CN101613537B - Method for preparing nano silicon dioxide coated by nano titanium dioxide - Google Patents
Method for preparing nano silicon dioxide coated by nano titanium dioxide Download PDFInfo
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Abstract
The invention discloses a method for preparing nano silicon dioxide coated by nano titanium dioxide, which is implemented by firstly dripping inorganic acid in silicate solution under the conditions of stirring and ultrasonic, controlling pH, reaction temperature and time of a reaction system to obtain white silicic acid collosol, drying to obtain silicic acid gel, then mixing the silicic acid gel with water followed by bal milling, rinsing and filtering to obtain gel, hot decomposing the silicic acid gel to obtain silicon dioxide powder; secondly, mixing the silicon dioxide powder with a mixed solution of glacial acetic acid, water and absolute alcohol under the conditions of stirring and ultrasonic; and thirdly, adding mixed solution of Tetrabutyl orthotita and absolute alcohol to the mixture, standing, drying and ball milling the mixture to obtain silicon dioxide powder coated by titanic acid gel, then heating for decomposition to obtain composite material powder. The grain diameter of the composite material of silicon dioxide coated by nano titanium dioxide is 1-100nm and the purity thereof is over 99.8%.
Description
Technical field
The present invention relates to fields such as photochemical catalyst, electrochemical catalyst, organic synthesis, meticulous article chemical industry, more specifically relate to a kind of preparation method of nano silicon dioxide coated by nano titanium dioxide.The prepared nano silicon dioxide coated by nano titanium dioxide matrix material of the present invention can be as photocatalyst, electrochemical catalyst, the catalyzer of organic synthesis and the additive of meticulous article Chemicals etc. of water treatment.
Background technology
Nano titanium oxide is behind the ultraviolet irradiation that receives sunshine or luminescent lamp, and inner electronics will excite.Consequently, produced the hole of electronegative electronics and positively charged.Electronics makes the hydrogen reduction in air or the water, generates ydrogen peroxide 50, then works to the direction of oxidized surface water molecules in the hole, produces hydroxyl atomic group.These all are active oxygens, and powerful oxidative decomposition capacity is arranged, thereby can decompose, remove the various organism attached to titania surface.Titanium oxide not only has powerful oxidative decomposition capacity, and the advantages such as light of self not decomposing, almost can permanently work and can utilize sunlight and luminescent lamp in addition.In exhaust gas purification, deodorization, water treatment, field such as antifouling, titanium dioxide optical catalyst has wide application prospect.Nano titanium oxide is tiny because of its particle, specific surface area has the not available special effects of conventional material greatly; Colour effect like quantum effect, tunnel effect, uniqueness; And photocatalysis and function such as ultraviolet shielded; Demonstrate wide application prospect at aspects such as functional coating, automobile, makeup, health care, wastewater treatment, environmental protection, related application research is extremely active.In recent years, nano titanium oxide is owing to its light stability, the nontoxic solar energy converting that becomes are that electric energy is the material that solar cell the most generally uses.In addition; The good ultraviolet screener effect that nano titanium oxide has, the transparency and characteristics such as nontoxic; Make its ideal that becomes sunscreen class skin-protection product add material, and have good dispersiveness, thereby adopt the Plastic Packaging Materials transparency of nano titanium oxide preparation very high; Because of its ultraviolet resistance that has and nontoxicity, can be used as natural and good ultraviolet line screener regenerated fiber.Simultaneously, nano titanium oxide also can be used as the additive of resin ink colorant, Zylox strengthening agent, solid lubricant, efficient light-sensitive catalyst, sorbent material etc.Nano titanium oxide is widely used at aspects such as sun care preparations, sedan limousine metal finish paint, electronic industry, duplicating machine industry, high voltage insulating materials, ic substrate, fluorescent tubes.
Characteristics such as nano silicon has that particle size is little, micropore is many, specific surface area is big, The adsorbed hydroxyl content is high, ultraviolet, visible light and infrared reflection ability are strong.Perfect along with the product surface treatment process particularly, the soft-agglomerated degree of nano particle obviously reduces, and is good with the consistency of organic polymer material, greatly widened the Application Areas of product.On the basis of water-thinned latex paint original formulation; After adding certain amount of nano silicon oxide, abundant dispersion; Performances such as the bonding strength between its suspension stability, thixotropy, coating and the matrix, smooth finish all obtain to significantly improve, and shorten time of drying, and the artificial ultraviolet ageing test period of quickening is multiplied; Abrasion resistance is brought up to up to ten thousand times by several thousand times, and the pollution resistance of coating also obviously improves simultaneously.Nano silicon oxide is well-dispersed in Vestolen PP 7052 (PP), the SE plastic raw materialss such as (PVC), can significantly improve intensity, toughness, wear resistance and the resistance to deterioration of plastics.Like nano modification PP, main performance index such as its water-intake rate, insulation resistance, compressed residual distortion, flexural strength all meet or exceed engineering plastic nylon 6, and the product weathering resistance is enhanced about more than once, and can substitute nylon 6 in some field.In rubber such as solution polymerized butylbenzene, add a small amount of nano silicon (alternative carbon black) as strengthening agent and inhibitor, the toughness of the colorful rubber goods of producing, intensity, elongation, fold resistance and performance such as anti-aging all meet or exceed terpolymer EP rubber.In the iron coke powder, add with the nano silicon oxide is that main composite granule carries out modification; The product salient features reaches the highest level of existing like product; Like remanence strength greater than 4100 Gausses (Gs); HCJ is greater than 3000 oersteds (Oe), and magnetic energy product is greater than 4,000,000 high (MGOe) difficult to understand, and the production cost of material obviously reduces simultaneously.In addition, nano silicon also can be widely used in numerous areas upgrading product such as pottery, gypsum, store battery, pigment, tackiness agent, makeup, glass reinforced plastic, chemical fibre, synthetic glass, environmental protection.
