CN1300001C - Preparation method of visible light photoactivated octahedrite type titanium oxide colloidal sols - Google Patents
Preparation method of visible light photoactivated octahedrite type titanium oxide colloidal sols Download PDFInfo
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Abstract
The present invention relates to preparation for titanium dioxide collosol with high visual light activity. The titanium dioxide collosol has the advantages of good dispersibility, uniform granularity, etc. In order to further increase the visual light activity of the collosol, a rare earth and other transition metal doping modification method can be used for changing the structure of an energy band of the titanium dioxide collosol, and titanium dioxide photocatalysis material which can be excited by visual light is prepared. The existing preparation method has the disadvantages of low crystallization degree, high impurity content and high production cost; the method provided by the present invention improves the entire preparation technology of the collosol and synthesizes the titanium dioxide collosol under low temperature and at ordinary pressure; after the titanium dioxide collosol is doped with rare earth and other transition metal, the visual light activity of the titanium dioxide collosol is greatly increased; the titanium dioxide collosol can be used for using solar energy to carry out air pollution treatment, indoor air purification, indoor sterilization, crop sterilization, etc.; the titanium dioxide collosol has significant application prospects.
Description
Technical field
The present invention relates to belong to nano material preparation technology and Application Areas.Belonging to the preparation of the TiO 2 sol with higher visible light activity, mainly is the preparation of rare earth and other transient metal doped TiO 2 sols.
Background technology
The necessary for growth of crops such as vegetables, fruit tree, paddy rice is used a large amount of sterilant, the sterilant that generally uses mainly contains following a few class at present: heterocyclic, triazole species, benzene class, organic phosphates, sulphur class, copper mercury class, organotin arsenic class, antibiotic class etc., these agricultural chemicals mostly be greatly have phenyl ring, the organic compound of heterocycle structure, organosulfur structure, organic heavy metal structure, long-term application, residual fairly obvious in soil.Specifically, at present, mainly have following problem in the chemical pesticide use: (1) is low to the target organisms activity, and big to non-target organism toxicity.(2) agricultural chemicals itself and degraded intermediate thereof are accumulated in environment or animal and plant body easily.(3) resistance of target organisms is obvious, need increase amount of application year by year, has increased the weight of agricultural environment pollution.(4) broad spectrum is poor, and a kind of agricultural chemicals is often only effective to a certain or several diseases.
On the other hand, along with the enhancing day by day of health of people consciousness, the indoor environment situation more and more attracts much attention.The healthy of people in the various objectionable impurities serious harms of the formaldehyde that interior decoration and furniture produce, ammonia, benzene series thing etc.
Titanium dioxide has very high photocatalytic activity, each type organic of degraded that can non-selectivity, kills various bacteriophagees, has anticorrosive, stable in properties, advantage such as nontoxic simultaneously, is the first-selection of taking into account the medicine of biological and chemical Pollution abatement.Aspect the preventing and treating of pollution such as water, air, soil, developed rapidly at present, and constantly be generalized in the practical application, in the huge economic benefit of generation, also brought huge social and environmental benefit.
Studies show that anatase titanium dioxide has very high photocatalysis performance, factors such as the globule size of titanium dioxide, condition of surface then influence its catalytic activity to a great extent.The powder of liquid phase method preparation is unformed, needs high-temperature calcination just can make lattice perfection, but calcining can bring crystal grain to become problems such as big and hard aggregation, has had a strong impact on its activity, and power consumption is very high.Though now had a lot of methods can prepare the very big powder of the very thin specific surface area of granularity, how to have made the well-proportioned dispersion of these powder be still a more scabrous problem.Adopt various dispersion agents dispersing nanometer powder particle preferably, but inevitably bring a large amount of objectionable impuritiess into, cause secondary pollution.
Nano titanic oxide sol is a kind of aqueous colloidal through low-temperature hydrothermal synthetic, high dispersing, crystallization, have following different with utilizing dispersion agent dispersive titania powder suspension liquid: (1) preparation method's difference: colloidal sol can directly adopt the titanium source synthetic, needn't be prepared into powder, the colloidal sol of crystallization can be avoided the agglomeration traits of calcination process, therefore, preparing product is economized energy consumption, good dispersity, good stability, modification conveniently.(2) titanium dioxide surface different in kind: the good hydrophilic property of colloidal sol, particle are generally about 10 nanometers, and be even littler, and adhesive power is strong.Therefore, as the important supplement of nano titanium oxide industry, the colloidal sol product can carry out more massive production and application.
