CN106745223A - Modifying titanium dioxide raw powder's production technology and modifying titanium dioxide powder - Google Patents
Modifying titanium dioxide raw powder's production technology and modifying titanium dioxide powder Download PDFInfo
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Abstract
The invention discloses a kind of modifying titanium dioxide raw powder's production technology, belong to material chemistry technical field.Modifying titanium dioxide raw powder's production technology is comprised the following steps：S1, metal ion compound and titania powder are mixed first, dispersant and absolute ethyl alcohol are added afterwards, be well mixed, obtain ball milling material；S2, the ball grinder that will be equipped with mill ball and ball milling material are placed in ball milling are carried out in ball mill；S3, the sample after ball milling is cooled to room temperature, then carry out successively ultrasound, dry, grinding, obtain modifying titanium dioxide powder.The invention also discloses a kind of modifying titanium dioxide powder prepared using above-mentioned modifying titanium dioxide raw powder's production technology.Modifying titanium dioxide raw powder's production technology of the invention is easy to operate, and easily the particle diameter of regulation and control titanium dioxide powder, applied widely, the high income of titanium dioxide powder, are capable of achieving industrialized production, low cost.
Description
Technical field
The invention belongs to material chemistry technical field, it is related to a kind of modifying titanium dioxide raw powder's production technology and uses this
Modifying titanium dioxide powder prepared by modifying titanium dioxide raw powder's production technology.
Background technology
Titanium dioxide is used as the semi-conducting material with photo-catalysis function, active height, good anti-bacterial effect, heat endurance
The advantages of good, permanently effective, price is low and pollution-free, is used as catalyst, antiseptic etc..Pure phase titanium dioxide is excited
Produced light induced electron and hole have recombination rate higher, and quantum efficiency is relatively low, and more energy are changed to luminous energy or heat
Can release.So, it would be highly desirable to modification is carried out to existing pure phase titanium dioxide by various means, it is empty to improve light induced electron
The separating power in cave pair, lifts its photocatalysis quantum efficiency as much as possible.The existing means being modified to titanium dioxide are main
Have：(1) nano particle with quantum size effect is prepared by modified technique, improves its photocatalytic activity；(2) by two
Titanium oxide is modified, and can extend the time of light induced electron and hole-recombination, improves the life-span that light induced electron and hole are present,
And then improve photo-quantum efficiency.
In order to be able to make full use of visible ray resource, researcher has been prepared by various methods the arrowband of different the Nomenclature Composition and Structure of Complexes
Gap titanium dioxide semiconductor, it is desired to be able to effective degradation of organic substances under excited by visible light.ChoiHyeok seminars report with
Sol-gel process prepares titanium dioxide nanocrystalline to improve its photocatalytic activity.Xu et al. is then reported and is prepared two with hydro-thermal method
The photocatalytic effect of titania surface in-situ growing carbon nano tube composite granule.These researchs are unanimously thought to carry out titanium dioxide
After doping vario-property, either in ultraviolet region or visible region, the utilization rate to visible ray of composite granule is obtained for
It is correspondingly improved.
Traditional physics, chemical method are widely used at titania modified aspect, but still exist each
From deficiency.For example, Physical can be obtained the easily-controllable ultrafine particle of particle diameter, but required apparatus expensive；Chemical method low cost, condition
Simply, it is easy to which by process control and adjustment particle size, but narrow application range, long flow path, yield is low, it is impossible to realize industrialization
Production.Therefore, need badly and seek a kind of easy to operate, easily regulate and control particle diameter, applied widely, high income is capable of achieving industry
Metaplasia is produced, the modifying titanium dioxide preparation technology of low cost.
The content of the invention
(1) technical problem to be solved
In order to solve the above mentioned problem of prior art, the present invention provides a kind of easy to operate, easily regulates and controls particle diameter, fits
Wide, the high income with scope, is capable of achieving industrialized production, the modifying titanium dioxide raw powder's production technology of low cost.
The present invention also provides a kind of modifying titanium dioxide prepared using above-mentioned modifying titanium dioxide raw powder's production technology
Powder, the particle diameter of the modifying titanium dioxide powder is easily-controllable, has excellent absorption in visible region, and the utilization rate to visible ray is high.