Nano titanium oxide and nano silicon have numerous good characteristics and application prospects; But simple nano titanium oxide is during as the additive of photocatalyst, electrochemical catalyst, organic catalyst compound or fine chemical product; The starting material of titanium oxide etc. have higher cost, and the practical efficiency of titanium oxide is lower; And simple nano silicon does not possess many good characteristics of nano titanium oxide.Therefore; Nano titanium oxide and nano silicon advantages are separately got up; Prepare nano silicon dioxide coated by nano titanium dioxide NEW TYPE OF COMPOSITE nano material; To advancing nano titanium oxide and silicon dioxide composite material application, the long-pending and service efficiency of raising titanium dioxide surface, have important significance for theories and actual application value in fields such as photochemical catalyst, electrochemical catalyst, organic synthesis, meticulous article chemical industry.
There is the patent of synthetic, modification and application of a large amount of relevant titanium oxide and silicon-dioxide open.Chinese patent (application number 200910116178.9) discloses " adopting the method for chemical nickel plating copper-phosphorus alloy solid support of modified nano titanium dioxide "; Chinese patent (application number 200910002490.8) discloses " a kind of preparation method of iron-doped nitrogen-doped nano titanium dioxide powder "; Chinese patent (application number 200810243732.8) discloses " a kind of preparation method of nano titanium oxide-zinc oxide composite powder "; Chinese patent (application number 200810123979.2) discloses " a kind of preparation method of doped nanometer titanium oxide photocatalyst "; Chinese patent (application number 200810031600.9) discloses " preparation method of Ag-carried nanometer titanium dioxide "; Chinese patent (ZL 200610085237.X) discloses " nanometer titanium dioxide/selenium dioxide composition and preparation method thereof "; Chinese patent (ZL 02147872.4) discloses " a kind of nano titanium oxide ", and Chinese patent (ZL 99116814.3) discloses " a kind of preparation method of nano titanium oxide ".USP (application number 20090110929) discloses " a kind of rare earth doped titanium oxide and preparation method thereof "; USP (application number 20090098042) discloses " a kind of preparation method of titanium oxide "; USP (application number 20090175757) discloses " preparation method of a kind of titanium oxide/SWCN matrix material "; USP (application number 20080064592 and 20080279760) discloses " a kind of synthetic, preparation method of titanium dioxide nanoparticle " respectively; USP (application number 20080044345) discloses " a kind of production technique of titanium oxide "; USP (application number 20080260626) discloses " a kind of titanium dioxide optical catalyst "; USP (application number 20080141905) discloses " a kind of surface modifying treatment of titanium dioxide pigment particles ", and USP (application number 20080108740) discloses " a kind of TiO 2 pigment of surface-treated ".Chinese patent (ZL 200510064682.5, ZL03105299.1) discloses " a kind of preparation method of nano silicon dioxide "; Chinese patent (ZL 02155203.7) discloses " nano silicon/Z 250 composite particulate material and preparation method thereof "; Chinese patent (application number 200610009601.4) discloses " method for preparing nano silicon with rice hull ash "; Chinese patent (ZL 200410010304.2) discloses " a kind of nano silicon dioxide particles preparation method "; Chinese patent (application number 20081004251.0) discloses " a kind of nano-silicon dioxide hollow sphere material and preparation method thereof ", and Chinese patent (application number 2006101300304.5) discloses " preparation method of a kind of hydrophobic nano-silica " or the like.The technology of the relevant nano silicon dioxide coated by nano titanium dioxide NEW TYPE OF COMPOSITE of Shang Weijian nano material preparation openly perhaps is used.
Summary of the invention
The objective of the invention is to be to provide a kind of preparation method of nano silicon dioxide coated by nano titanium dioxide; Easy to implement the method; Simple to operate, the nano silicon dioxide coated by nano titanium dioxide matrix material of preparation has little, the good characteristics such as dispersiveness of particle size distribution range.
The present invention realizes through following technical scheme: the preparation method of described a kind of nano silicon dioxide coated by nano titanium dioxide composite nano materials comprises the steps:
A kind of preparation method of nano silicon dioxide coated by nano titanium dioxide matrix material the steps include:
A, stir and the condition of UW effect under; To concentration is in the silicate solutions of 0.1～10mol/L; Drip the mineral acid of 0.1～10mol/L concentration, the pH value of control reaction system is 5.5～9.5,25～65 ℃ of temperature of reaction, reacts 30～120 minutes; Left standstill 0.5～12 hour, and promptly obtained white or transparent silicic acid sol; With white or transparent silicic acid sol, drying is 0.5～24 hour under 65～120 ℃ of conditions, promptly obtains white silicic acid gel; With white silicic acid gel and volume be that the water of 1～3 times of silicic acid gel volume mixes, silicic acid gel to elutant behind the ball milling 10～120 minutes, water washing ball milling for neutral or do not have acid ion detect, reduce pressure (less than 100Kpa) filter or spinning, promptly obtain white silicic acid gel; With the thermolysis under 150～500 ℃ of conditions of white silicic acid gel solid, promptly obtain white nano-silica powder end;
B, under UW effect and stirring, 25～55 ℃ temperature condition; The above-mentioned white nano-silica powder end of 5～100g is joined in the mixing solutions of 1～30ml Glacial acetic acid min. 99.5 and 1～45ml water and 5～100ml absolute ethyl alcohol; Thorough mixing obtains the mixture of nano silicon and Glacial acetic acid min. 99.5, water and absolute ethyl alcohol;
C, under UW effect and stirring, 25～55 ℃ temperature condition; In 10～60 minutes; 2.2～45ml butyl(tetra)titanate and 5～100ml absolute ethyl alcohol mixed solution are added drop-wise in the mixture of above-mentioned nano silicon and Glacial acetic acid min. 99.5, water and absolute ethyl alcohol, left standstill 0.5～24 hour, drying is 0.5～24 hour under 80～120 ℃ of conditions; Ball milling obtains white metatitanic acid gel and coats SiO 2 powder; White metatitanic acid gel is coated nano silicon place the temperature programmed control stove; Temperature rise rate with 1～10 ℃ of PM is warming up to 350～650 ℃; Constant temperature 0.5～24 hour, thermolysis obtains nano silicon dioxide coated by nano titanium dioxide particulate composite powder.