The raw material sources of TiO 2 sol are organic titanium source and inorganic ti sources.The organic titanium source is easy to prepare dispersed higher colloidal sol, but costs an arm and a leg, and contains large amount of organic, and toxic side effect is big, easily causes secondary pollution, so should not carry out large-scale production and application.At present existing patent and bibliographical information utilize inorganic ti sources to prepare dispersiveness colloidal sol preferably under low-temperature atmosphere-pressure, in application number is 00110406.3 and 00127951.3 Chinese patent, a kind of method that is prepared TiO 2 sol by titanium tetrachloride is disclosed, stable and the homogeneous grain diameter of this colloidal sol, but crystallization degree is very low, impurity (ammonium chloride) content is too high, so activity is restricted; In addition, the colloidal sol of this method preparation is anatase titanium dioxide, its Eg=3.2eV, and excitation wavelength＜388nm has limited its utilization ratio to visible light greatly, is difficult to be widely used in the actual environment.In order to adapt to the needs of practical application, be necessary further to improve the visible light activity of colloidal sol, therefore can adopt the method for rare earth and other transient metal doped modifications, titanium dioxide is carried out rare earth and transient metal doped, make it can be with recurring structure to change, prepare and under the exciting of natural light, can be produced a large amount of electronics and hole by the photocatalysis material of titanium dioxide of excited by visible light, strengthened catalytic performance.The Xie of Southeast China University etc. has reported Nd
3+, Ce
3+, Eu
3+Adulterated TiO 2 sol has visible light catalysis activity, for practical application provides good reference.But its preparation condition condition is comparatively harsh, as needing to adopt comparatively strict conditions such as microwave, ultrasonic or high-pressure sealed system in the dispergation process, if it is too high to carry out the scale operation cost with this.
Summary of the invention
The objective of the invention is to, on the basis of research at present the whole preparation process of colloidal sol is improved and optimized, synthetic dispersity of low-temperature atmosphere-pressure and degree of crystallization be colloidal sol preferably, adopts the limpid transparent and stable homogeneous of colloidal sol of this method preparation, do not contain organism, pollution-free; Through rare earth and other transient metal doped after, its visible light activity improves greatly, can utilize sun power to carry out air contaminant treatment, indoor air purification, indoor sterilization, farm crop sterilization etc., has important application prospects.This method is synthetic down in low-temperature atmosphere-pressure, and rare earth doped or other transition metal, specifically comprises the steps:
(1) hydrolytic precipitation
With the inorganic ti sources is raw material, slowly adds in the pure water under the ice-water bath condition, constantly stirs therebetween, wait to drip fully after, continue to stir about 1h, make the solution cooling; Then with alkali lye as precipitation agent, (its starting point concentration is not higher than 4M to control alkali lye starting point concentration when alkali lye is highly basic, its starting point concentration is not higher than 6M when alkali lye is weak base), and control its adding speed, dropwise drip, in the hydrolytic precipitation process, constantly reduce concentration of lye, minimum concentration is lower than 0.01M, treat abundant hydrolytic precipitation after, use concentration instead and be the alkali lye that is higher than 1M and regulate more than the pH to 9, constantly stir therebetween, and dripping follow-up continuous stirring fully more than 2 hours.
(2) filtration washing
Till washing and filtering is precipitated to inclusion-free ion (chlorion, sulfate ion etc.) and detects, with the Silver Nitrate more than the 1M or bariumchloride check chlorion or sulfate ion.
(3) dispergation crystallization
Slowly add mineral acid (concentration is to be advisable between the 5%-20%), adjusting pH is 0.3-2.0, and constantly stir, after adding mineral acid, at room temperature continue to stir more than 2 hours, also stir (or adopting ultrasonic, microwave replacement stirring) more than 3 hours in heating in water bath between the 40-90 degree then, promptly obtain stable homogeneous and translucent high-purity titanium dioxide colloidal sol.If will prepare the colloidal sol of high density, then can in the dispergation process, heat after 10 hours, container to be opened wide, synthermal continuation is down stirred, and moisture is evaporated in a large number, also can prepare the colloidal sol of high density colloidal sol or prescribed concentration thus as requested.