(2) technical scheme
In order to achieve the above object, the main technical schemes that the present invention is used include：
A kind of modifying titanium dioxide raw powder's production technology, comprises the following steps：
S1, metal ion compound and titania powder are mixed first, dispersant and absolute ethyl alcohol are added afterwards, mixed
Close uniform, obtain ball milling material；
S2, the ball grinder that will be equipped with mill ball and ball milling material are placed in ball milling are carried out in ball mill；
S3, the sample after ball milling is cooled to room temperature, then carry out successively ultrasound, dry, grinding, obtain modifying titanium dioxide
Powder.
In the present invention, the metal ion compound is the one kind in cobalt acetate, lithium sulfate, zinc nitrate, the metal
Ionic compound is 1 ﹕ 1-1 ﹕ 10 with the mol ratio of titania powder.
In the present invention, the dispersant is stearic acid, the mixing of the metal ion compound and titania powder
Thing is 50 ﹕ 1 with stearic mass ratio.
In the present invention, the mass ratio of the mixture of the metal ion compound and titania powder and absolute ethyl alcohol
It is 2 ﹕ 1.
In the present invention, the S2 is comprised the following steps：
S21, take mill ball particle diameter be 3-10mm zirconium oxide abrasive ball be sequentially placed into aluminum oxide according to size is descending
Ball grinder；
S22, ball milling material is laid on mill ball, be placed in carries out ball milling afterwards in ball mill.
In the present invention, in S21, the mill ball particle diameter is respectively 3mm, 5mm, 8mm, 10mm, and mass ratio is 1-
The ﹕ 1 of 3 ﹕ 1-2 ﹕ 1.
In the present invention, the mill ball and the mass ratio of ball milling material are 10 ﹕ 1-20 ﹕ 1.
In the present invention, the rotary speed of the ball mill is 300r/min, and revolution rotational velocity ratio is 1 ﹕ 1.5, ball milling
Time is 0.5-10h.
In the present invention, the drying temperature is 90-105 DEG C, and drying time is 12-24h.
A kind of modifying titanium dioxide powder, the modifying titanium dioxide powder is used as described in any of the above preferred scheme
Modifying titanium dioxide raw powder's production technology is prepared from.
(3) beneficial effect
The beneficial effects of the invention are as follows：
The present invention uses high-energy-milling, by material titania powder and metal ion compound and mill ball it
Between grinding with clash into, so as to reduce the particle diameter of material, titanium dioxide and metal ion compound is mutually penetrated into diffusion, shape
Into the tissue based on titanium dioxide and two-phase or multiphase heterojunction structure of distributed components, in this way, both remaining pure phase
Advantage in terms of the intrinsic physicochemical properties of titanium dioxide, is carried out auxiliary using the second newly-increased phase or other phase constituent elements to it again
Reinforcing is helped, the work of capture trap is played to the photo-generated carrier that intrinsic excitation is produced by second or the third element that produce
With, and an impurity energy level can be produced between the conduction band and valence band of titanium dioxide, and photoactivation process is participated in, expand spectrum
Response is interval, both ensure that titanium dioxide powder had Nano quantum dimensional effect, and its spectral response interval can be expanded again, from
And the recombination rate of photo-generate electron-hole pair is reduced, improve its sterilizing rate.
Compared with existing modifying titanium dioxide preparation method, modifying titanium dioxide raw powder's production technology of the invention
It is easy to operate, easily regulate and control the particle diameter of titanium dioxide powder, applied widely, the high income of titanium dioxide powder can be real
Existing industrialized production, low cost.
The average grain diameter of the modifying titanium dioxide powder prepared by the present invention is small, and specific surface area is big, has in visible region
Excellent absorption, its utilization rate to visible ray is high, and around-France large intestine bar is carried out to modifying titanium dioxide powder by using antibacterial
The anti-microbial property test of bacterium, the antibiotic property of modifying titanium dioxide powder is strong.