A kind of nano silicon dioxide coated by nano titanium dioxide matrix material of the present invention forms through method for preparing.
In order to realize the present invention better, described silicate comprises one or both any mixing in water glass, the potassium silicate;
Described mineral acid comprises any mixing of one or both or three kinds in hydrochloric acid, nitric acid or the sulfuric acid acetic acid;
Described water is natural water, tap water, zero(ppm) water or deionized water.
The present invention compared with prior art has following advantage and beneficial effect:
1, utilize synthetic nano silicon dioxide coated by nano titanium dioxide matrix material size distribution homogeneous of the present invention, purity height, the particle size distribution scope of matrix material is that 1～100nm, purity are higher than 99.8% (the mass percentage content sum of titanium oxide and silicon-dioxide);
2, utilize the thickness, content etc. of silica granules particle diameter, the coated by titanium dioxide layer of synthetic nano silicon dioxide coated by nano titanium dioxide matrix material of the present invention to be easy to control; Can change production technique according to different purposes in good time, produce content of titanium dioxide difference, different, the performance different composite materials of grain diameter;
3, the nano silicon dioxide coated by nano titanium dioxide NEW TYPE OF COMPOSITE nano material of utilizing the present invention to prepare; To advancing titanium oxide and silicon dioxide composite material application, raising titanium oxide specific surface area and service efficiency in fields such as photochemical catalyst, electrochemical catalyst, organic synthesis, meticulous article chemical industry; Reduce the production cost of nano titanium oxide associated materials; And can use repeatedly or recycling as catalyzer, have good social benefit and economic benefit;
4, utilize that synthetic nano silicon dioxide coated by nano titanium dioxide composite technology of the present invention is flexible, equipment is simple, starting material are cheap, the comprehensive production cost of material is low, be easy to realize large-scale industrial production.
Description of drawings
Fig. 1 (A, B) is respectively the transmission electron microscope picture of embodiment 5 and embodiment 7 synthetic nano silicon dioxide coated by nano titanium dioxide matrix materials, and (Figure 1A: particle size range is 10～25nm, and median size is about 20nm; Figure 1B: particle size range is 30～50nm, and median size is about 40nm);
Fig. 2 is the laser particle size analysis figure (the grain diameter scope is 20～50nm, and median size is about 35nm) of embodiment 10 synthetic nano silicon dioxide coated by nano titanium dioxide matrix materials;
Embodiment
Below in conjunction with accompanying drawing and embodiment, the present invention is done detailed description further.
Embodiment 1:
A kind of preparation method of nano silicon dioxide coated by nano titanium dioxide matrix material the steps include:
The first step is in the sodium silicate solution of 0.1mol/L to concentration under the condition of stirring and UW effect, drips the hydrochloric acid of 0.1mol/L concentration; The pH value of control reaction system is 5.5,25 ℃ of temperature of reaction; Reacted 30 minutes, left standstill 0.5 hour, promptly obtain white or transparent silicic acid sol; With white or transparent silicic acid sol, drying is 2 hours under 65 ℃ of conditions, promptly obtains white silicic acid gel; With white silicic acid gel and volume be that the zero(ppm) water of 1 times of silicic acid gel volume mixes, ball milling 10 minutes, use behind the distilled water wash ball milling silicic acid gel to elutant as neutrality or cl ions detect, filtration under diminished pressure (less than 100Kpa), promptly obtain white silicic acid gel solid; With the thermolysis under 150 ℃ of conditions of white silicic acid gel solid, promptly obtain white nano-silica powder end product;
Second step is under UW effect and stirring, 25 ℃ temperature condition; The above-mentioned white nano-silica powder end of 5g is joined in the mixing solutions of 1ml Glacial acetic acid min. 99.5 and 1ml water and 5ml absolute ethyl alcohol; Thorough mixing obtains the mixture of nano silicon and Glacial acetic acid min. 99.5, water and absolute ethyl alcohol;
The 3rd step is under UW effect and stirring, 25 ℃ temperature condition; In 10 minutes; 2.2ml butyl(tetra)titanate and 5ml absolute ethyl alcohol mixed solution are added drop-wise in the mixture of above-mentioned nano silicon and Glacial acetic acid min. 99.5, water and absolute ethyl alcohol; Left standstill 2 hours, drying is 2 hours under 80 ℃ of conditions, obtains white metatitanic acid gel and coats silica product; White metatitanic acid gel is coated silica product place the temperature programmed control stove, be warming up to 350 ℃ with the temperature rise rate of 2 ℃ of PMs, constant temperature 1 hour, thermolysis obtains the nano silicon dioxide coated by nano titanium dioxide composite powder.
Through laser particle size test and chemical analysis; The grain diameter scope of gained nano silicon dioxide coated by nano titanium dioxide matrix material is 1～15nm; Median size is about 10nm, and purity is 99.2% (the mass percentage content sum of titanium oxide and silicon-dioxide).
