CN103539135A - Preparation method of mesoporous silica suspension with stable colloidal state - Google Patents

Abstract

The invention discloses a preparation method of a mesoporous silica suspension with a stable colloidal state. The preparation method comprises the following steps of: grinding hydrothermally synthesized mesoporous silica nanoparticles into ultrafine powder; then preparing the ultrafine powder into a silica solution having a solid-to-liquid ratio of 0.001%-1.0%; adjusting pH value to 8.0-10.0 with inorganic/organic alkali; then transferring the solution to a reaction kettle; controlling reaction temperature and stirring time; centrifugally separating, and washing with anhydrous ethanol many times to obtain a powder product; re-dispersing the powder product in anhydrous ethanol and carrying out ultrasonic treatment to obtain the mesoporous silica suspension with the stable colloidal state. By using the preparation method, the technical problems of storage and re-dispersing of the mesoporous silica nanoparticles are effectively solved; and the synthetic method is simple, short in period, low in cost, good in repeatability and environment-friendly and can be put into large-scale production easily,.

Description

The preparation method of the meso-porous titanium dioxide silicon suspension that a kind of colloidal state is stable

Technical field

The present invention relates to inorganic chemical synthesis technical field, the preparation method of the meso-porous titanium dioxide silicon suspension that especially a kind of colloidal state is stable.

Background technology

Mesopore silicon dioxide nano material is a kind of novel inorganic nano material with characteristics such as high-specific surface area, large pore volume, pattern and size are controlled, and the applied research in fields such as Materials science, biological medicine, environment protection, biosensors in recent years attracts wide attention.The main policies of current synthesizing mesoporous silicon dioxide nano particle (MSN) comprising: first, use single cationicsurfactants as template (Angew. Chem. Int. Ed., 2002,2151,2317.), early stage what react, by carrying out cancellation particle growth by a large amount of water-reducible methods, thereby prepared the mesoporous silica nano-particle that size is less than 100 nm, but the silica dioxide granule of preparation cannot overcome out-of-shape and the uneven first-class defect of distribution of sizes; The second, by improved St ber method (J. Phys. Chem. B 2004,108,20122.), using ethanol as the cosurfactant of CTAB cats product, can obtain highly monodispersed mesoporous silica nano-particle, but particle size often surpasses 100 nm; The 3rd, Bein is by being used trolamine (TEAH ₃) replacement mineral alkali can synthesize size and be less than 200 nm meso-porous nano silica dioxide granules (Adv. Funct. Mater. 2007,17,605.), but trolamine (TEAH ₃) consumption very big, and product need be processed and just can obtain final particle through high speed centrifugation; The 4th, Kuroda has reported that a new synthesis strategy comes preparation size to be less than the mesoporous SiO of 50nm recently ₂nano particle, but the molar ratio of CTAB/TMOS is greater than 0.5, and the high and tensio-active agent of synthetic cost need could be removed (Chem. Commu., 2009,5094.) by complicated dialysis process; The 5th, Chinese patent CN1923684A utilizes sarcosyl to make template, (3-aminopropyl) Trimethoxy silane of take is co-structured directed agents, synthesized big or small even, the controlled nano SiO 2 particle of size, but synthetic cost is relatively high; The 6th, the synthesis strategy of mixed templates can be used for synthetic highly monodispersed mesoporous nano-grain equally, but the price limit of tensio-active agent costliness its apply widely (SCI, 2011,32,560.).At Chinese patent CN 102616795 A and research paper (J. Am. Chem. Soc., 2013,135,2427 2430.) in, reported that use cetyl trimethyl p-methyl benzenesulfonic acid ammonium salt (CTATos) is as template, can synthesize the controlled mesoporous silica nano-particle of highly monodispersed size, only need just can obtain final product by the way of direct suction filtration, the feather weight that has realized first mesoporous silica nano-particle is synthetic.Although the preparation of this synthetic method is simple, resulting particle is again after ultrasonic dispersion, colloidal stability extreme difference, and easily there is serious reunion and coagulation in several minutes later.Therefore researching and developing new rear synthesis modification technology is the top priority of the mesoporous silica nano-particle suspension that current preparation colloidal state is stable.

Summary of the invention

The object of the present invention is to provide a kind of hydro-thermal aftertreatment to prepare the green method of the meso-porous titanium dioxide silicon suspension that colloidal state is stable.

The object of the present invention is achieved like this:

The preparation method of the meso-porous titanium dioxide silicon suspension that a kind of colloidal state is stable, the method is: directly use the mesoporous silica nano-particle of Hydrothermal Synthesis as original material, grinding to form superfine powder, to be made into solid-to-liquid ratio be 0.001～1.0% silicon dioxde solution later, then utilize inorganic/organic bases adjust pH between 8.0～10.0, above-mentioned solution is transferred in reactor, control temperature of reaction and churning time, through centrifugation, absolute ethanol washing for several times, obtain powder product, product is scattered in dehydrated alcohol again through supersound process, finally prepare the meso-porous titanium dioxide silicon suspension that colloidal state is stable,

Described mesoporous silica nano-particle is of a size of 80～200nm, uses traditional cats product as template, and the synthesis strategy by self-assembly under alkaline condition prepares;

Described solid-to-liquid ratio is the weight ratio of silica solid in 95% ethanolic soln;

Described mineral alkali is sodium hydroxide, potassium hydroxide or ammoniacal liquor;

Described organic bases is Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, TPAOH or triethylamine;

Described temperature of reaction is 20～100 ℃, and churning time is 6～24 hours.