Brief description of the drawings
Fig. 1 is the flow chart of modifying titanium dioxide raw powder's production technology of the invention；
Fig. 2 is the SEM figures of the titanium dioxide powder of comparative example 1-5 of the present invention；
Fig. 3 is the XRD spectrum of the titanium dioxide powder of comparative example 1-5 of the present invention；
Fig. 4 is the BET figures of the titanium dioxide powder of comparative example 1-5 of the present invention；
Fig. 5 is the UV-Vis-DRS figures of the titanium dioxide powder of comparative example 1-5 of the present invention；
Fig. 6 is the SEM figures of the modifying titanium dioxide powder of embodiment of the present invention 1-5；
Fig. 7 is the XRD spectrum of the modifying titanium dioxide powder of embodiment of the present invention 1-5；
Fig. 8 is the BET figures of the modifying titanium dioxide powder of embodiment of the present invention 1-5；
Fig. 9 is the UV-Vis-DRS figures of the modifying titanium dioxide powder of embodiment of the present invention 1-5；
Figure 10 is the SEM figures of the modifying titanium dioxide powder of the embodiment of the present invention 3,6-7；
Figure 11 is the XRD spectrum of the modifying titanium dioxide powder of the embodiment of the present invention 3,6-11；
Figure 12 is the BET figures of the modifying titanium dioxide powder of the embodiment of the present invention 3,6-7；
Figure 13 is the UV-Vis-DRS figures of the modifying titanium dioxide powder of the embodiment of the present invention 3,6-7；
Figure 14 is the SEM figures of the modifying titanium dioxide powder of the embodiment of the present invention 3,8-9；
Figure 15 is the BET figures of the modifying titanium dioxide powder of the embodiment of the present invention 3,8-9；
Figure 16 is the UV-Vis-DRS figures of the modifying titanium dioxide powder of the embodiment of the present invention 3,8-9；
Figure 17 is the SEM figures of the modifying titanium dioxide powder of the embodiment of the present invention 3,10-11；
Figure 18 is the BET figures of the modifying titanium dioxide powder of the embodiment of the present invention 3,10-11；
Figure 19 is the UV-Vis-DRS figures of the modifying titanium dioxide powder of the embodiment of the present invention 3,10-11；
Figure 20 is the SEM figures of the modifying titanium dioxide powder of the embodiment of the present invention 12；
Figure 21 is the XRD spectrum of the modifying titanium dioxide powder of the embodiment of the present invention 12；
Figure 22 is the UV-Vis-DRS figures of the modifying titanium dioxide powder of the embodiment of the present invention 12；
Figure 23 is the SEM figures of the modifying titanium dioxide powder of the embodiment of the present invention 13；
Figure 24 is the XRD spectrum of the modifying titanium dioxide powder of the embodiment of the present invention 13；
Figure 25 is the UV-Vis-DRS figures of the modifying titanium dioxide powder of the embodiment of the present invention 13.
Specific embodiment
In order to preferably explain the present invention, in order to understand, below in conjunction with the accompanying drawings, by specific embodiment, to this hair
It is bright to be described in detail.
The characteristics of high-energy ball milling method is main is to make the material can be with recurring structure and physical chemistry in the presence of mechanical force
Change in matter, and have the advantages that cheap, environment-friendly, high efficiency and controllability are high, therefore can be used for industry
Metaplasia is produced.
The present invention proposes a kind of method that utilization high-energy-milling prepares titanium dioxide powder, and it is comprised the following steps：
The analysis pure titinium dioxide powder of certain mass is taken, the stearic acid dispersant and anhydrous second of certain mass are added afterwards
Alcoholic solvent, mixing and stirring obtains ball milling material；
Take the mill ball that size is 3-10mm and be put into the ball grinder that volume is 500ml, by above-mentioned equipped with mill ball and ball milling
The ball grinder of material is put into planetary high-energy ball mill and carries out ball milling together with the ball grinder equipped with fine sand equal quality；
Sample after ball milling is cooled to room temperature, then is carried out ultrasound successively, is dried, grinds, obtain titanium dioxide powder.
In the research of nanostructured formation mechenism, it is believed that Process During High Energy Ball Milling is a mistake for particle circulation shear deformation
Journey, in the process, crystal grain defect is constantly largely produced inside the particle of big crystal grain, so as to cause high-angle boundary in particle
Reconfigure so that crystallite dimension can decline 10 in particle3-104The individual order of magnitude.If two or more powder is same
When be put into the ball grinder of ball mill and carry out high-energy ball milling, repetitive process of the powder particle through rolling, pressing, pulverize, press again,
The small sample with heterogeneous structure can finally be obtained.