(4) mix
If the titanium salt (as titanium sulfate, other titanium salt of titanyl sulfate or sulphate-containing ion etc.) with sulphate-containing ion as the titanium source, then when doped with rare-earth elements, can only add rare earths salt in the heating in water bath whipping process of step (3); If with titanium tetrachloride, titanous chloride, chlorination oxygen titanium etc. not the titanium source of sulphate-containing ion be raw material, then add rare earths salt in the pure water in step (1), or in the heating in water bath whipping process of step (3), add rare earths salt; If which kind of titanium source no matter other transition metal (its vitriol is soluble salt) beyond rare earth doped then use, can in the pure water in the step (1) or in the heating in water bath whipping process of step (3), add transition metal salt solution.
Described inorganic ti sources is: titanium tetrachloride, titanous chloride, chlorination oxygen titanium, Titanium Nitrate, titanyl nitrate, titanium sulfate, titanyl sulfate etc., perhaps its any mixture.
Described precipitation agent: sodium hydroxide, potassium hydroxide, ammoniacal liquor, urea etc., perhaps its any mixture.
Described mineral acid: nitric acid, hydrochloric acid, sulfuric acid, perchloric acid etc., perhaps its any mixture.
Described transition metal: Fe
3+, Cu
2+Deng, perhaps its any mixture.
Described rare earth element: La
3+, Ce
3+, Nd
3+, Eu
3+Deng, perhaps its any mixture.
The preparation method of visible light photoactivated anatase type TiO 2 sol of the present invention, the collosol stability height of preparation, the concentration height, crystallization degree is better, and homogeneous is bright.Compared with prior art Tu Chu characteristics are:
1, with the inorganic ti sources is raw material, do not add any dispersion agent, do not contain organism, can not cause secondary pollution.
2, Zhi Bei transition metal is mixed TiO 2 sol concentration height, reach as high as more than 20%,
3, this collosol stability is good, can not assemble after placement for a long time or the dilution to be flocks.
4, its absorption spectrum of the colloidal sol behind overdoping is with respect to the obvious red shift of pure colloidal sol, and the visible light utilization ratio improves.
5, the titanium dioxide in the colloidal sol is Detitanium-ore-type, and crystallization degree is better, and crystal grain is grown up rapidly and the hard aggregation phenomenon when having avoided the high-temperature calcination crystallization.
6, the sol particle particle diameter is very little, has only 5-10 nanometer, and water-absorbent is strong, and specific surface is very big.
7, the dispergation process in this preparation is carried out under low-temperature atmosphere-pressure, mild condition, and technology is simple, is convenient to operation, thereby is easy to carry out scale operation.
8, the raw material sources of this colloidal sol preparation are extensive, cheap, pollute for a short time, help carrying out cleaner production.
Description of drawings
Fig. 1. the DRS spectrogram of the TiO 2 sol of different cerium dopings;
Fig. 2. the XRD spectra of the TiO 2 sol of different cerium dopings;
Fig. 3. the XRD spectra of the TiO 2 sol that difference is transient metal doped, doping is 1.0%;
Fig. 4. the transmittance of the pure titinium dioxide colloidal sol different time sections of example 6 preparations.Solid content is all 1.6%;
Fig. 5. the absorbancy of the pure titinium dioxide colloidal sol different time sections of example 6 preparations.Solid content is all 1.6%;
Fig. 6. the XRD spectra of the pure titinium dioxide colloidal sol different time sections sampling and testing of example 7 preparations;
Embodiment
Below by embodiment to method further instruction provided by the invention.
Example 1. is that the forerunner prepares high-purity titanium dioxide colloidal sol with the titanium tetrachloride
Measure the 50ml titanium tetrachloride in separating funnel, dropwise be added drop-wise to 200ml in the water of ice-water bath, after dropwising, stirred one hour, to drip starting point concentration again be the ammoniacal liquor of 4M and control its adding speed, and constantly reduce ammonia concn in the hydrolytic precipitation process, is low to moderate 0.05M most.After treating abundant hydrolytic precipitation, use concentration instead and be more than the adjusting pH to 9 of ammoniacal liquor of 1M, stirred 3 hours, filtration washing (silver nitrate solution with 1.0M drips check) till do not have chlorion and detect adds the water mixing according to required compound concentration with filter cake then, adds a certain amount of 10% nitric acid, regulating pH is 1.0, normal temperature stirred 4 hours down, and heated and stirred promptly obtained the vitreosol of nattier blue stable homogeneous more than 3 hours in 65 degree water-baths then.
