, the number of carbon atoms It is necessary to use 7 or less cationic surfactants.
- Patent Documents 1 to 3 and Non-Patent Documents 1 and 2 the types of cationic surfactants that can be used for synthesizing mesoporous silica are limited to those having a hydrophobic part of 8 or more.
- Non-Patent Documents 1 and 2 report that when a cationic surfactant having 6 carbon atoms is used, amorphous silica or zeolite-type products are obtained, and mesoporous silica is not obtained. ing.
- the cause of this is considered to be that the ability to form micelles in water decreases with a decrease in the carbon chain of the hydrophobic portion, and sufficient micelles cannot be formed as a template.
- Non-Patent Document 3 uses a fluorine-containing nonionic surfactant and synthesizes at a low temperature of ⁇ 20 ° C.
- such special surfactants and low-temperature reaction equipment are generally expensive, and there is a concern about generation of harmful substances containing fluorine when the surfactant is removed by baking. In this case, the cost of equipment for removing harmful substances is also required.
- Non-Patent Document 4 attempts to avoid this problem by using a gemini surfactant having a high micelle forming ability.
- gemini type surfactants are generally not readily available in large quantities as synthetic raw materials and are expensive. Therefore, it is necessary to establish a synthesis method using a general-purpose cationic surfactant.
- micropore volume depends on the ethylene glycol chain, which is the hydrophilic part of the nonionic surfactant, and only a micropore volume of 0.25 cm 3 / g is obtained at the maximum.
- mesoporous silica synthesized by a conventional method can be obtained with fine particles of several hundred nm to several ⁇ m. Therefore, in order to use as various materials, it is necessary to form a molded body using a binder or the like.
- Mesoporous silica is characterized by its thermal stability and transparency. Utilization of these characteristics is expected to be applied to recyclable adsorbents, photocatalyst carriers, chromic materials, and the like. However, there is a problem that these characteristics are remarkably deteriorated depending on the binder used for molding. Moreover, when a binder is not used, there exists a problem that the intensity
- the object of the present invention is that it can be easily molded into various shapes, has excellent transparency, can be made into nanoparticles, and can be obtained with high efficiency even when a cationic surfactant having 7 or less carbon atoms is used. It is an object of the present invention to provide porous silica that can be produced, a method for producing the same, and an aggregate.
- the mesoporous silica precursor solution is composed of silicate ions, a surfactant, 4 equivalents of alcohol molecules desorbed from alkoxysilane, and a small amount of acidic components used for pH adjustment.
- alcohol desorbed by natural transpiration or reduced pressure removal using a rotary evaporator or excess water generated by dehydration condensation may be removed.
- the entire system is gelled by stirring or leaving the mesoporous silica precursor at an arbitrary temperature. After the gel is dried, the surfactant is removed by washing or baking to obtain mesoporous silica with open pores.
- the amount of water to be added is suitably 2 to 4 equivalents, whereby stable micelles can be generated in silicate ions, and precursors that can be easily molded in various ways can be obtained.
- the pH after addition of water is suitably from 0 to 2. If the pH is 2 or more, hydrolysis and gelation of alkoxysilane proceed instantaneously, and the desired pores cannot be obtained. Since the hydrolysis / gelation rate of alkoxysilane becomes the slowest at pH 2, a uniform precursor can be formed. In addition, although the hydrolysis rate is accelerated at pH 0 to 1, the gelation rate is sufficient for forming micelles of surfactant and molding mesoporous silica, so that mesoporous silica having desired pores and shapes can be obtained. it can.
- alkoxysilane The order of adding alkoxysilane, water, and surfactant is arbitrary.
- reaction temperature may be increased, or a precursor may be added to a basic solution or vapor.
- the surfactant is a cationic surfactant and more preferably has a hydrophobic group having 2 to 7 carbon atoms, or a hydrophobic group such as a benzyl group or a phenyl group.
- the average pore diameter varies in the range of 0.5 nm or more and less than 2 nm, preferably 0.5 to 1.4 nm, more preferably 0.5 to 1 nm.
- the specific surface area is in the range of 300 to 1800 m 2 / g, preferably 450 to 1200 m 2 / g, and the micropore volume is 0.1 to 2.0 cm 3 / g, preferably 0.1 to 0.5 cm 3. In the range of / g.
- the average pore diameter can be measured by, for example, BJH analysis and GCMS method, and the specific surface area can be measured by, for example, BET method.
- the surfactant may be a cationic surfactant having a hydrophobic group having 8 to 24 carbon atoms.
- the average pore diameter can be arbitrarily changed within the range of 1.4 to 4 nm.
- the generated mesoporous silica can be made into nanoparticles. That is, the structure of the mesoporous silica to be generated can be controlled by the molecular weight and the added amount of the aqueous polymer added.
- the generated mesoporous silica is a nanoparticle of 10 to 20 nm, but the particles are bonded to each other, and is obtained as a white monolith body (porous body) composed of nanoparticles.
- Mesoporous silica precursors are monolithic using the property of maintaining the shape of the container when gelled, beaded by dripping into the liquid, thin film by spin coating or dip coating, spinner etc. Can be processed into various shapes such as a fibrous shape.
- organic silane compound for example, a compound having a short carbon chain such as triethoxyvinylsilane is used as a silica source together with alkoxysilane.
- the effect of reducing the pores due to the addition of the organic silane is considered to be due to the reduction of the diameter of the micelles using the organic silane having a short carbon chain as a template.
- the organic functional group of the organosilane can exist on the pore wall surface or outside the particle, but can be removed by heat treatment or the like.
- the surfactant may be washed away to form porous silica containing the organic functional group.
- Porous silica that is easy to mold, excellent in transparency, and can be made into nanoparticles can be obtained with high efficiency even when a cationic surfactant having 7 or less carbon atoms is used.
- FIG. 6 is a chart showing the analysis results of the pores of porous silica obtained in the second embodiment. It is a graph which shows the change of the average pore diameter with respect to carbon number. 6 is a graph showing a small-angle X-ray diffraction result of porous silica obtained in the second embodiment. 10 is a chart showing the analysis results of the pores of porous silica obtained in the third embodiment. 6 is a graph showing a small-angle X-ray diffraction result of porous silica obtained in the third embodiment.
- an alkoxysilane and a cationic surfactant are mixed as they are without using a solvent, and a precursor solution obtained by adjusting the pH by adding water as a reactant is gelled.
- pH 2 which is the isoelectric point of alkoxysilane.
- the hydrolysis rate of alkoxysilane and the gelation rate of silicate ions are the slowest, so that sufficient time for micelle formation of the surfactant can be secured. Hydrolysis is accelerated at pH 0 to 1, but the same effect can be obtained because the gelation rate of silicate ions is sufficiently slow. Therefore, the pH of the water to be added needs to be adjusted in the range of 0-2. If the pH is 3 or higher, the hydrolysis and gelation rate is too fast, so that sufficient time for dissolving the surfactant and forming micelles cannot be secured, and the desired mesoporous silica having a pore structure cannot be obtained.
- inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid, and organic acids such as acetic acid can be used.
- the amount of water added to the alkoxysilane is from 2 equivalents (eq) necessary for the reaction to 4 equivalents necessary for completing the hydrolysis of the alkoxysilane, and 4 equivalents is preferable.
- the cationic surfactant is a surfactant represented by the general formula R 1 R 2 R 3 R 4 N + X — , and R 1 is an alkyl group having 1 to 24 carbon atoms, a benzyl group, or a phenyl group.
- R 2 R 3 R 4 is a quaternary cationic surfactant in which a methyl group, an ethyl group, a propyl group, or a butyl group is present, and X is a halogen ion of F, Cl, Br, or I.
- the alkyl group for R 1 may be linear or branched.
- a cationic surfactant having a short carbon chain is used.
- An example of a synthesis method using water or ethanol as a general solvent is shown below.