Embodiment 2:
A kind of preparation method of nano silicon dioxide coated by nano titanium dioxide matrix material the steps include:
The first step is under the condition of stirring and UW effect; To concentration is in the sodium silicate solution of 2mol/L; Drip balanced mix, total concn is hydrochloric acid, the vitriolic mixing solutions of 2mol/L, the pH value of control reaction system is 9.5,25 ℃ of temperature of reaction, reacts 30 minutes; Left standstill 1 hour, and promptly obtained white or transparent silicic acid sol; With white or transparent silicic acid sol, drying is 12 hours under 100 ℃ of conditions, promptly obtains white silicic acid gel; With white silicic acid gel and volume be that the zero(ppm) water of 2 times of silicic acid gel volumes mixes, ball milling 10 minutes, use silicic acid gel to elutant behind the distilled water wash ball milling as neutrality or do not have that cl ions detects, filtration under diminished pressure (less than 100Kpa) or spinning; Obtain white silicic acid gel; With the thermolysis under 250 ℃ of conditions of white silicic acid gel, obtain white nano-silica powder end;
Second step is under UW effect and stirring, 25 ℃ temperature condition; The above-mentioned white nano-silica powder end of 80g is joined in the mixing solutions of 5ml Glacial acetic acid min. 99.5 and 10ml water and 15ml absolute ethyl alcohol; Thorough mixing obtains the mixture of nano silicon and Glacial acetic acid min. 99.5, water and absolute ethyl alcohol;
The 3rd step is under UW effect and stirring, 25 ℃ temperature condition; In 30 minutes; 3.5ml butyl(tetra)titanate and 13ml absolute ethyl alcohol mixed solution are added drop-wise in the mixture of above-mentioned nano silicon and Glacial acetic acid min. 99.5, water and absolute ethyl alcohol; Left standstill 1 hour, drying is 24 hours under 120 ℃ of conditions, obtains white metatitanic acid gel and coats silica product; White metatitanic acid gel is coated silica product place the temperature programmed control stove, be warming up to 450 ℃ with the temperature rise rate of 5 ℃ of PMs, constant temperature 2 hours, thermolysis obtains the nano silicon dioxide coated by nano titanium dioxide composite powder.
Through laser particle size test and chemical analysis; The grain diameter scope of gained nano silicon dioxide coated by nano titanium dioxide matrix material is 5～20nm; Median size is about 10nm, and purity is 99.1% (the mass percentage content sum of titanium oxide and silicon-dioxide).
Embodiment 3:
A kind of preparation method of nano silicon dioxide coated by nano titanium dioxide matrix material the steps include:
The first step is in the potassium silicate solution of 1mol/L to concentration under the condition of stirring and UW effect, drips the nitric acid of 1mol/L concentration; The pH value of control reaction system is 6.5,35 ℃ of temperature of reaction; Reacted 60 minutes, left standstill 1 hour, promptly obtain white or transparent silicic acid sol; With white or transparent silicic acid sol, drying is 2～24 hours under 80 ℃ of conditions, promptly obtains white silicic acid gel; With white silicic acid gel and volume be that the zero(ppm) water of 3 times of silicic acid gel volumes mixes, ball milling 20 minutes, to use silicic acid gel to elutant behind the distilled water wash ball milling be neutral, filtration under diminished pressure (less than 100Kpa) or spinning; Obtain white silicic acid gel; With the thermolysis under 250 ℃ of conditions of white silicic acid gel, obtain white nano-silica powder end;
Second step is under UW effect and stirring, 30 ℃ temperature condition; The above-mentioned white nano-silica powder end of 10g is joined in the mixing solutions of 5ml Glacial acetic acid min. 99.5 and 8ml water and 12ml absolute ethyl alcohol; Thorough mixing obtains the mixture of nano silicon and Glacial acetic acid min. 99.5, water and absolute ethyl alcohol;
The 3rd step in 20 minutes, was added drop-wise to 8.5ml butyl(tetra)titanate and 20ml absolute ethyl alcohol mixed solution in the mixture of above-mentioned nano silicon and Glacial acetic acid min. 99.5, water and absolute ethyl alcohol under UW effect and stirring, 30 ℃ temperature condition; Left standstill 4 hours, drying is 4 hours under 90 ℃ of conditions, ball milling; Obtain white metatitanic acid gel and coat SiO 2 powder; White metatitanic acid gel is coated SiO 2 powder place the temperature programmed control stove, be warming up to 450 ℃, constant temperature 2 hours with the temperature rise rate of 5 ℃ of PMs; Thermolysis obtains the nano silicon dioxide coated by nano titanium dioxide composite powder.
Through laser particle size analysis and chemical analysis; The grain diameter scope of gained nano silicon dioxide coated by nano titanium dioxide matrix material is 5～30nm; Median size is about 15nm, and purity is 99.8% (the mass percentage content sum of titanium oxide and silicon-dioxide).
Embodiment 4:
A kind of preparation method of nano silicon dioxide coated by nano titanium dioxide matrix material the steps include:
The first step is under the condition of stirring and UW effect; To concentration is in the potassium silicate solution of 3mol/L; Drip balanced mix, total concn is hydrochloric acid, nitric acid and the vitriolic mixture of 3mol/L, the pH value of control reaction system is 7.5,45 ℃ of temperature of reaction, reacts 80 minutes; Left standstill 2 hours; Obtain white or transparent silicic acid sol,, obtain white silicic acid gel white or transparent silicic acid sol under 90 ℃ of conditions dry 6 hours; White silicic acid gel and volume are that the zero(ppm) water of 1 times of silicic acid gel volume mixes, ball milling 40 minutes, use silicic acid gel to elutant behind the distilled water wash ball milling as neutrality or do not have cl ions or sulfate ion detects, filtration under diminished pressure (less than 100Kpa) or spinning; Obtain white silicic acid gel powder,, obtain white nano-silica powder end the thermolysis under 300 ℃ of conditions of white silicic acid gel powder;
Second step is under UW effect and stirring, 35 ℃ temperature condition; The above-mentioned white nano-silica powder end of 20g is joined in the mixing solutions of 10ml Glacial acetic acid min. 99.5 and 18ml water and 22ml absolute ethyl alcohol; Thorough mixing obtains the mixture of nano silicon and Glacial acetic acid min. 99.5, water and absolute ethyl alcohol;
The 3rd step in 30 minutes, was added drop-wise to 16ml butyl(tetra)titanate and 40ml absolute ethyl alcohol mixed solution in the mixture of above-mentioned nano silicon and Glacial acetic acid min. 99.5, water and absolute ethyl alcohol under UW effect and stirring, 35 ℃ temperature condition; Left standstill 6 hours, drying is 6 hours under 90 ℃ of conditions, ball milling; Obtain white metatitanic acid gel and coat SiO 2 powder; White metatitanic acid gel is coated SiO 2 powder place the temperature programmed control stove, be warming up to 550 ℃, constant temperature 6 hours with the temperature rise rate of 5 ℃ of PMs; Thermolysis obtains the nano silicon dioxide coated by nano titanium dioxide composite powder.