Example 2. changes pH and temperature prepares colloidal sol
Step hydrolytic precipitation, filtration washing according to example 1, according to required compound concentration filter cake is added the water mixing then, add a certain amount of 8% nitric acid, regulating pH is 1.5, normal temperature stirred 6 hours down, heated and stirred more than 3 hours in 90 degree water-baths promptly obtains stable sol then, but the colloidal sol muddiness that obtains than example 1.
Still according to step hydrolytic precipitation, the filtration washing of example 1, according to required compound concentration filter cake is added the water mixing then, add a certain amount of 15% nitric acid, regulating pH is 0.3, normal temperature stirred 3 hours down, heated and stirred more than 10 hours in 40 degree water-baths promptly obtains stable sol then, but the colloidal sol muddiness that obtains than example 1.
The preparation and the sign of example 3. cerium doped titanium dioxide colloidal sols
Accurately take by weighing a certain amount of cerous nitrate, be dissolved in the 250ml water, and be refrigerated to below 4 degree, measure in 50ml titanium tetrachloride and the separating funnel, dropwise be added drop-wise to 250ml in the cerous nitrate solution of ice-water bath, after dropwising, stirred 1 hour, to drip starting point concentration again be the ammoniacal liquor of 3.5M and control its adding speed, and constantly reduce ammonia concn in the hydrolytic precipitation process, is low to moderate 0.025M most.After treating abundant hydrolytic precipitation, using concentration instead is more than the ammoniacal liquor adjusting pH to 9 of 1.5M, stirred 4 hours, filtration washing adds the water mixing according to required compound concentration with filter cake till do not have chlorion and detect then, adds a certain amount of 10% nitric acid, regulating pH is 0.9, normal temperature stirred 4 hours down, and heated and stirred promptly obtained the vitreosol of the stable homogeneous of different cerium dopings more than 3 hours in 68 degree water-baths then.According to this step, prepare 0.5%, 1%, 2% respectively, 5%, 10% Ce doped titanium dioxide collosol and pure titinium dioxide colloidal sol, oven dry is more than 12 hours under 65 degree, grind in agate mortar and obtain powder, its DRS test result is seen Fig. 1, its XRD test result such as Fig. 2.As shown in Figure 1, its absorption spectrum band edge is with doping increase " red shift " gradually, and visible-light absorptivity increases.As shown in Figure 2, along with the cerium doping increases, its anatase octahedrite (101) peak weakens gradually, illustrates that the doping of cerium has suppressed the growth of anatase crystal to a certain extent.
The preparation of example 4. other transient metal doped TiO 2 sols
Accurately take by weighing a certain amount of transition metal salt (Fe
3+, La
3+, Eu
3+, Nd
3+Deng) mixing in the 250m frozen water, measuring the 50ml titanium tetrachloride adds in the separating funnel, dropwise be added drop-wise to 250ml in the transition metal salt solution of ice-water bath, after dropwising, stirred one hour, to drip starting point concentration again be the ammoniacal liquor of 3.5M and control its adding speed, and constantly reduce ammonia concn in the hydrolytic precipitation process, is low to moderate 0.03M most.After treating abundant hydrolytic precipitation, using concentration instead is more than the ammoniacal liquor adjusting pH to 10 of 1.8M, stirred 4 hours, filtration washing adds the water mixing according to required compound concentration with filter cake till do not have chlorion and detect then, adds a certain amount of 10% nitric acid, regulating pH is 0.9, normal temperature stirred 4 hours down, and heated and stirred promptly obtained the vitreosol of transient metal doped modification more than 3 hours in 67 degree water-baths then.Oven dry was ground in agate mortar and is obtained powder, its XRD test result such as Fig. 3 more than 12 hours under 65 degree.
Example 5. prepares the lanthanum doped titanium dioxide collosol with the titanyl sulfate for the titanium source
Accurately take by weighing a certain amount of titanyl sulfate mixing in the 300ml pure water, stir fully dissolving, after the cooling, to drip starting point concentration again be the ammoniacal liquor of 4M and control its adding speed, and constantly reduce ammonia concn in the hydrolytic precipitation process, is low to moderate 0.05M most.After treating abundant hydrolytic precipitation, using concentration instead is more than the ammoniacal liquor adjusting pH to 10 of 2M, stirred 4 hours, (barium chloride solution with 1.0M drips check) added the water mixing according to required compound concentration with filter cake then till filtration washing to sulfate radical-free ion detected, add a certain amount of 10% nitric acid, regulating pH is 1.0, and normal temperature stirred 4 hours down, then heated and stirred more than 10 hours in 60 degree water-baths, add a certain amount of lanthanum nitrate hexahydrate therebetween, promptly obtain the vitreosol of lanthanum doping vario-property.