- a cationic surfactant is dissolved in an aqueous hydrochloric acid solution, alkoxysilane is added, and after stirring, an aqueous ammonia solution is added to gel the mesoporous silica.
- a cationic surfactant up to carbon chain 10 is used, gelation is completed almost simultaneously with the addition of ammonia, and mesoporous silica is obtained quantitatively.
- nano particles of mesoporous silica can also be formed.
- mesoporous silica can be nanoparticulated by adding a water-soluble polymer to the reaction system.
- polyethylene glycol PEG
- PEG polyethylene glycol
- the average molecular weight of polyethylene glycol is not limited, but is preferably from several hundred to several thousand.
- a water-soluble polymer such as polyethylene glycol is also soluble in silicate ions and produces a uniform solution.
- the silanol groups on the outer wall of the silica enclosing the rod-like micelle aggregate of the cationic surfactant and the oxygen atom of polyethylene glycol form hydrogen bonds.
- silica and polyethylene glycol are phase-separated to produce mesoporous silica nanoparticles.
- polyethylene glycol does not affect the micelle formation of the cationic surfactant, mesoporous silica nanoparticles having the desired pore structure are generated.
- gelation of silicate ions is suppressed by hydrogen bonds formed between polyethylene glycol and silicate ions, and the time until gelation is extended up to about one month at room temperature.
- Gelation rate can be accelerated by increasing the reaction temperature, dropping into a basic aqueous solution, or making the pH of the entire system basic.
- This method of adding a water-soluble polymer can produce 10 to 20 nm mesoporous silica particles.
- the product can be obtained as an aggregate in which nanoparticles are bonded to each other.
- the nanoparticles themselves form an aggregate, but the pores in the interstices function as new mesopores because they are connected to each other.
- the average pore diameter of the particle gap is about 50 nm.
- the aggregate of nanoparticles is obtained as a white monolith (porous) and has sufficient strength against impact.
- assembly of a nanoparticle is obtained, for example by photographing and observing the particle
- TEM transmission electron microscope
- a stable precursor solution can be obtained, so that a mesoporous silica molded body can be produced by the following molding method.
- a monolithic mesoporous silica molded body depending on the shape of the reaction vessel can be produced by standing or stirring in the reaction vessel.
- the shape of the reaction vessel it can be formed into an arbitrary shape such as a pellet, a sphere, a rod, or a disk.
- Spherical mesoporous silica beads can be produced by dropping the precursor solution into a heated liquid or a basic aqueous solution.
- beads having an arbitrary size can be molded by changing the viscosity depending on the dropping nozzle diameter, the dropping speed, and the gelation degree of the precursor solution.
- hollow beads can also be produced by enclosing bubbles.
- the basic solution an aqueous ammonia solution, an aqueous sodium hydroxide solution, or the like can be used conveniently.
- Thin film mesoporous silica can be obtained by spin coating or dip coating the precursor solution. After film formation, gelation can be completed by drying as it is or by exposing it to ammonia vapor. A dip coat can be applied to a molded body such as a honeycomb, paper, cloth, etc., and both a spin coat and a dip coat can be applied to a substrate surface.
- Fibrous mesoporous silica can be produced by blowing the precursor solution from a nozzle such as a spinner. Fibrous mesoporous silica can be produced by gelation in the air by blowing at a higher temperature than the spinner, or by blowing into ammonia vapor from the spinner.
- the mesoporous silica of the present invention When used as an adsorbent, it can be used as an efficient adsorbent for a wide range of adsorbates because of the ease of controlling the pore diameter.
- an adsorbent having a pore diameter of about 1 to 1.5 times the molecular diameter of the adsorbate is desired, but the target harmful adsorbate has a molecular diameter of 1 nm or less.
- micropores of 1.5 nm or less are desired.
- the mesoporous silica obtained by the present invention achieved a reduction in pore diameter while using a general-purpose surfactant. Further, since nanoparticulation can be achieved at the same time, the diffusion of the adsorbate can be facilitated and used as an efficient adsorbent. In addition, the product can be synthesized in any shape, and because it is solvent-free, the production equipment and the drying equipment can be significantly downsized. Is possible.
- the present invention can greatly contribute from an industrial point of view because the main factor that has prevented the spread of conventional mesoporous silica to the general public is the lack of cost and moldability.
- the effect as a photocatalyst carrier is particularly high because of its high transparency and resistance to scattering. This is obtained in the form of a colorless and transparent monolith rather than a powder of several microns as in the past, and the particle size and pore size of the pores, which were not able to be achieved in the past even when converted to nanoparticles, are 10 nm or less. This is due to the effect of successfully reducing the thickness to 5 nm. Moreover, since it can be easily molded into various shapes such as a film shape and a fiber shape, it is highly advantageous. Further, as in the case of the adsorbent, reduction of raw materials and manufacturing costs greatly contributes to the spread.
- Mesoporous silica is used for various purposes, and its application to functional materials such as phosphors and electronic materials is being studied by enclosing various molecules in the pores. Moreover, it can be predicted that the pore diameter for the molecule confined in the nano space to begin to exhibit specific properties is 1 nm or less, which is close to the diameter of the encapsulated molecule. Also in these applications, the mesoporous silica obtained by the present invention exhibits effects such as a controllable pore size, ease of moldability, transparency, and high impact resistance.
- the obtained mesoporous silica was evaluated using the following apparatus.
- TECNAI F20 FEI
- the observation sample was prepared by dispersing the pulverized sample in a copper mesh with a collodion film.
- Example 1 Synthesis of monolithic mesoporous silica] Tetraethoxysilane (TEOS) 8 g (0.038 mol; 1 eq) as a silica source is put in a polypropylene container, followed by surfactants hexadecyltrimethylammonium chloride (C16TAC), octyltrimethylammonium bromide (C8TAB), hexyltrimethyl. 2.4 g (0.0075 mol in the case of C16TAC; 0.2 eq) of either ammonium bromide (C6TAB) or benzyltrimethylammonium chloride (BzTAC) was dispersed and stirred.
- C16TAC hexadecyltrimethylammonium chloride
- C8TAB octyltrimethylammonium bromide
- BzTAC benzyltrimethylammonium chloride
- the nitrogen adsorption / desorption isotherm of the obtained mesoporous silica is shown in FIG.
- the isotherm indicates type IV of the classification of IUPAC (International Pure Applied Chemistry Association), indicating the presence of mesopores.
- the isotherms using C8TAB, C6TAB, and BzTAC indicate the type I of the IUPAC classification, indicating the presence of micropores.
- Table 1 summarizes the carbon number of the surfactant and the specific surface area, pore volume, and average pore diameter of the obtained mesoporous silica.
- the BET specific surface area was 1203 m 2 / g, and the pore volume was 0.58 cm 3 / g. Further, from the result of BJH pore analysis, it was found that the average pore diameter was 2.1 nm.
- the BET specific surface areas were 552, 617, and 480 m 2 / g, respectively, and the pore volumes were 0.28, 0.32, and 0.25 cm 3 / g, respectively.
- the average pore diameter was less than 2 nm and could not be accurately determined by BJH analysis.
- the GCMC analysis results of mesoporous silica synthesized by a conventional method using dodecyltrimethylammonium bromide (C12TAB) are also shown in FIG. According to BJH analysis, the pore diameter of C12TAB is 2 nm. From this, assuming that the GCMC method is about 0.5 to 0.6 nm and the pore diameter is excessively estimated, the pore diameter of mesoporous silica synthesized using C8TAB is about 1 to 1.2 nm and C6TAB is used. Can be estimated to be about 0.8 to 1 nm.
- Example 2 [Synthesis of monolithic mesoporous silica nanoparticles by addition of PEG] TEOS 8 g (0.038 mol; 1 eq) as a silica source is placed in a polypropylene container, and then 2.4 g (0.0075 mol; 0.2 eq) of any one of C16TAC, C8TAB, and C6TAB is dispersed, and further polyethylene glycol (average The molecular weight was 1000; 7.5 g) was added and stirred. To this, 2.74 g (0.152 mol; 4 eq) of water adjusted to pH 2 with hydrochloric acid was added and stirred.