Mesoporous silica nano-particle used in the present invention is with reference to preparing gained as Publication about Document: kun Zhang , * Lang-Lang Xu, Jin-Gang Jiang, Koon-Fung Lam, San-Jun Zhang, hai-Hong Wu, * Guang-Dong Wu, B é len Albela, laurent Bonneviot, * Peng Wu, Facile Large-Scale Synthesis of Monodisperse Mesoporous Silica Nanospheres with Tunable Pore Structure, j. Am. Chem. Soc., 2013, 135,2,427 2430.

The present invention compared with prior art tool has the following advantages:

(1) can effectively solve the technical barrier that mesoporous silica nano-particle stores and again disperses.

(2) simple, the synthetic cost of preparation method is low.

(3) the method for sample by simple supersound process just can be distributed in the middle of ethanol polar protic solvent, obtains high stability colloidal solution.

Embodiment

Below by embodiment, the invention will be further described, and its object is only better to understand research contents of the present invention but not limits the scope of the invention.

The preparation of mesoporous silica nano-particle:

First 2.74g cetyl trimethyl p-methyl benzenesulfonic acid ammonium salt (CTATos) is joined to the trolamine (TEAH that contains 144ml deionized water, 0.38g ₃) beaker in, 80 ℃ of constant temperature stir and become clarification to solution in 1 hour, then 20.83g tetraethoxy silicon ester (TEOS) are joined rapidly in this beaker, 80 ℃ of constant temperature continue to stir 2 hours, obtain white precipitate, the mol ratio of this each component of mixture is SiO ₂: CTATos:TEAH ₃: H ₂o=1:0.06:0.026:0.02:80; To obtain the direct suction filtration of mixture, washing, oven dry, obtain mesoporous SiO ₂nano particle, productive rate 85%, median size 100 nm.

Embodiment 1

First use mortar to grind the 1.0g mesoporous silicon dioxide powder of preparing above and evenly obtain superfine powder; join in the ethanolic soln that contains 100ml 90%; ultrasonic dispersion treatment 15 minutes, is used the pH value of NaOH (0.1M) solution regulation system 8.0～9.0; Then in the reactor of transferase 12 00 ml, 60 ℃ of constant temperature stir 12 hours, centrifugation, use absolute ethanol washing three times, then within ultrasonic 15 minutes, be scattered in dehydrated alcohol, obtain the meso-porous titanium dioxide silicon suspension that colloidal state is stable, in 24 hours, do not have apparent coagulation phenomenon to occur.

Embodiment 2

First use mortar to grind evenly the 1.0 g mesoporous silicon dioxide powders of preparing above, join in the ethanolic soln that contains 100 ml 90%, ultrasonic dispersion treatment 15 minutes, is used the pH value of ammoniacal liquor (28%) solution regulation system 8.0～9.0; Then in the reactor of transferase 12 00 ml, 60 ℃ of constant temperature stir 12 hours, centrifugation, use absolute ethanol washing three times, then within ultrasonic 15 minutes, be scattered in dehydrated alcohol, obtain the meso-porous titanium dioxide silicon suspension that colloidal state is stable, in 24 hours, do not have apparent coagulation phenomenon to occur.

Embodiment 3

First use mortar to grind evenly the 1.0 g mesoporous silicon dioxide powders of preparing above; join in the ethanolic soln that contains 100 ml 90%; ultrasonic dispersion treatment 15 minutes, is used the pH value of Tetramethylammonium hydroxide (0.1M) solution regulation system 8.0～9.0; Then in the reactor of transferase 12 00 ml, 30 ℃ of constant temperature stir 24 hours, centrifugation, use absolute ethanol washing three times, then within ultrasonic 15 minutes, be scattered in dehydrated alcohol, obtain the meso-porous titanium dioxide silicon suspension that colloidal state is stable, in 24 hours, do not have apparent coagulation phenomenon to occur.

Claims (1)

1. the preparation method of the meso-porous titanium dioxide silicon suspension that a colloidal state is stable, it is characterized in that the method is by the mesoporous silica nano-particle of Hydrothermal Synthesis, grinding to form and being made into solid-to-liquid ratio after superfine powder is 0.001～1.0% silicon dioxde solution, use again inorganic/organic bases adjust pH between 8.0～10.0, then above-mentioned solution is transferred in reactor, control temperature of reaction and churning time, through centrifugation, absolute ethanol washing for several times, obtain powder product, product is scattered in dehydrated alcohol and through supersound process again, obtain the meso-porous titanium dioxide silicon suspension that colloidal state is stable, wherein:

Described mesoporous silica nano-particle superfine powder is of a size of 80～200nm;

Described solid-to-liquid ratio is the weight ratio of silica solid in 95% ethanolic soln;

Described mineral alkali is sodium hydroxide, potassium hydroxide or ammoniacal liquor;

Described organic bases is Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, TPAOH or triethylamine;

Described temperature of reaction is 20～100 ℃, and churning time is 6～24 hours.