The 6. dispergation times of example are to the influence of transmittance, absorbancy, grain size
According to embodiment 1 step, respectively at 3h, 5h, 8h, 12h, 24h, 36h, the 48h sampling is diluted to same concentrations 1.6%, goes up in UV-Vis and surveys its transmittance and absorbancy.Comprehensive contrast.Know that by Fig. 4 along with the dispergation time lengthening, transmittance descends.Know by Fig. 5, its spectral line of absorption obviously moves to right, but do not represent its excitation wavelength " red shift ", but because prolong in time, crystal grain is grown up gradually, it is big that the influence of scattering process becomes, so the spectral line of absorption rising edge moves to right, also can see the situation that grain-size changes thus, promptly prolong crystal grain in time and become big, but grain size changes not quite after 36 hours, illustrates that this period dispergation reaches balance substantially.
The 7. dispergation times of example are to the influence of crystallization degree
According to the experimental procedure of embodiment 1, respectively at 3h, 8h, 12h, 24h, 36h, 48h sampling, oven dry is more than 12 hours down in 65 degree with 6 kinds of samples in the dispergation process, and grinding obtains powder in agate mortar, surveys its XRD, and the result as shown in Figure 6.As seen from the figure, prolong with crystallization time, crystallization degree improves constantly, but after 36 hours, crystallization degree changes not obvious.In conjunction with the variation of transmittance in the example 7 and absorbancy, select crystallization time can reach best crystallization degree in 36 hours.
The adding mode of example 8. ammoniacal liquor is to the influence of washing of precipitate and peptization effect
As the step of embodiment 1, adopt three kinds of different modes that add ammoniacal liquor respectively:
(1). when adding ammoniacal liquor, the ammoniacal liquor with excessive 50% directly adds in the titanium tetrachloride solution, then generates a large amount of flockss rapidly.
(2). when adding ammoniacal liquor, at the uniform velocity drip, and guarantee that the ammoniacal liquor total amount is consistent with ammoniacal liquor total amount in (1) with same concentration (as 2M).Then when being added drop-wise to a certain degree, explosive a large amount of gelatinous precipitates that generate occur, continuation drips to stir and then after this sedimentary phenomenon do not occurring breaking out.
(3). when adding ammoniacal liquor, drip earlier with higher concentration (as 4M), after reduce ammonia concn gradually, make and do not produce explosive deposited phenomenon in the precipitation process, and guarantee that the ammoniacal liquor total amount is consistent with ammoniacal liquor total amount in (1).
The precipitation that three kinds of modes are obtained adopts static layering respectively, and then its subsidence rate is V1＞V2＞V3, illustrates that thus three kinds of differences add the amorphous precipitated particle size that the ammoniacal liquor mode obtains and are d1＞d2＞d3 in proper order.And the size of this size is very big to follow-up dispergation process influence, and size is more little, and dispergation is easy more, and the colloidal sol that obtains is got over stable homogeneous.Be (3) described method so add the best mode of ammoniacal liquor.
Stir in the example 9. water-bath processes, the influence of ultrasonic, microwave
According to the experimental procedure of embodiment 1, adopt following dual mode during dispergation:
(1). only under 65 degree, carry out heating in water bath, and do not stir.The colloidal sol that the result obtains is very muddy, and begins precipitation after fortnight, and final upper strata is comparatively clarifying colloidal sol, and lower floor is the powdery precipitation of cohesion.
(2). under 65 degree, carry out heating in water bath, constantly stir simultaneously.The colloidal sol that obtains is then very limpid, and long-time the placement do not have the precipitation generation.
This be because, the reactive force of reuniting between amorphous precipitated: Van der Waals force, hydrogen bond etc.Adopt to stir, form such as ultrasonic, microwave can provide enough energy to break these weak reactive forces, thereby reach the purpose of disperseing amorphous pellets; Modes such as stirring simultaneously can make in the dispergation process reaction in the whole system even, and uniform crystal particles is grown up.If (1) mode of employing, because heating in water bath on, pedesis is more violent, and the mutual random collision of particle forms new amorphous pellets, does not reach the purpose of orderly crystallization.Best mode is described by (2), and then effect is better if employing mode ultrasonic or microwave replaces stirring.