- the isotherms indicate type IV for C16TAC and type I for C8TAB and C6TAB, indicating the presence of mesopores and micropores, respectively. Furthermore, a sudden increase in the amount of adsorption is observed near the relative pressure of 0.8 to 0.9. This is because the mesoporous silica itself constituting the monolith body itself becomes nanoparticles of 10 to 20 nm and is generated in the particle gap. This is due to capillary condensation into the second mesopores. Table 2 shows the specific surface area, pore volume, and average particle pore diameter of each mesoporous silica nanoparticle.
- C16TAC, C8TAB, and C6TAB had BET specific surface areas of 1670, 954, and 630 m 2 / g, and pore volumes of 1.70, 1.96, and 1.60 cm 3 / g, respectively. From the results of BJH pore analysis, it was found that the average pore diameter derived from the nanoparticle gap was about 40 nm in any sample. As shown in FIG. 6, the particle size and the particle gap size can be confirmed by a transmission electron microscope (TEM) image of the same sample.
- TEM transmission electron microscope
- Example 3 The precursor solution before gelation in Example 2 was dropped into a 28% aqueous ammonia solution by a syringe. The dropped precursor solution gelled while maintaining the spherical shape as soon as it entered the aqueous ammonia solution. The precipitated spherical gel was collected, dried and baked at 600 ° C. for 3 hours to remove the surfactant and polyethylene glycol. A photograph of the obtained beaded mesoporous silica is shown in FIG. As can be seen from the photograph, when polyethylene glycol was added to the precursor solution, it became a white sphere due to scattering. The obtained beads had a spherical shape of about 2 to 3 mm.
- Example 4 The precursor solutions before gelation in Examples 1 to 3 were each spin-coated on a glass substrate with a spin coater. Each coated glass substrate was exposed to ammonia vapor for tens of seconds to complete the gelation. Thereafter, it was dried and calcined at 600 ° C. for 3 hours to remove the surfactant and polyethylene glycol. The photograph was shown in FIG. 8 taking the case where the precursor solution of Example 1 was used among the obtained thin films as an example.
- Example 5 In order to evaluate the performance of the mesoporous silica obtained in Example 1 as an adsorbent, the dynamic adsorption ability of toluene was measured.
- a dynamic adsorption evaluation apparatus manufactured by Okura Giken Co., Ltd.
- the measurement was performed at a toluene concentration of 100 ppm, a wind speed of 1 m / second, a flow rate of 10.6 L / min, a sample amount of 6.4 mL, and a sample tube inner diameter of 15 mm.
- the sample was pretreated for about one hour at 200 ° C. under a flow of dry air.
- a cylindrical silica (SiO 2 ) having pores is formed by hydrolyzing alkoxysilane using a rod-like micelle of a surfactant formed in water as a template.
- Such silica is called porous silica (porous silica).
- the number of types of cationic surfactants studied was increased, and further verification was performed.
- the obtained porous silica was evaluated using the following apparatus.
- TECNAI F20 FEI
- the observation sample was prepared by dispersing the pulverized sample in a copper mesh with a collodion film.
- octadecyltrimethylammonium chloride (C18TAC) Hexadecyltrimethylammonium chloride (C16TAC), tetradecyltrimethylammonium bromide (C14TAB), dodecyltrimethylammonium bromide (C12TAB), decyltrimethylammonium bromide (C10TAB), octyltrimethylammonium bromide (C8TAB), hexyltrimethylammonium bromide (C6TAB), Porous silica was synthesized using 8 types of butyltrimethylammonium chloride (C4TAC).
- silica can be promoted without inhibiting the micelle formation of the surfactant by solvent molecules or the like.
- micelles can be formed even when a surfactant having a small number of carbon atoms (for example, 7 or less), which has been difficult in the past, can be formed, and porous silica having fine pores can be formed.
- the nitrogen adsorption / desorption isotherm of the obtained porous silica is shown in FIG.
- FIG. 10 nitrogen adsorption and desorption isotherms of porous silica when C18TAC, C16TAC, C14TAB, C12TAB, C10TAB, C8TAB, C6TAB, and C4TAC are used in order from the top.
- up to about 18 to 14 carbon atoms (C18TAC, C16TAC, C14TAB)
- the graph bends and the slope changes between the low pressure portion and the high pressure portion Such changes are based on capillary condensation and correspond to type IV of the IUPAC classification. Thereby, the existence of mesopores is presumed.
- FIG. 11 shows the analysis result of the pores of the obtained porous silica.
- Specific surface area (SSA), pore volume (TPV), and average pore diameter (D) were summarized.
- the specific surface area (SSA) was measured by the BET method.
- the average pore diameter was measured using BJH method, HK method, and GCMC method.
- BJH method BJH method
- HK method HK method
- GCMC method GCMC method.
- the average pore diameter it is possible to calculate (analyze) a finer pore diameter in the HK method than in the BJH method. Further, it is possible to calculate (analyze) a finer pore diameter in the GCMC method than in the HK method.
- the porous silica (C18) using C18TAC had a BET specific surface area of 1361 m 2 / g and a pore volume of 0.96 cm 3 / g.
- the average pore diameter was 3.00 nm for the BJH method, 3.36 nm for the HK method, and 3.27 nm for the GCMC method.
- the porous silica (C16) using C16TAC had a BET specific surface area of 1452 m 2 / g and a pore volume of 0.79 cm 3 / g.
- the average pore diameter was 2.70 nm for the BJH method, 2.86 nm for the HK method, and 2.82 nm for the GCMC method.
- the porous silica (C14) using C14TAB had a BET specific surface area of 1234 m 2 / g and a pore volume of 0.60 cm 3 / g.
- the average pore diameter was 2.40 nm by the HK method and 2.26 nm by the GCMC method.
- the porous silica (C12) using C12TAB had a BET specific surface area of 1056 m 2 / g and a pore volume of 0.53 cm 3 / g.
- the average pore diameter was 2.00 nm in the HK method and 1.82 nm in the GCMC method.
- the porous silica (C10) using C10TAB had a BET specific surface area of 916 m 2 / g and a pore volume of 0.45 cm 3 / g.
- the average pore diameter was 1.60 nm in the HK method and 1.58 nm in the GCMC method.
- the porous silica (C8) using C8TAB had a BET specific surface area of 810 m 2 / g and a pore volume of 0.41 cm 3 / g.
- the average pore diameter was 1.28 nm in the GCMC method.
- the porous silica (C6) using C6TAB had a BET specific surface area of 632 m 2 / g and a pore volume of 0.32 cm 3 / g.
- the average pore diameter was 1.12 nm in the GCMC method.
- the porous silica (C4) using C4TAC had a BET specific surface area of 586 m 2 / g and a pore volume of 0.29 cm 3 / g.
- the average pore diameter was 0.92 nm in the GCMC method.
- porous silica having pores corresponding to the chain length was obtained. That is, it was found that the average pore diameter (D) decreases as the carbon number decreases from 18 to 4.
- the average pore diameter of porous silica using a surfactant having 12 or less carbon atoms was 2 nm or less, and micropores were confirmed.
- the average pore diameter of porous silica using C6TAB having 6 carbon atoms is It was 1.12 nm by the GCMC method, and the average pore diameter of the porous silica using C4TAB having 4 carbon atoms was 0.92 nm by the GCMC method.
- the pore volume is large and the formation of the porous silica of 0.25 cm ⁇ 3 > / g or more is possible.
- the BET specific surface area decreases and the pore volume decreases.
- the pore wall thickness (Dwall) increases.
- the pore wall thickness that is, the thickness of the wall constituting the cylinder can be calculated from the X-ray diffraction result or the like.
- the pore wall thickness (Dwall) can be changed by adjusting the surfactant concentration or the like. For example, the pore volume can be increased by reducing the pore wall thickness (Dwall).