Measure through laser particle size test and chemical analysis; The grain diameter scope of gained nano silicon dioxide coated by nano titanium dioxide matrix material is 1～20nm; Median size is about 10nm, and purity is 99.82% (the mass percentage content sum of titanium oxide and silicon-dioxide).
Embodiment 5:
A kind of preparation method of nano silicon dioxide coated by nano titanium dioxide matrix material the steps include:
The first step is in the sodium silicate solution of 6mol/L to concentration under the condition of stirring and UW effect, and dripping concentration is the hydrochloric acid of 6mol/L; The pH value of control reaction system is 8.5,55 ℃ of temperature of reaction, reacts 100 minutes, leaves standstill 4 hours; Promptly obtain white or transparent silicic acid sol; With white or transparent silicic acid sol, drying is 12 hours under 100 ℃ of conditions, promptly obtains white silicic acid gel; With white silicic acid gel and volume be that the zero(ppm) water of 3 times of silicic acid gel volumes mixes, ball milling 60 minutes, use silicic acid gel to elutant behind the distilled water wash ball milling as neutrality or do not have that cl ions detects, filtration under diminished pressure (less than 100Kpa) or spinning; Obtain white silicic acid gel; With the thermolysis under 350 ℃ of conditions of white silicic acid gel, obtain white nano-silica powder end;
Second step is under UW effect and stirring, 45 ℃ temperature condition; The above-mentioned white nano-silica powder end of 40g is joined in the mixing solutions of 20ml Glacial acetic acid min. 99.5 and 30ml water and 40ml absolute ethyl alcohol; Thorough mixing obtains the mixture of nano silicon and Glacial acetic acid min. 99.5, water and absolute ethyl alcohol;
The 3rd step in 40 minutes, was added drop-wise to 30ml butyl(tetra)titanate and 85ml absolute ethyl alcohol mixed solution in the mixture of above-mentioned nano silicon and Glacial acetic acid min. 99.5, water and absolute ethyl alcohol under UW effect and stirring, 45 ℃ temperature condition; Left standstill 10 hours, drying is 14 hours under 100 ℃ of conditions, ball milling; Obtain white metatitanic acid gel and coat SiO 2 powder; White metatitanic acid gel is coated SiO 2 powder place the temperature programmed control stove, be warming up to 450 ℃, constant temperature 3 hours with the temperature rise rate of 5 ℃ of PMs; Thermolysis obtains the nano silicon dioxide coated by nano titanium dioxide composite powder.
Measure and chemical analysis through TEM analysis; The grain diameter scope of gained nano silicon dioxide coated by nano titanium dioxide matrix material is 10～25nm; Median size is about 20nm (accompanying drawing 1A), and purity is 99.9% (the mass percentage content sum of titanium oxide and silicon-dioxide).
Embodiment 6:
A kind of preparation method of nano silicon dioxide coated by nano titanium dioxide matrix material the steps include:
The first step is in the sodium silicate solution of 8mol/L to concentration under the condition of stirring and UW effect, and dripping concentration is the hydrochloric acid of 8mol/L; The pH value of control reaction system is 9.5,50 ℃ of temperature of reaction; Reacted 60 minutes, left standstill 18 hours, obtain white or transparent silicic acid sol; With white or transparent silicic acid sol under 100 ℃ of conditions dry 24 hours; Obtain white silicic acid gel, with white silicic acid gel and volume be that the zero(ppm) water of 2 times of silicic acid gel volumes mixes, ball milling 20 minutes, use silicic acid gel to elutant behind the distilled water wash ball milling as neutrality or do not have that cl ions detects, filtration under diminished pressure (less than 100Kpa) or spinning, obtain white silicic acid gel; With the thermolysis under 450 ℃ of conditions of white silicic acid gel, obtain white nano-silica powder end;
Second step is under UW effect and stirring, 50 ℃ temperature condition; The above-mentioned white nano-silica powder end of 80g is joined in the mixing solutions of 30ml Glacial acetic acid min. 99.5 and 45ml water and 60ml absolute ethyl alcohol; Thorough mixing obtains the mixture of nano silicon and Glacial acetic acid min. 99.5, water and absolute ethyl alcohol;
The 3rd step in 30 minutes, was added drop-wise to 40ml butyl(tetra)titanate and 85ml absolute ethyl alcohol mixed solution in the mixture of above-mentioned nano silicon and Glacial acetic acid min. 99.5, water and absolute ethyl alcohol under UW effect and stirring, 50 ℃ temperature condition; Left standstill 18 hours, drying is 20 hours under 100 ℃ of conditions, ball milling; Obtain white metatitanic acid gel and coat SiO 2 powder; White metatitanic acid gel is coated SiO 2 powder place the temperature programmed control stove, be warming up to 500 ℃, constant temperature 6 hours with the temperature rise rate of 5 ℃ of PMs; Thermolysis obtains the nano silicon dioxide coated by nano titanium dioxide composite powder.