Further, as shown in figure 1, the present invention proposes that a kind of utilization high-energy-milling prepares modified titanium dioxide powder
The method of body, it is comprised the following steps：
Metal ion compound and the titania powder mixing of certain mol proportion are taken, the tristearin of certain mass is added afterwards
Acid dispersant and anhydrous ethanol solvent, mixing and stirring obtain ball milling material；
Take the mill ball that size is 3-10mm and be put into the ball grinder that volume is 500ml, by above-mentioned equipped with mill ball and ball milling
The ball grinder of material is put into planetary high-energy ball mill and carries out ball milling together with the ball grinder equipped with fine sand equal quality；
Sample after ball milling is cooled to room temperature, then is carried out ultrasound successively, is dried, grinds, obtain modifying titanium dioxide powder
Body.
In above-mentioned titanium dioxide powder and modifying titanium dioxide raw powder's production technology, stearic addition can be right
Mixed material is preferably disperseed, and prevents material from agglomeration occurring.
Additionally, during mill ball is added, be added sequentially in ball grinder according to the size of mill ball is descending,
Can so avoid the space taken in ball grinder by mill ball excessive and it is follow-up add material when beyond the general of charging
It is required that (material of addition ensures 2nd/1st to three/2nd of vessel volume).
In order to avoid titanium dioxide powder and the agglomerate grain phenomenon of modifying titanium dioxide powder sample, after ball milling
Sample carries out ultrasound again after the cooling period, so as to improve the dispersing uniformity of final sample, and then improves sample in photocatalysis
The antibiotic property of antibiosis.
The nano TiO 2 powder of the metal ion mixing prepared by high-energy ball milling method had both been retained titanium-dioxide photo and urged
Change the advantage in terms of the intrinsic physicochemical properties of antiseptic, it is carried out using the second newly-increased phase constituent element again assisted and strengthened.
At newly-established effective heterostructure interface, energy with carrier or photon as carrier carry out it is efficient transport and transmit,
Spectral response interval is expanded, the recombination rate of photo-generate electron-hole pair has been reduced and is improved its sterilizing rate.At present, the country does not have also
There is the evaluation criterion of unified inorganic antiseptic service check, in order to inquire into the nano titania after being prepared through high-energy ball milling method
Effect of the powder in terms of photocatalysis antibacterial, the present invention uses for reference the bacteriologic test method of food and health and epidemic prevention department, using suppression
Collarium method carries out the qualitative evaluation of the anti-microbial property of Escherichia coli to made sample.For example following comparative example of concrete condition and implementation
Example：
Comparative example 1
Comparative example 1 provides a kind of preparation method of titanium dioxide powder, and it is comprised the following steps：
A1,100g analysis pure titinium dioxide powder is taken, and add the stearic acid of 2g and the absolute ethyl alcohol of 50g, mixed
Uniformly, ball milling material is obtained；
A21, the zirconium oxide abrasive ball that mass ratio is the ﹕ 1, particle diameter of 2 ﹕, 2 ﹕ 1 respectively 3mm, 5mm, 8mm, 10mm is taken, by size
It is descending to be sequentially placed into the alumina balls grinding jar that volume is 500ml；
A22, it is that the ball milling material of 10 ﹕ 1 is laid on mill ball by ratio of grinding media to material, will be equipped with the ball of mill ball and ball milling material
Grinding jar is put into planetary high-energy ball mill and carries out ball milling together with the ball grinder equipped with fine sand equal quality, wherein, the public affairs of ball mill
Speed walk around for 300r/min, revolution rotational velocity ratio is 1：1.5, Ball-milling Time is 0.5h；
A3, the reactant after ball milling is cooled to room temperature, is 220V in voltage, frequency is 50Hz, the bar that temperature is 30 DEG C
Ultrasound 20min under part, 100 DEG C dry 12h, uniform grinding, obtain titanium dioxide powder.
Comparative example 2-5
The step of with comparative example 1 is similar to, and comparative example 2-5 is the Ball-milling Time in only set-up procedure A22 to be realized, remaining
Part is constant.Specifically, the Ball-milling Time in comparative example 2,3,4,5 is respectively 1h, 3h, 5h, 10h.