- FIG. 12 is a graph showing a change in average pore diameter (Dpore; nm) with respect to the number of carbons. From this, it can be seen that the average pore diameter decreases as the carbon number decreases from 18 to 4.
- the average pore diameter required according to the adsorbate (for example, molecular diameter, etc.) is calculated, and the pore diameter is controlled by selecting the carbon number of the surfactant so as to match the average pore diameter. be able to.
- the difference in pore diameter is about 0.1 to 0.6 nm, and the fine pore diameter can be adjusted.
- FIG. 13 is a result of small-angle X-ray diffraction of the obtained porous silica.
- the vertical axis is intensity (Intensity; au), and the horizontal axis is 2 ⁇ (deg).
- the small-angle X-ray diffraction results of porous silica when C18TAC, C16TAC, C14TAB, C12TAB, C10TAB, C8TAB, C6TAB, and C4TAC are used are shown. Since both graphs show a broad diffraction pattern, the obtained porous silica is a so-called wormhole type (shape) in which the arrangement of cylinders (pores) is disturbed compared to the hexagonal close packed cylinder type. It was found to have the following structure.
- Alignment can be improved by removing alcohol generated during hydrolysis of alkoxysilane.
- the pore arrangement is low, the adsorption characteristics are good and the effect as an adsorbent can be sufficiently exerted. Therefore, when priority is given to the convenience of production, it is not always necessary to remove the alcohol.
- Example A 2 to 4 eq of water was used, but it was confirmed that hydrolysis proceeded well even when 8 eq of water was used.
- no solvent in other words, no water as a solvent is contained.
- Water as a solvent is, for example, water (solvent) of several tens times equivalent (for example, 50 times equivalent or more) of these materials necessary for dissolution and dispersion of alkoxysilane, cationic surfactant and the like.
- the solvent-free in the present invention refers to the amount of water added to the alkoxysilane, from the minimum 2 equivalents (eq) required for the reaction, to about 10 times, that is, 2 equivalents or more 20
- the range is equal to or less than the equivalent amount. More preferably, it is in the range of 2 to 10 equivalents.
- an alkoxysilane and an organic silane compound are mixed without using a solvent, a cationic surfactant is further mixed, and then a precursor solution obtained by adding water as a reactant is gelled.
- pH 2 which is the isoelectric point of alkoxysilane.
- the hydrolysis rate of alkoxysilane and the gelation rate of silicate ions are the slowest, so that sufficient time for micelle formation of the surfactant can be secured.
- Hydrolysis is accelerated at pH 0 to 1, but the same effect can be obtained because the gelation rate of silicate ions is sufficiently slow. Therefore, the pH of the water to be added needs to be adjusted in the range of 0-2. If the pH is 3 or higher, the hydrolysis and gelation rate is too fast, so that sufficient time for dissolution of the surfactant and micelle formation cannot be secured, and porous silica having the desired pore structure cannot be obtained.
- inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid, and organic acids such as acetic acid can be used.
- the amount of water added to the alkoxysilane is in the range of 2 to 20 equivalents, more preferably in the range of 2 to 10 equivalents, as in the second embodiment.
- the cationic surfactant is a surfactant represented by the general formula R 1 R 2 R 3 R 4 N + X — , and R 1 is an alkyl group having 1 to 24 carbon atoms, a benzyl group, or a phenyl group.
- R 2 R 3 R 4 is a quaternary cationic surfactant in which a methyl group, an ethyl group, a propyl group, or a butyl group is present, and X is a halogen ion of F, Cl, Br, or I.
- the alkyl group for R 1 may be linear or branched.
- porous silica having pores having a diameter of 1 nm or less can be formed, and porous silica excellent in adsorption performance for harmful volatile organic substances (VOC) can be obtained.
- the organosilane compound is added to the mixed solution of the alkoxysilane, which is the silica source, and the cationic surfactant, the diameter of the rod-like micelle is reduced and the pore diameter (diameter) is reduced.
- the alkoxysilane which is the silica source, and the cationic surfactant
- TEVS triethoxyvinylsilane
- the addition amount of the organosilane compound can be adjusted in the range of 1 to 50%. However, the pore shrinkage effect is large even at about 5%. Moreover, since excessive administration of an organosilane compound can be an inhibitory factor for micelle formation, it is preferably 20% or less, more preferably 10% or less. In particular, in a surfactant having a small number of carbon atoms (less than 8 carbon atoms), it is preferable to reduce the addition amount of the organosilane compound, and preferably 10% or less.
- the organosilane compound used in this embodiment has a bond between silicon and carbon (Si—C) and has an alkoxyl group. Since it has the structure which the alkoxyl group couple
- the organic functional group (that is, the group having carbon) has a relatively short carbon chain such as a vinyl group. In this method, it is considered that the diameter (diameter) of the micelle serving as a template is shortened by the interaction between TEVS and the micelle.
- the organic functional group can be present on the pore wall surface of the synthesized porous silica or outside the particles, but can be easily removed by subsequent firing (heat treatment).
- the organic functional group may be left inside.
- an organic functional group itself or another organic compound may be added to function as a surface modifier. In this way, when it is better to remove the organic functional group without removing the organic functional group, the surfactant may be washed away without firing.
- the product can be obtained, for example, as a colorless and transparent monolith (porous). In this case, it has sufficient strength against impact.
- a monolithic porous silica molded body depending on the shape of the reaction vessel can be produced by gelling the precursor solution in a reaction vessel and allowing it to stand or stir.
- the shape of the reaction vessel it can be formed into an arbitrary shape such as a pellet, a sphere, a rod, or a disk.
- spherical porous silica beads can be produced by dropping the precursor solution into a heated liquid or a basic aqueous solution.
- beads having an arbitrary size can be molded by changing the viscosity depending on the dropping nozzle diameter, the dropping speed, and the gelation degree of the precursor solution.
- hollow beads can also be produced by enclosing bubbles.
- the basic solution an aqueous ammonia solution, an aqueous sodium hydroxide solution, or the like can be used conveniently.
- thin film-like porous silica can be obtained by spin coating or dip coating the above precursor solution. After film formation, gelation can be completed by drying as it is or by exposing it to ammonia vapor. A dip coat can be applied to a molded body such as a honeycomb, paper, cloth, etc., and both a spin coat and a dip coat can be applied to a substrate surface.
- fibrous porous silica can be produced by blowing the precursor solution from a nozzle such as a spinner. Fibrous porous silica can be produced by gelation in the air by blowing at a higher temperature than the spinner, or by blowing into ammonia vapor from the spinner.
- the pore diameter of the porous silica can be controlled by adding an organic silane in addition to the carbon number of R1.
- pore diameter control according to adsorbate can be performed. Therefore, the porous silica of the present embodiment can be used as an efficient adsorbent for a wide range of adsorbates.
- an adsorbent having a pore diameter of about 1 to 1.5 times the molecular diameter of the adsorbate is desired, but the target harmful adsorbate has a molecular diameter of 1 nm or less.
- micropores of 1.5 nm or less are desired.
- the porous silica obtained by the present invention achieved a reduction in pore diameter while using a general-purpose surfactant. Moreover, it can also be made into nanoparticles, which can increase the adsorption efficiency. Also, the product can be synthesized in any shape and is useful. In addition, because of the solvent-free condition, it is possible to greatly reduce the size of manufacturing equipment and drying equipment. Thereby, cost reduction from both the raw material cost and the manufacturing cost is possible. In addition, the major factors that prevented the spread of conventional mesoporous silica to the general public were the lack of cost and moldability. By improving these problems, the industrial use was greatly promoted. Is possible.
- the porous silica of the present embodiment can be made into a colorless and transparent monolith.
- the conventional powder form of several microns is difficult to apply to a catalyst carrier. Therefore, the porous silica of the present embodiment can be used for a catalyst carrier, for example.