Through laser particle size analysis and chemical analysis; The grain diameter scope of gained nano silicon dioxide coated by nano titanium dioxide matrix material is 10～80nm; Median size is about 40nm, and purity is 99.81% (the mass percentage content sum of titanium oxide and silicon-dioxide).
Embodiment 7:
A kind of preparation method of nano silicon dioxide coated by nano titanium dioxide matrix material the steps include:
The first step is in the sodium silicate solution of 2mol/L to concentration under the condition of stirring and UW effect, and dripping concentration is the hydrochloric acid of 2mol/L; The pH value of control reaction system is 9.5,25 ℃ of temperature of reaction; Reacted 30 minutes, left standstill 1 hour, promptly obtain white or transparent silicic acid sol; With white or transparent silicic acid sol, drying is 12 hours under 100 ℃ of conditions, promptly obtains white silicic acid gel; With white silicic acid gel and volume be that the zero(ppm) water of 1.5 times of silicic acid gel volumes mixes, ball milling 10 minutes, use silicic acid gel to elutant behind the distilled water wash ball milling as neutrality or do not have that cl ions detects, filtration under diminished pressure (less than 100Kpa) or spinning; Obtain white silicic acid gel; With the thermolysis under 250 ℃ of conditions of white silicic acid gel, obtain white nano-silica powder end;
Second step is under UW effect and stirring, 25 ℃ temperature condition; The above-mentioned white nano-silica powder end of 45g is joined in the mixing solutions of 20ml Glacial acetic acid min. 99.5 and 35ml water and 45ml absolute ethyl alcohol; Thorough mixing obtains the mixture of nano silicon and Glacial acetic acid min. 99.5, water and absolute ethyl alcohol;
The 3rd step in 30 minutes, was added drop-wise to 30ml butyl(tetra)titanate and 65ml absolute ethyl alcohol mixed solution in the mixture of above-mentioned nano silicon and Glacial acetic acid min. 99.5, water and absolute ethyl alcohol under UW effect and stirring, 25 ℃ temperature condition; Left standstill 2 hours, drying is 24 hours under 120 ℃ of conditions, ball milling; Obtain white metatitanic acid gel and coat SiO 2 powder; White metatitanic acid gel cladding titanium dioxide Si powder is placed the temperature programmed control stove, be warming up to 450 ℃, constant temperature 3 hours with the temperature rise rate of 5 ℃ of PMs; Thermolysis obtains the nano silicon dioxide coated by nano titanium dioxide composite powder.
Through transmission electron microscope and chemical analysis; The grain diameter scope of gained nano silicon dioxide coated by nano titanium dioxide matrix material is 30～50nm; Median size is about 40nm (accompanying drawing 1B), and purity is 99.85% (the mass percentage content sum of titanium oxide and silicon-dioxide).
Embodiment 8:
A kind of preparation method of nano silicon dioxide coated by nano titanium dioxide matrix material the steps include:
The first step is under the condition of stirring and UW effect; To total concn is in the mixing solutions of equimolar water glass, potassium silicate of 10mol/L; Moles such as dropping mix, total concn is the sulfuric acid of 10mol/L and the mixing solutions of nitric acid, and the pH value of controlling reaction system is 9.5,65 ℃ of temperature of reaction, reacts 120 minutes; Left standstill 12 hours, and obtained white or transparent silicic acid sol; With white or transparent silicic acid sol; Drying is 24 hours under 120 ℃ of conditions; Obtain white silicic acid gel; With white silicic acid gel and volume be that the deionized water of 2.5 times of silicic acid gel volumes mixes, ball milling 120 minutes, use behind the deionized water wash ball milling silicic acid gel to elutant as neutrality or sulfate ion detect, filtration under diminished pressure (less than 100Kpa) or spinning; Obtain white silicic acid gel,, obtain white nano-silica powder end the thermolysis under 500 ℃ of conditions of white silicic acid gel;
Second step is under UW effect and stirring, 55 ℃ temperature condition; The above-mentioned white nano-silica powder end of 100g is joined in the mixing solutions of 30ml Glacial acetic acid min. 99.5 and 40ml water and 100ml absolute ethyl alcohol; Thorough mixing obtains the mixture of nano silicon and Glacial acetic acid min. 99.5, water and absolute ethyl alcohol;
The 3rd step in 60 minutes, was added drop-wise to 45ml butyl(tetra)titanate and 100ml absolute ethyl alcohol mixed solution in the mixture of above-mentioned nano silicon and Glacial acetic acid min. 99.5, water and absolute ethyl alcohol under UW effect and stirring, 55 ℃ temperature condition; Left standstill 24 hours, drying is 12 hours under 120 ℃ of conditions, ball milling; Obtain white metatitanic acid gel and coat SiO 2 powder; White metatitanic acid gel is coated SiO 2 powder place the temperature programmed control stove, be warming up to 650 ℃, constant temperature 24 hours with the temperature rise rate of 10 ℃ of PMs; Thermolysis obtains the nano silicon dioxide coated by nano titanium dioxide composite powder.
Measure through laser particle size analysis and chemical analysis; The grain diameter scope of gained nano silicon dioxide coated by nano titanium dioxide matrix material is 10～50nm; Median size is about 35nm, and purity is 99.28% (the mass percentage content sum of titanium oxide and silicon-dioxide).