With reference to comparative example 1-5, titanium dioxide powder prepared by titanium dioxide powder and comparative example 1-5 to non-ball milling is carried out
ESEM (SEM), X-ray diffraction (XRD), surface analysis (BET), UV-vis DRS (UV-Vis-DRS) etc. are surveyed
Examination, each test result difference is as shown in Figure 2-5.The titanium dioxide powder of non-ball milling and comparative example 1-5 are passed through into ball-milling technology system
Standby titanium dioxide powder is used for the anti-microbial property test of Escherichia coli, and test result is as follows.
With reference to Fig. 2 to Fig. 5, make a concrete analysis of as follows：Fig. 2 a-f are shown the titanium dioxide powder and ball milling of non-ball milling
The particle diameter distribution of the titanium dioxide powder after 0.5-10h.As can be seen from Figure 2, the particle diameter distribution of the titanium dioxide powder of non-ball milling
Between 1-5um；With the increase of Ball-milling Time, the particle diameter of titanium dioxide powder is gradually decreased, most one stabilization of Zhongdao it is flat
Weighing apparatus state, particle diameter is reduced to 100-500nm and no longer changes after ball milling 3h, finally can obtain nano TiO 2 powder.
From figure 3, it can be seen that the product after comparative example 1-5 ball millings is containing 98% anatase phase titanium dioxide and 2% gold
Red stone phase titanic oxide, compared with the titanium dioxide of non-ball milling, without the change that ore deposit phase occurs and the generation of novel substance.
From fig. 4, it can be seen that the titanium dioxide powder specific surface area of the titanium dioxide powder of non-ball milling and ball milling 0.5-10h
Increase with the increase of Ball-milling Time, finally no longer change, reach a poised state for stabilization.
From fig. 5, it can be seen that the extinction of each titanium dioxide powder of comparative example 1-5 is interval and absorbance is basically identical,
I.e. titanium dioxide powder has stronger light absorpting ability in ultraviolet region, and in visible region, the light absorbs of titanium dioxide powder
Ability is significantly reduced, and with the increase of Ball-milling Time, the ABSORPTION EDGE of titanium dioxide powder does not change.Because titanium dioxide
Used as a kind of N-type semiconductor, its larger band gap causes that only ultraviolet light could effectively excite titanium dioxide valence band electricity to titanium
Son transits to conduction band, to visible ray almost without absorption.
The titanium dioxide powder of non-ball milling and the titanium dioxide powder of ball milling 0.5h do not have bactericidal effect to Escherichia coli, with
The increase of Ball-milling Time, the diameter of antibacterial ring size gradually increases, averagely in 1-2cm.
As can be seen here, high-energy ball milling method is only capable of reducing the grain size of titanium dioxide powder, can not expand titanium dioxide
The spectral response of powder is interval, and the present invention carries out high-energy ball milling doping vario-property using metal ion to titanium dioxide, by producing
Second or third element the photo-generated carrier that intrinsic excitation is produced is played a part of to capture trap, and one can be produced
Individual impurity energy level participates in photoactivation process between the conduction band and valence band of titanium dioxide, expands spectral response interval, both ensures two
Titanium oxide powder has Nano quantum dimensional effect, and its spectral response interval can be expanded again, reduces photo-generate electron-hole pair
Recombination rate, improves its sterilizing rate.
Embodiment 1
Embodiment 1 provides a kind of modifying titanium dioxide raw powder's production technology, comprises the following steps：
S1, mol ratio is taken for 1 ﹕ 1, gross mass is cobalt acetate and the titania powder mixing of 100g, and sequentially adds 2g
Stearic acid and 50g absolute ethyl alcohol (concentration is 99.7%), mixing and stirring obtains ball milling material；
S21, the zirconium oxide abrasive ball that mass ratio is the ﹕ 1, particle diameter of 2 ﹕, 2 ﹕ 1 respectively 3mm, 5mm, 8mm, 10mm is taken, by size
It is descending to be sequentially placed into the alumina balls grinding jar that volume is 500ml；
S22, it is that the ball milling material of 10 ﹕ 1 is laid on mill ball by ratio of grinding media to material, will be equipped with the ball of mill ball and ball milling material
Grinding jar is put into planetary high-energy ball mill and carries out ball milling together with the ball grinder equipped with fine sand equal quality, wherein, the public affairs of ball mill
Speed walk around for 300r/min, revolution rotational velocity ratio is 1：1.5, Ball-milling Time is 0.5h；
S3, the reactant after ball milling is cooled to room temperature, is 220V in voltage, frequency is 50Hz, the bar that temperature is 30 DEG C
Ultrasound 20min under part, 90 DEG C dry 12h, uniform grinding, obtain cobalt acetate modifying titanium dioxide powder.