Example 10. ammoniacal liquor add the influence of the excessive degree of total amount to foreign matter content in the colloidal sol
The complete sedimentary pH of unformed titanium hydroxide is 2.5-3.0, when being the precipitation agent hydrolytic precipitation with alkali lye, is reaching complete post precipitation, should continue to add excessive ammoniacal liquor more than 50%, regulates more than the pH to 9, and continues vigorous stirring 4 hours.More as can be known, ammonium chloride content seldom in the colloidal sol that present method makes by XRD.On the other hand, when ammoniacal liquor is excessive, can effectively promote the growth of anatase titanium dioxide crystalline, so the colloidal sol degree of crystallization that obtains is higher.
The preparation (concentration technique) of example 11. high density TiO 2 sols
Hydrolytic precipitation and washing step are with embodiment 1, and the precipitation of washes clean is gel, and volume is big, dispergation must add the water mixing again, and water content is very big like this, and the colloidal sol of preparing is difficult to surpass 10%.Adopt following concentration technique then can prepare concentration at the stable homogeneous colloidal sol more than 15%.Add water and will precipitate mixing, add nitric acid then,, reduce the water vapour volatilization as far as possible at the colloidal sol dispergation process initial stage, when about 20 hours, glue is transparent, and crystallization promptly allows container open to a certain degree this moment, and continue to keep former temperature heated and stirred, moisture is volatilized in a large number, can prepare the colloidal sol of higher concentration like this, also can prepare prescribed concentration colloidal sol according to actual needs.
The every index of example 12. TiO 2 sols
Survey the proportion of each different sample, as can be known the proportion of colloidal sol between 1.01-1.04, basic identical in the proportion of water, illustrate that colloidal sol is aqueous colloidal, adhesive power is strong; Know that through SEM and TEM test its median size is about 10nm, and size evenly; With colloidal sol dilution clear still more than 100 times, there is not any deposited phenomenon; Colloidal sol is taken place in long-time down (more than half a year) the no deposited phenomenon of placing of normal temperature.
Example 13. crop disease control measure of merit
(1). test method
The colloidal sol that example 1 is made be diluted to content of titanium dioxide be directly spray after 0.05% on the test plant body till drip, make blank with clear water and handle.3～6 repetitions are established in each processing.The real condition of oestrusing of a dispenser " Invest, Then Investigate " plant-growth in month and disease.
(2) test-results
Choosing lichee, mango, Pachyrhizua angulatus, corn and paddy rice is test materials, and the prevention effect of medicament to its common diseases of garden stuff investigated in the field, and test-results sees Table 1.
The field test results of all kinds of common diseases of garden stuff of table 1. control
| Test plant | Plant diseases | Disease index before the dispenser | Disease index after the dispenser | Prevention effect (%) | ||
| The check plot | Treatment zone | The check plot | Treatment zone | |||
| Lichee | Oidium | 0 | 0 | 0.25 | 0.077 | 69.2 |
| Pachyrhizua angulatus | Leaf spot | 0 | 0 | 0.57 | 0.30 | 47.3 |
| Corn | Leaf spot | 0 | 0 | 0.24 | 0.10 | 58.3 |
| Paddy rice | Rice blast | 0 | 0 | 0.136 | 0.095 | 30.1 |
Know that by experimental result pure titinium dioxide colloidal sol has best prevention effect to downy mildew of lichee.
Example 14. Quinn experimental tests
(1) substratum
[1] .DPA substratum: potato 200g, glucose or sucrose 10 ~ 20g, agar 17 ~ 20g, water 1000ml.Sterilization.
[2] .TiO
2The medicament substratum: the solid content of example 1 preparation is 5% pure titinium dioxide colloidal sol 16ml, potato 200g, glucose or sucrose 10 ~ 20g, agar 17 ~ 20g, water 1000ml.Sterilization.
(2) bacteriostasis property testing method
Carry out with the Quinn test method(s) in Ministry of Health of the People's Republic of China's 1999 (disinfection technology standard-bacteriostatic test).
The DPA substratum of reagent agent and thawing is mixed, make TiO
2The medicament substratum.With DPA substratum (sterilized water, not injection) is blank.Every processing is established repetition 3 times.
To mix with the blank substratum that melts respectively for the disease pathogenic fungi nutrient solution of examination, pour in the culture dish of sterilization, put into thermostat container (28 ℃) and cultivated 7 days, mycelia is evenly growth in culture dish, uses for inoculation.