Embodiment 9:
A kind of preparation method of nano silicon dioxide coated by nano titanium dioxide matrix material the steps include:
The first step is in the sodium silicate solution of 1mol/L to concentration under the condition of stirring and UW effect, and dripping concentration is the hydrochloric acid of 1mol/L; The pH value of control reaction system is 9.0,25 ℃ of temperature of reaction; Reacted 45 minutes, left standstill 2 hours, obtain white or transparent silicic acid sol; With white or transparent silicic acid sol under 110 ℃ of conditions dry 12 hours; Obtain white silicic acid gel, with white silicic acid gel and volume be that the zero(ppm) water of 3 times of silicic acid gel volumes mixes, ball milling 10 minutes, use silicic acid gel to elutant behind the distilled water wash ball milling as neutrality or do not have that cl ions detects, filtration under diminished pressure (less than 100Kpa) or spinning, obtain white silicic acid gel; With the thermolysis under 280 ℃ of conditions of white silicic acid gel, obtain white nano-silica powder end;
Second step is under UW effect and stirring, 25 ℃ temperature condition; The above-mentioned white nano-silica powder end of 30g is joined in the mixing solutions of 10ml Glacial acetic acid min. 99.5 and 10ml water and 20ml absolute ethyl alcohol; Thorough mixing obtains the mixture of nano silicon and Glacial acetic acid min. 99.5, water and absolute ethyl alcohol;
The 3rd step in 30 minutes, was added drop-wise to 1.5ml butyl(tetra)titanate and 10ml absolute ethyl alcohol mixed solution in the mixture of above-mentioned nano silicon and Glacial acetic acid min. 99.5, water and absolute ethyl alcohol under UW effect and stirring, 25 ℃ temperature condition; Left standstill 1 hour, drying is 24 hours under 120 ℃ of conditions, ball milling; Obtain white metatitanic acid gel and coat SiO 2 powder; White metatitanic acid gel is coated SiO 2 powder place the temperature programmed control stove, be warming up to 450 ℃, constant temperature 2 hours with the temperature rise rate of 5 ℃ of PMs; Thermolysis obtains the nano silicon dioxide coated by nano titanium dioxide composite powder.
Measure through laser particle size analysis and chemical analysis; The grain diameter scope of gained nano silicon dioxide coated by nano titanium dioxide matrix material is 30～100nm; Median size is about 60nm, and purity is 99.82% (the mass percentage content sum of titanium oxide and silicon-dioxide).
Embodiment 10:
A kind of preparation method of nano silicon dioxide coated by nano titanium dioxide matrix material the steps include:
The first step is in the sodium silicate solution of 1mol/L to concentration under the condition of stirring and UW effect, and dripping concentration is the hydrochloric acid of 1mol/L; The pH value of control reaction system is 9.0,25 ℃ of temperature of reaction; Reacted 45 minutes, left standstill 2 hours, obtain white or transparent silicic acid sol; With white or transparent silicic acid sol under 110 ℃ of conditions dry 12 hours; Obtain white silicic acid gel, with white silicic acid gel and volume be that the zero(ppm) water of 2 times of silicic acid gel volumes mixes, ball milling 10 minutes, use silicic acid gel to elutant behind the distilled water wash ball milling as neutrality or do not have that cl ions detects, filtration under diminished pressure (less than 100Kpa) or spinning, obtain white silicic acid gel; With the thermolysis under 280 ℃ of conditions of white silicic acid gel, obtain white nano-silica powder end;
Second step is under UW effect and stirring, 25 ℃ temperature condition; The above-mentioned white nano-silica powder end of 30g is joined in the mixing solutions of 10ml Glacial acetic acid min. 99.5 and 10ml water and 20ml absolute ethyl alcohol; Thorough mixing obtains the mixture of nano silicon and Glacial acetic acid min. 99.5, water and absolute ethyl alcohol;
The 3rd step in 30 minutes, was added drop-wise to 1.5ml butyl(tetra)titanate and 10ml absolute ethyl alcohol mixed solution in the mixture of above-mentioned nano silicon and Glacial acetic acid min. 99.5, water and absolute ethyl alcohol under UW effect and stirring, 25 ℃ temperature condition; Left standstill 1 hour, drying is 24 hours under 120 ℃ of conditions, ball milling; Obtain white metatitanic acid gel and coat SiO 2 powder; White metatitanic acid gel is coated silica product in placing the temperature programmed control stove, be warming up to 450 ℃, constant temperature 12 hours with the temperature rise rate of 5 ℃ of PMs; Thermolysis obtains the nano silicon dioxide coated by nano titanium dioxide composite powder.
Measure through laser particle size analysis and chemical analysis; The grain diameter scope of gained nano silicon dioxide coated by nano titanium dioxide matrix material is 20～50nm; Median size is about 35nm (accompanying drawing 2), and purity is 99.86% (the mass percentage content sum of titanium oxide and silicon-dioxide).
Embodiment 11:
A kind of preparation method of nano silicon dioxide coated by nano titanium dioxide matrix material the steps include:
The first step is in the sodium silicate solution of 9mol/L to concentration under the condition of stirring and UW effect, and dripping concentration is the hydrochloric acid of 3mol/L; The pH value of control reaction system is 8.5,35 ℃ of temperature of reaction; Reacted 60 minutes, left standstill 16 hours, obtain white or transparent silicic acid sol; With white or transparent silicic acid sol under 110 ℃ of conditions dry 14 hours; Obtain white silicic acid gel, with white silicic acid gel and volume be that the zero(ppm) water of 1 times of silicic acid gel volume mixes, ball milling 30 minutes, use silicic acid gel to elutant behind the distilled water wash ball milling as neutrality or do not have that cl ions detects, filtration under diminished pressure (less than 100Kpa) or spinning, obtain white silicic acid gel; With the thermolysis under 280 ℃ of conditions of white silicic acid gel, obtain white nano-silica powder end;
Second step is under UW effect and stirring, 35 ℃ temperature condition; The above-mentioned white nano-silica powder end of 20g is joined in the mixing solutions of 20ml Glacial acetic acid min. 99.5 and 20ml water and 40ml absolute ethyl alcohol; Thorough mixing obtains the mixture of nano silicon and Glacial acetic acid min. 99.5, water and absolute ethyl alcohol;
The 3rd step in 45 minutes, was added drop-wise to 3ml butyl(tetra)titanate and 10ml absolute ethyl alcohol mixed solution in the mixture of above-mentioned nano silicon and Glacial acetic acid min. 99.5, water and absolute ethyl alcohol under UW effect and stirring, 35 ℃ temperature condition; Left standstill 8 hours, drying is 16 hours under 100 ℃ of conditions, ball milling; Obtain white metatitanic acid gel and coat SiO 2 powder; White metatitanic acid gel is coated SiO 2 powder in placing the temperature programmed control stove, be warming up to 450 ℃, constant temperature 16 hours with the temperature rise rate of 10 ℃ of PMs; Thermolysis obtains the nano silicon dioxide coated by nano titanium dioxide composite powder.