Embodiment 2-5
The step of with embodiment 1 is similar to, and embodiment 2-5 is the Ball-milling Time in only set-up procedure S22 to be realized, remaining
Part is constant.Specifically, the Ball-milling Time in embodiment 2,3,4,5 is respectively 1h, 3h, 5h, 10h.
1-5, SEM, XRD, BET, UV- are carried out to modifying titanium dioxide powder prepared by embodiment 1-5 in conjunction with the embodiments
Vis-DRS etc. is tested, and each test result difference is as Figure 6-9.The modified dioxy that embodiment 1-5 is prepared by ball-milling technology
Changing titanium valve body is used for the anti-microbial property test of Escherichia coli, and test result is as follows.
With reference to Fig. 6 to Fig. 9, make a concrete analysis of as follows：Fig. 6 a-e are shown the acetic acid cobalt doped after high-energy ball milling 0.5-10h
Titanium dioxide powder particle diameter distribution.As can be seen from Figure 6, with the increase of Ball-milling Time, the titanium dioxide of acetic acid cobalt doped
The particle diameter of powder is gradually decreased, most one poised state of stabilization of Zhongdao, and particle diameter is reduced to 100-500nm no longer after ball milling 3h
Change, finally can obtain the nano TiO 2 powder after acetic acid cobalt doped.
In the figure 7, A and B are respectively the XRD of material after ball milling 0.5h and 1h, and C is the XRD of material after ball milling 3-10h
Figure.From figure 7 it can be seen that with the increase of Ball-milling Time, starting the new constituent element CoTiO of generation3, the thing phase of the material after ball milling
Mainly there is Anatase TiO2、CoTiO3、Co(C2H3O2)2And a small amount of Rutile Type TiO2。
From figure 8, it is seen that with the increase of Ball-milling Time, the ratio of the nano TiO 2 powder of cobalt acetate doping vario-property
Surface area gradually increases, and finally no longer changes, and reaches a poised state for stabilization.
From fig. 9, it can be seen that ball milling initial stage titanium dioxide powder has stronger light absorpting ability in ultraviolet region；With ball
The increase of time consuming, the ABSORPTION EDGE of titanium dioxide powder is moved to visible ray, and this is probably the second phase constituent element pair because newly-increased
Titanium dioxide powder carries out assisted and strengthened, and it is interval to have expanded spectral response, reduces the recombination rate of photo-generate electron-hole pair.Ball milling
Light area is absorbed after 3h no longer to change.
The modified titanium dioxide doped nano-powder of cobalt acetate after ball milling 1h, 3h, 5h and 10h has sterilization to Escherichia coli
Effect, antibacterial ring size is respectively 2.7cm, 3.3cm, 3.3cm, 3.3cm.
Embodiment 6
Embodiment 6 provides a kind of modifying titanium dioxide raw powder's production technology, comprises the following steps：
S1, mol ratio is taken for 1 ﹕ 10, gross mass is cobalt acetate and the titania powder mixing of 100g, and sequentially adds 2g
Stearic acid and 50g absolute ethyl alcohol (concentration is 99.7%), mixing and stirring obtains ball milling material；
S21, the zirconium oxide abrasive ball that mass ratio is the ﹕ 1, particle diameter of 2 ﹕, 2 ﹕ 1 respectively 3mm, 5mm, 8mm, 10mm is taken, by size
It is descending to be sequentially placed into the alumina balls grinding jar that volume is 500ml；
S22, it is that the ball milling material of 10 ﹕ 1 is laid on mill ball by ratio of grinding media to material, will be equipped with the ball of mill ball and ball milling material
Grinding jar is put into planetary high-energy ball mill and carries out ball milling together with the ball grinder equipped with fine sand equal quality, wherein, the public affairs of ball mill
Speed walk around for 300r/min, revolution rotational velocity ratio is 1：1.5, Ball-milling Time is 3h；
S3, the reactant after ball milling is cooled to room temperature, is 220V in voltage, frequency is 50Hz, the bar that temperature is 30 DEG C
Ultrasound 20min under part, 90 DEG C dry 12h, uniform grinding, obtain cobalt acetate modifying titanium dioxide powder.