- it is suitable for use as a photocatalyst support because of its high transparency and resistance to scattering.
- it can be easily molded into various shapes such as a film shape and a fiber shape, it is highly advantageous.
- similarly to the case of using it as an adsorbent when using it as a catalyst carrier, it is possible to reduce raw material costs and manufacturing costs.
- the porous silica of the present embodiment has a wide variety of uses, and can be used as a functional material such as a phosphor or an electronic material by enclosing various molecules in the pores.
- the pore diameter is 1 nm or less, molecules confined in the inside (nanospace) begin to express specific properties. This is presumably because the pore diameter approximates the diameter of the molecule to be encapsulated, and the molecule is encapsulated by the molecule alone or in the unit of a quantifier within the pore diameter.
- the porous silica obtained in the present embodiment has a fine pore diameter and can be controlled in a wide range with a fine width, ease of moldability, transparency, high impact resistance, etc. It has the effect of.
- TECNAI F20 FEI
- the observation sample was prepared by dispersing the pulverized sample in a copper mesh with a collodion film.
- Example B [Control of pore size by addition of organosilane]
- 8 g (0.038 mol; 1 eq) of tetraethoxysilane (TEOS) and 8 g ⁇ 5% (0.038 mol ⁇ 5%) of triethoxyvinylsilane (TEVS) are mixed as a silica source, followed by surface activity. 0.2-1.2 equivalents of the agent was added and stirred. To this mixture, water adjusted to pH 0-2 with hydrochloric acid was added in an amount of 2-4 equivalents and stirred at room temperature. The TEOS hydrolysis proceeded with stirring for about 1 hour, and an almost uniform solution was obtained.
- this solution (precursor solution) was kept at room temperature or 60 ° C. and continuously stirred or allowed to stand. Gelation was completed in 12 hours to several days, and the whole solution became a colorless and transparent gel. This gel was dried at 60 ° C. and calcined at 600 ° C. for 3 hours to remove the surfactant.
- Three types of surfactants octyltrimethylammonium bromide (C8TAB), hexyltrimethylammonium bromide (C6TAB), and butyltrimethylammonium chloride (C4TAC), which are cationic surfactants, are used to form porous silica. did.
- FIG. 14 shows the analysis results of the pores of the obtained porous silica.
- Specific surface area (SSA), pore volume (TPV), average pore diameter (D) and pore wall thickness (Dwall) were summarized.
- the specific surface area (SSA) was measured by the BET method.
- the average pore diameter was measured using the GCMC method.
- the pore wall thickness that is, the thickness of the wall constituting the cylinder can be calculated from the X-ray diffraction result or the like.
- the porous silica (C8V) using C8TAB had a BET specific surface area of 519 m 2 / g and a pore volume of 0.25 cm 3 / g.
- the average pore diameter was 0.99 nm.
- the pore wall thickness was 2.37 nm.
- the porous silica (C6V) using C6TAB had a BET specific surface area of 582 m 2 / g and a pore volume of 0.25 cm 3 / g.
- the average pore diameter was 0.82 nm.
- the pore wall thickness was 2.00 nm.
- the porous silica (C4V) using C4TAC had a BET specific surface area of 355 m 2 / g and a pore volume of 0.16 cm 3 / g.
- the average pore diameter was 0.77 nm.
- the pore wall thickness was 1.98 nm.
- Example A when C8TAB was used (see FIG. 11), the average pore diameter was 1.28 nm, so that the average pore diameter of 1.28 nm was increased by the addition of the organosilane compound. A reduction effect to 0.99 nm was confirmed. The difference in pore diameter is 0.29 nm.
- Example A when C6TAB was used (see FIG. 11), the effect of reducing the average pore diameter from 1.12 nm to 0.82 nm was confirmed by the addition of the organosilane compound. .
- the difference in pore diameter is 0.30 nm.
- the pore diameter of the porous silica can be finely adjusted by adding the organosilane compound.
- a surfactant having 8 carbon atoms it is possible to form porous silica having super micropores having an average pore diameter of 0.7 nm to 1.5 nm.
- a porous material having super micropores having an average pore diameter of 0.7 nm or more and 1.5 nm or less is obtained by addition of an organosilane compound. There is a high possibility that silica is formed.
- FIG. 15 is a result of small-angle X-ray diffraction of the obtained porous silica.
- the vertical axis is intensity (Intensity; au), and the horizontal axis is 2 ⁇ (deg).
- the small-angle X-ray diffraction results of porous silica when C8TAB, C6TAB, and C4TAC are used are shown. Since both graphs show a broad diffraction pattern, the obtained porous silica is a so-called wormhole type (shape) in which the arrangement of cylinders (pores) is disturbed compared to the hexagonal close packed cylinder type. It was found to have the following structure.
- FIG. 16 is a graph showing changes in average pore diameter in the porous silica obtained in Example A and Example B.
- the porous silica obtained in Example B is indicated by adding V after Cn indicating the carbon number (n). That is, the porous silica using C8TAB having 8 carbon atoms in Example B is indicated as “C8V”.
- the required average pore diameter according to the adsorbate for example, molecular diameter, etc.
- the adsorbate for example, molecular diameter, etc.
- select the number of carbon atoms of the surfactant to match the average pore diameter or add an organosilane compound.
- fine control of the pore diameter can be performed.
- fine control of the pore diameter can be performed on the order of sub-nanometers, in other words, in units of m ⁇ 10 ⁇ 10 (m is 1 to 9).
- the porous silica is made into nanoparticles. That is, by adding a water-soluble polymer to the reaction system and bringing it into contact with a basic aqueous solution (basic solution, alkaline solution having a pH greater than 7), porous silica nanoparticles can be formed.
- a basic aqueous solution basic solution, alkaline solution having a pH greater than 7
- porous silica nanoparticles can be formed.
- the shape of the synthesized porous silica was analyzed in more detail and the verification was deepened.
- water-soluble polymer an inexpensive and general-purpose polymer such as polyethylene glycol (PEG) can be used.
- PEG polyethylene glycol
- the average molecular weight of polyethylene glycol is not limited, but is preferably from several hundred to several thousand.
- polyethylene oxide or the like may be used in addition to the above PEG.
- a water-soluble polymer such as PEG is also soluble in silicate ions and produces a uniform solution.
- porous silica particles having a particle diameter (diameter) of 10 to 20 nm can be produced.
- a product can be obtained as an aggregate
- the nanoparticles themselves form an aggregate, but the pores in the interstices function as new mesopores because they are connected to each other.
- the average pore diameter of the particle gap is, for example, about 50 nm.
- the aggregate of nanoparticles is obtained as a white monolith (single lump) and has sufficient strength against impact.
- Example C [Synthesis of porous silica nanoparticles]
- TEOS 8 g (0.038 mol; 1 eq) as a silica source was placed in a polypropylene container, 0.2 to 1.2 equivalents of a surfactant was added, and 7.5 g of PEG having an average molecular weight of 1000 was further added.
- water adjusted to pH 0-2 with hydrochloric acid was added in an amount of 2-4 equivalents and stirred at room temperature.
- the TEOS hydrolysis proceeded with stirring for 1 hour, and an almost uniform solution in which the surfactant and polyethylene glycol were dissolved was obtained. This solution (precursor solution) was kept at room temperature or 60 ° C.
- Cationic surfactants include octadecyltrimethylammonium chloride (C18TAC), hexadecyltrimethylammonium chloride (C16TAC), tetradecyltrimethylammonium bromide (C14TAB), dodecyltrimethylammonium bromide (C12TAB), decyltrimethylammonium bromide (C10TAB), Any of octyltrimethylammonium bromide (C8TAB), hexyltrimethylammonium bromide (C6TAB), and butyltrimethylammonium chloride (C4TAC) can be used.
- C18TAC octadecyltrimethylammonium chloride
- C16TAC hexadecyltrimethylammonium chloride
- tetradecyltrimethylammonium bromide C14TAB
- dodecyltrimethylammonium bromide C12TAB
- the precursor solution formed using C6TAB was dropped into the basic aqueous solution.