Measure through laser particle size analysis and chemical analysis; The grain diameter scope of gained nano silicon dioxide coated by nano titanium dioxide matrix material is 50～100nm; Median size is about 75nm, and purity is 99.81% (the mass percentage content sum of titanium oxide and silicon-dioxide).
Embodiment 12:
A kind of preparation method of nano silicon dioxide coated by nano titanium dioxide matrix material the steps include:
The first step is in the sodium silicate solution of 3mol/L to concentration under the condition of stirring and UW effect, and dripping concentration is the sulfuric acid of 6mol/L; The pH value of control reaction system is 7.0,45 ℃ of temperature of reaction, reacts 1 hour, leaves standstill 3 hours; Obtain white or transparent silicic acid sol; With white or transparent silicic acid sol, drying is 20 hours under 100 ℃ of conditions, obtains white silicic acid gel; With white silicic acid gel and volume be that the zero(ppm) water of 2 times of silicic acid gel volumes mixes, ball milling 10 minutes, use behind the distilled water wash ball milling silicic acid gel to elutant as neutrality or sulfate radical-free ion detect, filtration under diminished pressure (less than 100Kpa) or spinning; Obtain white silicic acid gel,, obtain white nano-silica powder end the thermolysis under 280 ℃ of conditions of white silicic acid gel;
Second step is under UW effect and stirring, 25 ℃ temperature condition; The above-mentioned white nano-silica powder end of 10g is joined in the mixing solutions of 20ml Glacial acetic acid min. 99.5 and 20ml water and 40ml absolute ethyl alcohol; Thorough mixing obtains the mixture of nano silicon and Glacial acetic acid min. 99.5, water and absolute ethyl alcohol;
The 3rd step in 60 minutes, was added drop-wise to 0.5ml butyl(tetra)titanate and 10ml absolute ethyl alcohol mixed solution in the mixture of above-mentioned nano silicon and Glacial acetic acid min. 99.5, water and absolute ethyl alcohol under UW effect and stirring, 45 ℃ temperature condition; Left standstill 8 hours, drying is 12 hours under 120 ℃ of conditions, ball milling; Obtain white metatitanic acid gel and coat SiO 2 powder; White metatitanic acid gel is coated SiO 2 powder in placing the temperature programmed control stove, be warming up to 450 ℃, constant temperature 20 hours with the temperature rise rate of 2 ℃ of PMs; Thermolysis obtains the nano silicon dioxide coated by nano titanium dioxide composite powder.
Measure through laser particle size analysis and chemical analysis; The grain diameter scope of gained nano silicon dioxide coated by nano titanium dioxide matrix material is 20～80nm; Median size is about 55nm, and purity is 99.83% (the mass percentage content sum of titanium oxide and silicon-dioxide).
As stated, can realize the present invention preferably.
Claims (1)
1. the preparation method of a nano silicon dioxide coated by nano titanium dioxide the steps include:
A, stir and the condition of UW effect under, be in the silicate solutions of 0.1～10mol/L to concentration, drip the mineral acid of 0.1～10mol/L concentration; The pH value of control reaction system is 5.5～9.5,25～65 ℃ of temperature of reaction, reacts 30～120 minutes, leaves standstill 0.5～12 hour; Obtain white or transparent silicic acid sol; With white or transparent silicic acid sol, drying is 0.5～24 hour under 65～120 ℃ of conditions, obtains white silicic acid gel; With white silicic acid gel and volume be that the water of 1～3 times of silicic acid gel volume mixes, silicic acid gel to elutant behind the ball milling 10～120 minutes, water washing ball milling for neutral or do not have that acid ion detects, filtration under diminished pressure or spinning, promptly obtain white silicic acid gel; With the thermolysis under 150～500 ℃ of conditions of white silicic acid gel solid, promptly obtain white nano-silica powder end;
B, under UW effect and stirring, 25～55 ℃ temperature condition; The above-mentioned white nano-silica powder end of 5～100g is joined in the mixing solutions of 1～30ml Glacial acetic acid min. 99.5 and 1～45ml water and 5～100ml absolute ethyl alcohol; Thorough mixing obtains the mixture of nano silicon and Glacial acetic acid min. 99.5, water and absolute ethyl alcohol;
C, under UW effect and stirring, 25～55 ℃ temperature condition; In 10～60 minutes; 2.2～45ml butyl(tetra)titanate and 5～100ml absolute ethyl alcohol mixed solution are added drop-wise in the mixture of above-mentioned nano silicon and Glacial acetic acid min. 99.5, water and absolute ethyl alcohol, left standstill 0.5～24 hour, drying is 0.5～24 hour under 80～120 ℃ of conditions; Ball milling obtains white metatitanic acid gel and coats SiO 2 powder; White metatitanic acid gel is coated nano silicon place the temperature programmed control stove; Temperature rise rate with 1～10 ℃ of PM is warming up to 350～650 ℃; Constant temperature 0.5～24 hour, thermolysis obtains nano silicon dioxide coated by nano titanium dioxide particulate composite powder;
Described silicate comprises one or both any mixing in water glass, the potassium silicate;
Described mineral acid comprises any mixing of one or both or three kinds in hydrochloric acid, nitric acid or the sulfuric acid;
Described water is natural water, tap water, zero(ppm) water or deionized water.
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