Embodiment 7
The step of with embodiment 6, is similar to, and embodiment 7 is rubbing for cobalt acetate in only set-up procedure S1 and titania powder
You compare to realize, remaining condition is constant.Specifically, the mol ratio of cobalt acetate and titania powder is 1 ﹕ 5 in embodiment 7.
In conjunction with the embodiments 3,6,7, modifying titanium dioxide powder prepared by embodiment 3,6,7 is carried out SEM, XRD, BET,
UV-Vis-DRS etc. is tested, and each test result difference is as shown in figures 10-13.Embodiment 3,6,7 is prepared by ball-milling technology
Modifying titanium dioxide powder is used for the anti-microbial property test of Escherichia coli, and test result is as follows.
With reference to Figure 10 to Figure 13, make a concrete analysis of as follows：Figure 10 a-c are shown the acetic acid cobalt doped after high-energy ball milling 3h
Particle diameter distribution of the titanium dioxide powder under different dopings.As can be seen from Figure 10, with the increase of doping, acetic acid cobalt doped
The particle diameter of titanium dioxide powder there is no significant changes, be substantially distributed between 100-500nm.
It can be seen from figure 11 that cobalt acetate and titanium dioxide mol ratio generate new constituent element when being 1 ﹕ 10,1 ﹕ 5 and 1 ﹕ 1
CoTiO3, the thing of material mutually mainly has Anatase TiO after ball milling2、CoTiO3、Co(C2H3O2)2And a small amount of Rutile Type
TiO2。
It can be recognized from fig. 12 that in embodiment 3,6,7 nano TiO 2 powder of cobalt acetate doping vario-property specific surface
Product is average in 23-24m2Between/g.
As can be seen from Figure 13, cobalt acetate and titanium dioxide mol ratio are the material of 1 ﹕ 10,1 ﹕ 5 and 1 ﹕ 1 after ball milling 3h
Its ABSORPTION EDGE is moved to visible region, wherein, when mol ratio is 1 ﹕ 1, its moving area is larger.
When cobalt acetate is 1 ﹕ 10,1 ﹕ 5 and 1 ﹕ 1 with titanium dioxide mol ratio, the titanium dioxide powder of acetic acid cobalt doped is to big
Enterobacteria has bactericidal effect, and antibacterial ring size is 3.5cm when mol ratio is 1 ﹕ 10, and antibacterial ring size is 4.0cm when mol ratio is 1 ﹕ 5, is rubbed
Antibacterial ring size is 4.5cm when you are than for 1 ﹕ 1.
Embodiment 8
Embodiment 8 provides a kind of modifying titanium dioxide raw powder's production technology, comprises the following steps：
S1, mol ratio is taken for 1 ﹕ 1, gross mass is cobalt acetate and the titania powder mixing of 100g, and sequentially adds 2g
Stearic acid and 50g absolute ethyl alcohol (concentration is 99.7%), mixing and stirring obtains ball milling material；
S21, the zirconium oxide abrasive ball that mass ratio is the ﹕ 1, particle diameter of 2 ﹕, 2 ﹕ 1 respectively 3mm, 5mm, 8mm, 10mm is taken, by size
It is descending to be sequentially placed into the alumina balls grinding jar that volume is 500ml；
S22, it is that the ball milling material of 15 ﹕ 1 is laid on mill ball by ratio of grinding media to material, will be equipped with the ball of mill ball and ball milling material
Grinding jar is put into planetary high-energy ball mill and carries out ball milling together with the ball grinder equipped with fine sand equal quality, wherein, the public affairs of ball mill
Speed walk around for 300r/min, revolution rotational velocity ratio is 1：1.5, Ball-milling Time is 3h；
S3, the reactant after ball milling is cooled to room temperature, is 220V in voltage, frequency is 50Hz, the bar that temperature is 30 DEG C
Ultrasound 20min under part, 90 DEG C dry 12h, uniform grinding, obtain cobalt acetate modifying titanium dioxide powder.