- a 28% aqueous ammonia solution was used as the basic aqueous solution.
- the pH is about 13.
- the dripped substantially granular precursor solution became a gel and precipitated in an aqueous ammonia solution.
- the obtained gel was dried at 60 ° C. and calcined at 600 ° C. for 3 hours to remove the surfactant and polyethylene glycol.
- the obtained porous silica was obtained in the form of colorless beads.
- the bead shape corresponds to the dripping shape of the precursor solution.
- an aqueous solution of an amine can be used in addition to the aqueous ammonia solution.
- These bases are easy to remove in the drying and firing processes, and are suitable for use as a basic aqueous solution.
- silica begins to dissolve in a high pH region of pH 14 or higher, when a basic aqueous solution in the high pH region is used, it is preferable to take it out of the solution immediately after the reaction (after gelation and after polymerization). .
- the dissolution rate of silica increases. More preferred.
- FIG. 17 shows nitrogen adsorption and desorption isotherms of porous silica nanoparticles synthesized using C16TAC and porous silica nanoparticles synthesized using C6TAB.
- the porous silica nanoparticles (C16) synthesized using C16TAC are simply gelled and fired.
- the porous silica nanoparticles (C6) synthesized using C6TAB are gelled in a basic aqueous solution.
- part (a) the graph is bent and the inclination is changed.
- a part (a) corresponds to the IV type of the IUPAC classification, and the presence of mesopores is presumed.
- a bent portion of the graph exists also in the (b) portion, and a hysteresis loop can also be confirmed.
- This part (b) also corresponds to the above-mentioned type IV, and the existence of larger mesopores is presumed.
- part (c) a sudden increase in the amount of adsorption is confirmed in part (c).
- a part (c) corresponds to the IUPAC classification type I, and the presence of micropores is presumed.
- a bent portion of the graph exists in the portion (d), and a hysteresis loop can also be confirmed.
- Such a (d) part corresponds to the above IV type, and the existence of mesopores is also assumed.
- FIG. 18 is a graph showing the pore size distribution of porous silica nanoparticles synthesized using C16TAC.
- the average pore diameter was measured using the BJH method.
- two pore sizes are confirmed in the porous silica. That is, the structure of porous silica having two pores, a mesopore derived from a surfactant of about 2 nm and a mesopore corresponding to a particle gap of about 20 to 50 nm was confirmed.
- FIG. 19 is a graph showing the pore size distribution of porous silica synthesized using C6TAB.
- the average pore diameter was measured using the GCMC method.
- two pore diameters are confirmed in the porous silica nanoparticles. That is, the structure of porous silica having two pores, that is, a micropore derived from a surfactant of about 1 nm and a mesopore corresponding to a particle gap of about 5 to 10 nm was confirmed.
- the above phenomenon can be considered as follows.
- the silicate ions are neutral or positively charged. Therefore, the silicate ion interacts with polyethylene glycol through hydrogen bonds and electrostatically interacts with the surfactant via the counter anion.
- the ability to form micelles is low. I can't do it. Therefore, only amorphous silica can be obtained.
- the pH of the system is drastically increased by dropwise addition to a basic aqueous solution, the silicate ion is negatively charged, and it is stronger than the cationic surfactant, without a counter anion. Electrostatic interaction occurs.
- Example D The dynamic adsorption ability of toluene of the porous silica (sample) synthesized in Example A and Example B was measured.
- a dynamic adsorption evaluation apparatus manufactured by Okura Giken Co., Ltd.
- the measurement was performed at a toluene concentration of 100 ppm, a wind speed of 1 m / second, a flow rate of 10.6 L / min, a sample amount of 6.4 mL, and a sample tube inner diameter of 15 mm.
- the sample was pretreated for about one hour at 200 ° C. under a flow of dry air.
- porous silica (C8V) synthesized using C8TAC examined in Example B by adding an organic silane and the porous silica (C6V) synthesized using C6TAC are more than the above C16, C8 and C6. It was found that the amount of adsorption increased and the adsorption performance was comparable to activated carbon.
- the parenthesis indicates the average pore diameter.
- suction performance of toluene is improving, so that a pore diameter is small.