Beat with concentric(al) circles with the punch tool of diameter 1.0cm and to get the substratum that carries disease germs, obtain the bacterium cake, take the photograph sub-gripping bacterium cake and be put in TiO with sterilization then
2On the medicament substratum plane, each culture dish is put 1 of bacterium cake, cultivates under room temperature black lamp illumination condition.
Cultivate if after the week, the bacterium colony in contrast (sterilized water, not injection) culture dish has covered with whole culture dish.Measure the colony diameter of all culture dish, each bacterium colony right-angled intersection is measured 2 times, calculates the mean diameter that each handles bacterium colony.Be calculated as follows germ and suppress growth rate (bacteriostasis rate).
Suppress growth rate=[1-(handling colony diameter-bacterium cake diameter/contrast colony diameter-bacterium cake diameter)] * 100%.
(3) the black lamp irradiation is cultivated
With the uninterrupted irradiation in 24 hours of 4 40W black lamps, the culture dish of inoculation bacterium cake is placed on the middle part of lamp at random and lines up two rows on the experiment frame.With the light intensity in the 365nm light source probe experiment with measuring district, light intensity basically identical everywhere, strength is 2.07w/cm
2, the weakest point is 1.91w/cm
2, the light intensity difference is in 10%.Adjust the culture dish putting position every day at random twice, eliminate the experimental error that the light intensity difference is brought as far as possible.
Test temperature: between 20 ℃～25 ℃;
Test humidity: 60%～80%.
(4) indoor weak light is cultivated
The culture dish of inoculation bacterium cake is placed on the experiment frame at random, does not turn on light.With the light intensity in the 365nm light source probe experiment with measuring district, strength is 1.4 μ w/cm
2, the weakest point is 1.1 μ w/cm
2Other temperature and humidity condition is the same.
Table 2. Quinn experimental test result
| Catalyzer | Ultraviolet (black lamp) | Visible light (fluorescent lamp) | Room light |
| Pure TiO 2 | 45.3 | 31.2 | 13.6 |
| 0.5％ Ce 3+-TiO 2 | 62.3 | 46.1 | 21.6 |
| 1.0％ Ce 3+-TiO 2 | 85.6 | 53.5 | 33.8 |
| 2.0％ Ce 3+-TiO 2 | 72.1 | 48.7 | 41.5 |
| 5.0％ Ce 3+-TiO 2 | 56.2 | 46.6 | 31.7 |
| 10％ Ce 3+-TiO 2 | 48.9 | 45.2 | 28.9 |
| 1.0％ Fe 3+-TiO 2 | 78.6 | 50.2 | 25.5 |
| 1.0％ La 3+-TiO 2 | 76.1 | 46.2 | 24.2 |
Know that by the result best cerium doping is 1.0% under black lamp and the fluorescent lamp condition.
Example 15. indoor air purifications (is example with formaldehyde)
(1). the glass casing is built-in with a 15w blower fan, is beneficial to keep concentration of formaldehyde balance in the casing;
(2). spraying is dried after clean with sheet glass cleaning, and the colloidal sol sample evenly is applied to the surface, treats directly to insert in the glass casing after air-dry and detects, and the colloidal sol quantity for spray is 30ml;
(3). reference sample is commercially available sprays sample;
(4). testing conditions
Detect and use instrument: the Interscan methylene oxide detecting instrument;
Detected temperatures: 33 degree;
Sense cycle: 24h;
Detect and use glass casing: 1200*600*600mm;
Spraying sheet glass: 500*500mm;
Quantity: 5;
Total effective area: 1.25m
2
Irradiation lamp: one of fluorescent lamp (18w), one of ultraviolet lamp (18w);
Titanium dioxide solid content: 0.05%.
Table 3. formaldehyde detects data
| Catalyzer | Ultraviolet (black lamp) | Visible light (fluorescent lamp) |
| Pure TiO 2 | 71.2 | 33.1 |
| 0.5％ Ce 3+-TiO 2 | 78.3 | 46.1 |
| 1.0％ Ce 3+-TiO 2 | 88.7 | 52.4 |
| 2.0％ Ce 3+-TiO 2 | 80.4 | 47.9 |
| 5.0％ Ce 3+-TiO 2 | 77.6 | 48.3 |
| 10％ Ce 3+-TiO 2 | 76.7 | 49.4 |
| 1.0％ Fe 3+-TiO 2 | 81.2 | 47.2 |
| 1.0％ La 3+-TiO 2 | 80.4 | 48.7 |
| Reference sample | 53.5 | 25.2 |
By the result as can be known, the Degradation Formaldehyde ability of TiO 2 sol and doping preparation thereof is apparently higher than the effect of commercially available sprays.And best Ce doping is 1.0%.