- the adsorption performance varies depending on the consistency between the adsorbate, the size, and the pore diameter, and the adsorption performance is not necessarily improved as the pore diameter is smaller for any substance. Therefore, as described in detail in the above embodiment, the adsorption performance can be improved by designing the porous silica having pores corresponding to the adsorbate.
- porous silica of the present invention since a main component SiO 2, less risk of such as activated carbon ignition. In particular, when an organic solvent is adsorbed, the ignitability increases, but the porous silica of the present invention can reduce such a risk. Therefore, it is suitable for use as an adsorbent.
- the porous silica of the present invention is superior in adsorbate desorption properties than activated carbon. Therefore, the adsorbate can be reused as an adsorbent after desorption, for example, immediately after heat treatment or solvent treatment. Further, by utilizing the desorption property, the adsorbate can be easily recovered and reused.
- a cationic surfactant having a hydrophobic part having 2 to 7 carbon atoms is used as a template, mesoporous silica having a pore diameter of less than 2 nm obtained under solvent-free conditions, a water-soluble polymer is added, or a surface-active property is added.
- mesoporous silica nanoparticles obtained by excessively adding the agent monolithic, bead-like, thin-film, and fibrous mesoporous silica obtained by molding the mesoporous silica precursor solution, and their production method it can.
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Abstract
Description
本発明では、溶媒を用いずにアルコキシシランとカチオン性界面活性剤をそのまま混合し、反応剤として水を添加してpHを調整することで得られる前駆体溶液をゲル化する。
〔モノリス状メソポーラスシリカの合成〕
ポリプロピレン製容器にシリカ源としてテトラエトキシシラン(TEOS)8g(0.038mol;1eq)を入れ、続いて界面活性剤であるヘキサデシルトリメチルアンモニウムクロライド(C16TAC)、オクチルトリメチルアンモニウムブロミド(C8TAB)、ヘキシルトリメチルアンモニウムブロミド(C6TAB)、ベンジルトリメチルアンモニウムクロライド(BzTAC)のいずれかを2.4g(C16TACの場合0.0075mol;0.2eq)を分散させ、撹拌した。ここに、塩酸を用いてpH2に調整した水を2.74g(0.152mol;4eq)入れ、室温で撹拌した。一時間の撹拌でTEOSの加水分解が進行し、界面活性剤が溶解した。この溶液(前駆体溶液)を室温または60℃に保持し、継続して撹拌あるいは静置した。12時間から数日でゲル化が完了し、溶液全体が目視で無色透明のゲル状となった。このゲルを60℃で乾燥、600℃で3時間焼成し、界面活性剤を除去した。図1に示すように、得られたメソポーラスシリカは、無色透明のモノリス状(多孔質状)で得られた。得られたメソポーラスシリカの窒素吸脱着等温線を、図2に示した。C16TACを用いた場合には、等温線はIUPAC(国際純正応用化学連合)の分類のIV型を示し、メソ細孔の存在を示している。C8TAB、C6TAB、BzTACを用いた等温線はIUPACの分類のI型を示し、ミクロ孔の存在を示している。界面活性剤の炭素数と得られたメソポーラスシリカの比表面積、細孔容積、平均細孔径を表1にまとめた。C16TACの場合、BET比表面積は1203m2/g、細孔容積は0.58cm3/gであった。また、BJH細孔解析の結果から、平均細孔径は2.1nmであることがわかった。C8TAB、C6TAB、BzTACを用いた場合、BET比表面積はそれぞれ、552、617、480m2/g、細孔容積はそれぞれ、0.28、0.32、0.25cm3/gであった。C8以下の界面活性剤を用いた場合、平均細孔径は2nm未満であり、BJH解析では正確に求められないため、BzTACを除いてGCMC法を用いて解析を行った。GCMC法は細孔径を大きく見積もる傾向があるため、ドデシルトリメチルアンモニウムブロミド(C12TAB)を用いて従来法で合成したメソポーラスシリカのGCMC解析結果もあわせて図3に示した。BJH解析によれば、C12TABの細孔径は2nmである。ここから、GCMC法が0.5~0.6nm程度、細孔径を過剰に見積もると仮定すると、C8TABを用いて合成されたメソポーラスシリカの細孔径は1~1.2nm程度、C6TABを用いた場合にはさらに減少し、0.8~1nm程度と見積もることができる。
〔PEG添加によるモノリス状メソポーラスシリカナノ粒子の合成〕
ポリプロピレン製容器にシリカ源としてTEOS8g(0.038mol;1eq)を入れ、続いてC16TAC、C8TAB、C6TABのいずれかを2.4g(0.0075mol;0.2eq)を分散させ、さらにポリエチレングリコール(平均分子量1000;7.5g)を入れ、撹拌した。ここに、塩酸を用いてpH2に調整した水を2.74g(0.152mol;4eq)入れ、撹拌した。一時間の撹拌でTEOSの加水分解が進行し、界面活性剤およびポリエチレングリコールが溶解した。この溶液を室温あるいは60℃に保持し、撹拌あるいは静置した。12時間から数日でゲル化が完了し、溶液全体が目視で無色透明のゲル状となった。このゲルを60℃で乾燥、600℃で3時間焼成し、界面活性剤およびポリエチレングリコールを除去した。図4に示すように、得られたメソポーラスシリカは、白色のモノリス状で得られた。得られたメソポーラスシリカの窒素吸脱着等温線を、図5に示した。等温線は、C16TACではIV型、C8TABおよびC6TABではI型を示し、メソ細孔およびミクロ孔の存在をそれぞれ示している。さらに、相対圧0.8~0.9付近に急激な吸着量の増加が見られるが、これは、モノリス体を構成するメソポーラスシリカ自体が10~20nmのナノ粒子となることで粒子間隙に生成した、第2のメソ孔への毛管凝縮によるものである。それぞれのメソポーラスシリカナノ粒子の比表面積、細孔容積、平均粒子間隙細孔直径を表2にまとめた。C16TAC、C8TAB、C6TABそれぞれ、BET比表面積が1670、954、630m2/g、細孔容積は1.70、1.96、1.60cm3/gであった。BJH細孔解析の結果から、いずれの試料でもナノ粒子間隙由来の平均細孔直径は約40nmであることがわかった。粒子サイズと粒子間隙サイズは、図6に示すように、同試料の透過型電子顕微鏡(TEM)像によっても確認できる。
実施例2のゲル化前の前駆体溶液を、シリンジで28%のアンモニア水溶液に、それぞれ滴下した。滴下した前駆体溶液は、アンモニア水溶液に入った瞬間に球形を保ったままゲル化した。沈降した球状ゲルを回収し、乾燥させ、600℃で3時間焼成し、界面活性剤およびポリエチレングリコールを除去した。得られたビーズ状メソポーラスシリカの写真を、図7に示した。写真からもわかるように、前駆体溶液中に、ポリエチレングリコールを添加した場合には散乱のため白色球状となった。得られたビーズは、約2~3mmの球形であった。
実施例1~3のゲル化前の前駆体溶液を、スピンコーターでガラス基板状に、それぞれスピンコートした。コートしたガラス基板ごとにアンモニア蒸気中に数十秒曝露し、ゲル化を完了させた。その後乾燥、600℃で3時間焼成し、界面活性剤およびポリエチレングリコールを除去した。得られた薄膜のうち、実施例1の前駆体溶液を用いた場合を例として、写真を図8に示した。
実施例1で得られたメソポーラスシリカの吸着材としての性能を評価するために、トルエンの動的吸着能を測定した。測定には動的吸着評価装置(大倉技研社製)を用い、トルエン濃度100ppm、風速1m/秒、風量10.6L/分、サンプル量6.4mL、サンプル管内径15mmで行った。試料は、乾燥空気流通下200℃で約一時間の前処理を行った。図9に、各試料1gあたりのトルエンの動的吸着量、および非特許文献5に記載されている市販シリカゲルQ3と繊維状メソポーラスシリカ(SBA-15 fiber)の動的吸着量をあわせて示した。本発明で得られたC6TABを鋳型とするメソポーラスシリカは、既存のメソポーラスシリカ(SBA-15 fiber)と比較して約2倍のトルエン動的吸着量を有していた。これは、メソポーラスシリカ細孔のミクロ孔化により、従来法では不可能であった大きなミクロ孔容積を有していることに起因する。
本実施の形態2では、実施の形態1と同様に、溶媒を用いずにアルコキシシランとカチオン性界面活性剤をそのまま混合し、反応剤として水を添加してpHを調整することで得られる前駆体溶液をゲル化する。水中で形成される界面活性剤の棒状ミセルを鋳型とし、アルコキシシランを加水分解することで、細孔を有する筒状のシリカ(SiO2)を形成する。このようなシリカを、ポーラスシリカ(多孔質シリカ)という。ここでは、検討したカチオン性界面活性剤種を増やし、さらに、検証を深めた。
〔モノリス状ポーラスシリカの合成〕
ポリプロピレン製容器にシリカ源としてテトラエトキシシラン(TEOS)8g(0.038mol;1eq)を入れ、続いてカチオン性界面活性剤を、0.2~1.2eq(0.038mol×0.2~0.038mol×1.2)を分散させ、撹拌した。この時点で、TEOSと界面活性剤とは混じり合わない。即ち、均一な混合液とならない。カチオン性界面活性剤としては、オクタデシルトリメチルアンモニウムクロライド(C18TAC)
ヘキサデシルトリメチルアンモニウムクロライド(C16TAC)、テトラデシルトリメチルアンモニウムブロミド(C14TAB)、ドデシルトリメチルアンモニウムブロミド(C12TAB)、デシルトリメチルアンモニウムブロミド(C10TAB)、オクチルトリメチルアンモニウムブロミド(C8TAB)、ヘキシルトリメチルアンモニウムブロミド(C6TAB)、ブチルトリメチルアンモニウムクロライド(C4TAC)の8種類を用いて、それぞれポーラスシリカを合成した。
本実施の形態では、有機シラン化合物を添加することにより、細孔の微細化を図る。
次いで、ポーラスシリカの形状加工について説明する。例えば、反応容器中で上記前駆体溶液をゲル化し、静置、あるいは撹拌することで、反応容器の形状に依存したモノリス状ポーラスシリカ成型体が製造可能である。反応容器の形状を選択することで、ペレット、球状、ロッド状、ディスク状など、任意の形状に成型することができる。
本実施の形態においては、これまでに説明した内容により、以下の効果を奏することができる。
〔有機シラン添加による細孔径制御〕
ポリプロピレン製容器にシリカ源としてテトラエトキシシラン(TEOS)8g(0.038mol;1eq)とトリエトキシビニルシラン(TEVS)を8g×5%(0.038mol×5%)とを混合し、続いて界面活性剤を0.2~1.2等量を添加し、撹拌した。この混合物に、塩酸を用いてpH0~2に調整した水を2~4等量の範囲で添加し、室温で撹拌した。1時間程度の撹拌でTEOSの加水分解が進行し、ほぼ均一な溶液が得られた。さらに、この溶液(前駆体溶液)を室温または60℃に保持し、継続して撹拌あるいは静置した。12時間から数日でゲル化が完了し、溶液全体が目視で無色透明のゲル状となった。このゲルを60℃で乾燥、600℃で3時間焼成し、界面活性剤を除去した。界面活性剤としては、カチオン性界面活性剤である、オクチルトリメチルアンモニウムブロミド(C8TAB)、ヘキシルトリメチルアンモニウムブロミド(C6TAB)、ブチルトリメチルアンモニウムクロライド(C4TAC)の3種類を用いて、それぞれについてポーラスシリカを形成した。
本実施の形態4では、実施の形態1と同様に、ポーラスシリカのナノ粒子化を図る。即ち、反応系に、水溶性高分子を添加するとともに、塩基性水溶液(塩基性溶液、pHが7より大きいアルカリ液)と接触させることで、ポーラスシリカのナノ粒子化が可能となる。ここでは、合成されたポーラスシリカの形状をさらに詳細に解析し、検証を深めた。
〔ポーラスシリカナノ粒子の合成〕
ポリプロピレン製容器にシリカ源としてTEOS8g(0.038mol;1eq)を入れ、界面活性剤を0.2~1.2等量を添加した後、さらに、平均分子量1000のPEGを7.5g添加し、撹拌した。この混合物に、塩酸を用いてpH0~2に調整した水を2~4等量の範囲で添加し、室温で撹拌した。1時間の撹拌でTEOSの加水分解が進行し、界面活性剤およびポリエチレングリコールが溶解したほぼ均一な溶液が得られた。この溶液(前躯体溶液)を室温あるいは60℃に保持し、撹拌あるいは静置した。12時間から数日でゲル化が完了し、溶液全体が目視で無色透明のゲル状となった。このゲルを60℃で乾燥、600℃で3時間焼成し、界面活性剤およびポリエチレングリコールを除去した。
本実施の形態5では、実施例Aおよび実施例Bで合成したポーラスシリカの吸着性能について検討した。吸着質としては、トルエンを用いた。
実施例Aおよび実施例Bで合成したポーラスシリカ(試料)のトルエンの動的吸着能を測定した。測定には動的吸着評価装置(大倉技研社製)を用い、トルエン濃度100ppm、風速1m/秒、風量10.6L/分、サンプル量6.4mL、サンプル管内径15mmで行った。試料は、乾燥空気流通下200℃で約一時間の前処理を行った。図20に、各試料1gあたりのトルエンの動的吸着量(Vads)、および非特許文献5に記載されている市販の活性炭(Activated carbon)と繊維状メソポーラスシリカ(SBA-15 fiber)の動的吸着量をあわせて示した。また、市販シリカゲルQ3の動的吸着量についても同様に測定した。
Claims (20)
- アルコキシシランの加水分解により多孔質シリカを製造する方法であって、界面活性剤、アルコキシシランおよび水の存在下にて、前記アルコキシシランは、溶媒としての水を含有しない系で加水分解されることを特徴とする多孔質シリカの製造方法。
- 請求項1に記載の多孔質シリカの製造方法において、前記アルコキシシランと前記水との化学量論比をアルコキシシラン:水=1:nとした場合、nを20以下とし、pHを0~2とした条件下で加水分解されることを特徴とする多孔質シリカの製造方法。
- 請求項2に記載の多孔質シリカの製造方法において、疎水部の炭素数が2~7であるカチオン性界面活性剤のミセルを鋳型としてシリカを形成することにより、前記炭素数に対応する細孔を有する多孔質シリカを形成することを特徴とする多孔質シリカの製造方法。
- 請求項3に記載の多孔質シリカの製造方法において、前記細孔の平均細孔直径は、0.7以上1.5nm以下であることを特徴とする多孔質シリカの製造方法。
- 請求項1に記載の多孔質シリカの製造方法において、カチオン性界面活性剤の疎水部の炭素数と細孔径との相関を調べる工程と、吸着質に応じた細孔径を設計する工程と、前記相関から設計された前記細孔径に対応する炭素数を選択する工程と、選択された前記炭素数を有する前記カチオン性界面活性剤の存在下にて前記アルコキシシランを加水分解することを特徴とする多孔質シリカの製造方法。
- 請求項1または5に記載の多孔質シリカの製造方法において、前記界面活性剤、前記アルコキシシランおよび前記水に加え、有機シランの存在下において、前記アルコキシシランを加水分解することを特徴とする多孔質シリカの製造方法。
- 請求項6に記載の多孔質シリカの製造方法において、前記有機シランは、炭素とシリコンとの結合部と、前記シリコンと結合し、前記炭素を含む有機官能基と、前記シリコンと結合するアルコキシル基と、を有することを特徴とする多孔質シリカの製造方法。
- 請求項7に記載の多孔質シリカの製造方法において、前記有機官能基は、ビニル基であることを特徴とする多孔質シリカの製造方法。
- 請求項1に記載の多孔質シリカの製造方法において、前記界面活性剤、前記アルコキシシランおよび前記水に加え、水溶性高分子の存在下において、前記アルコキシシランを加水分解することを特徴とする多孔質シリカの製造方法。
- 請求項9に記載の多孔質シリカの製造方法において、前記界面活性剤、前記アルコキシシラン、前記水および前記水溶性高分子を有する混合液を、塩基性溶液と接触させることを特徴とする多孔質シリカの製造方法。
- 請求項10に記載の多孔質シリカの製造方法において、前記塩基性溶液はアンモニア水溶液であることを特徴とする多孔質シリカの製造方法。
- 請求項10に記載の多孔質シリカの製造方法において、前記混合液を、前記塩基性溶液に滴下させることを特徴とする多孔質シリカの製造方法。
- 請求項9に記載の多孔質シリカの製造方法において、前記水溶性高分子は、ポリエチレングリコールまたはポリエチレンオキシドであることを特徴とする多孔質シリカの製造方法。
- 請求項10に記載の多孔質シリカの製造方法において、前記多項質シリカは、多項質シリカの粒子の集合体であって、前記粒子を構成する多孔質シリカの第1細孔の平均細孔直径は、0.7以上1.5nm以下であり、
前記粒子間の第2細孔の平均細孔直径は、10以上50nm以下であることを特徴とする多孔質シリカの製造方法。 - 細孔を有する多孔質シリカであって、平均細孔直径が、0.7以上1.5nm以下であることを特徴とする多孔質シリカ。
- 請求項15記載の多孔質シリカにおいて、細孔容積が、0.25cm3/g以上であることを特徴とする多孔質シリカ。
- 請求項16記載の多孔質シリカにおいて、前記細孔は、疎水部の炭素数が2~7であるカチオン性界面活性剤のミセルと対応することを特徴とする多孔質シリカ。
- 請求項15記載の多孔質シリカにおいて、前記多孔質シリカは、前記細孔を有する粒状物の集合体であって、前記粒状物間に隙間を有することを特徴とする多孔質シリカ。
- 請求項18記載の多孔質シリカにおいて、前記隙間よりなる第2細孔の平均細孔直径は、10以上50nm以下であることを特徴とする多孔質シリカ。
- 請求項15記載の多孔質シリカにおいて、ビーズ状、膜状または繊維状であることを特徴とする多孔質シリカ。
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JP2019023255A (ja) * | 2017-07-24 | 2019-02-14 | 株式会社アドヴィックス | 乾式ブレーキ用摩擦材 |
JP2020029394A (ja) * | 2018-08-17 | 2020-02-27 | 地方独立行政法人東京都立産業技術研究センター | 多孔質シリカ、機能材料および多孔質シリカの製造方法 |
JP7352936B2 (ja) | 2018-08-17 | 2023-09-29 | 地方独立行政法人東京都立産業技術研究センター | 多孔質シリカ、機能材料および多孔質シリカの製造方法 |
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KR101750584B1 (ko) | 2017-06-23 |
EP2543636A4 (en) | 2015-12-09 |
JP5647669B2 (ja) | 2015-01-07 |
KR20130001255A (ko) | 2013-01-03 |
CN102834355A (zh) | 2012-12-19 |
JP2015003860A (ja) | 2015-01-08 |
US20130052117A1 (en) | 2013-02-28 |
CN102834355B (zh) | 2015-06-24 |
JP5827735B2 (ja) | 2015-12-02 |
JPWO2011108649A1 (ja) | 2013-06-27 |
EP2543636A1 (en) | 2013-01-09 |
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