Claims (5)
1, a kind of preparation method of visible light photoactivated anatase type TiO 2 sol, low-temperature atmosphere-pressure is synthetic, and rare earth doped or other transition metal, it is characterized in that this method comprises the steps:
(1) hydrolytic precipitation
With the inorganic ti sources is raw material, slowly adds in the pure water under the ice-water bath condition, constantly stirs therebetween, wait to drip fully after, continue to stir 1h, make the solution cooling; Then with alkali lye as precipitation agent, control its starting point concentration, promptly its starting point concentration is not higher than 4M when alkali lye is highly basic, and its starting point concentration is not higher than 6M when alkali lye is weak base, and adding speed is for dropwise dripping, in the hydrolytic precipitation process, constantly reduce concentration of lye, minimum concentration is lower than 0.01M, treat abundant hydrolytic precipitation after, use concentration instead and be the alkali lye that is higher than 1M and regulate more than the pH to 9, constantly stir therebetween, and dripping follow-up continuous stirring fully more than 2 hours;
(2) filtration washing
Till washing and filtering is precipitated to the inclusion-free ion and detects, with the Silver Nitrate more than the 1M or bariumchloride check chlorion or sulfate ion;
(3) dispergation crystallization
Slowly adding concentration is the mineral acid of 5%-20%, adjusting pH is 0.3-2.0, and constantly stir, after adding mineral acid, at room temperature continue to stir more than 2 hours, in heating in water bath between the 40-90 degree and stir more than 3 hours, promptly obtain stable homogeneous and translucent high-purity titanium dioxide colloidal sol then;
(4) mix
A, with the titanium salt of sulphate-containing ion as the titanium source, during doped with rare-earth elements, be in the heating in water bath whipping process of step (3), to add rare earths salt then;
B, be raw material, then add rare earths salt in the pure water in step (1), or in the heating in water bath whipping process of step (3), add rare earths salt with the titanium source of sulphate-containing ion not;
Which kind of titanium source no matter C, rare earth doped other transition metal in addition then use, and all add transition metal salt solution in the pure water in step (1) or in the heating in water bath whipping process of step (3), and described other transition metal is Fe
3+, Cu
2+' or its any mixture.
2,, it is characterized in that the described mineral acid of dispergation crystallization steps (3) is: nitric acid, hydrochloric acid, sulfuric acid, perchloric acid, the perhaps any mixture of above-mentioned acid according to the preparation method of the visible light photoactivated anatase type TiO 2 sol described in the claim 1.
3, according to the preparation method of the visible light photoactivated anatase type TiO 2 sol described in the claim 1, the titanium salt of the sulphate-containing ion described in step (4) A that it is characterized in that mixing is titanium sulfate or titanyl sulfate.
4, according to the preparation method of the visible light photoactivated anatase type TiO 2 sol described in the claim 1, the rare earth element described in step (4) A and the B that it is characterized in that mixing is La
3+, Ce
3+, Nd
3+, Eu
3+Perhaps its any mixture.
5,, it is characterized in that among described doping step (4) B that the titanium source raw material of sulphate-containing ion is not titanium tetrachloride, titanous chloride or chlorination oxygen titanium according to the preparation method of the visible light photoactivated anatase type TiO 2 sol described in the claim 1.
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| CN107456966A (en) * | 2016-12-12 | 2017-12-12 | 伦慧东 | The preparation method of the in-situ modified titanium dioxide of one metal ion species |
| CN108569720A (en) * | 2017-05-05 | 2018-09-25 | 广州绿色医药科技有限公司 | A kind of novel antibacterial titanium dioxide medical dressing production technology |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1323743A (en) * | 2000-05-12 | 2001-11-28 | 中国科学院大连化学物理研究所 | Process of preparing titania sol from titanium tetrachloride |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107456966A (en) * | 2016-12-12 | 2017-12-12 | 伦慧东 | The preparation method of the in-situ modified titanium dioxide of one metal ion species |
| CN108569720A (en) * | 2017-05-05 | 2018-09-25 | 广州绿色医药科技有限公司 | A kind of novel antibacterial titanium dioxide medical dressing production technology |
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