Embodiment 9
The step of with embodiment 8 is similar to, and embodiment 9 is the ratio of grinding media to material in only set-up procedure S22 to be realized, remaining condition is not
Become.Specifically, the ratio of grinding media to material in embodiment 9 is 20 ﹕ 1.
In conjunction with the embodiments 3,8,9, modifying titanium dioxide powder prepared by embodiment 3,8,9 is carried out SEM, XRD, BET,
UV-Vis-DRS etc. is tested, and each test result is respectively as shown in Figure 14, Figure 11, Figure 15-16.Embodiment 3,8,9 is passed through into ball milling
Modifying titanium dioxide powder prepared by technique is used for the anti-microbial property test of Escherichia coli, and test result is as follows.
With reference to Figure 14,11,15 to Figure 16, make a concrete analysis of as follows：Figure 14 a-c are shown the cobalt acetate after high-energy ball milling 3h
Particle diameter distribution of the titanium dioxide powder of doping under different ratios of grinding media to material.As can be seen from Figure 14, with the increase of material, cobalt acetate
The particle diameter of the titanium dioxide powder of doping is gradually reduced on the contrary, and this is probably because working as the timing of quality one of mill ball, when ball material
Than high, material is relatively fewer, is so also easy to produce empty mill and only the material of fraction is captured by the interface between ball and ball,
Others spread apart due to shearing force and the effect rubbed, so as to cause particle diameter bigger than normal.
Figure 11 shows, when ratio of grinding media to material is 10 ﹕ 1,15 ﹕ 1 and 20 ﹕ 1, the thing of material mutually mainly has Anatase after ball milling
TiO2、CoTiO3、Co(C2H3O2)2And a small amount of Rutile Type TiO2。
Figure 15 shows that the specific surface area of the nano TiO 2 powder of cobalt acetate doping vario-property is average in embodiment 3,8,9
In 12-24m2Between/g.
Knowable to Figure 16, cobalt acetate its suction after ball milling 3h with the material that titanium dioxide ratio of grinding media to material is 10 ﹕ 1,15 ﹕ 1 and 20 ﹕ 1
Side is received to be moved to visible region.
When ratio of grinding media to material is 10 ﹕ 1,15 ﹕ 1 and 20 ﹕ 1, the titanium dioxide powder material of acetic acid cobalt doped has to Escherichia coli
Bactericidal effect, antibacterial ring size is 5.0cm when ratio of grinding media to material is 10 ﹕ 1, and antibacterial ring size is 4.5cm when ratio of grinding media to material is 15 ﹕ 1, and ratio of grinding media to material is 20 ﹕ 1
When antibacterial ring size be 3.7cm.
Embodiment 10
Embodiment 10 provides a kind of modifying titanium dioxide raw powder's production technology, comprises the following steps：
S1, mol ratio is taken for 1 ﹕ 1, gross mass is cobalt acetate and the titania powder mixing of 100g, and sequentially adds 2g
Stearic acid and 50g absolute ethyl alcohol (concentration is 99.7%), mixing and stirring obtains ball milling material；
S21, the zirconium oxide abrasive ball that mass ratio is the ﹕ 1, particle diameter of 2 ﹕, 1 ﹕ 1 respectively 3mm, 5mm, 8mm, 10mm is taken, by size
It is descending to be sequentially placed into the alumina balls grinding jar that volume is 500ml；
S22, it is that the ball milling material of 10 ﹕ 1 is laid on mill ball by ratio of grinding media to material, will be equipped with the ball of mill ball and ball milling material
Grinding jar is put into planetary high-energy ball mill and carries out ball milling together with the ball grinder equipped with fine sand equal quality, wherein, the public affairs of ball mill
Speed walk around for 300r/min, revolution rotational velocity ratio is 1：1.5, Ball-milling Time is 3h；
S3, the reactant after ball milling is cooled to room temperature, is 220V in voltage, frequency is 50Hz, the bar that temperature is 30 DEG C
Ultrasound 20min under part, 90 DEG C dry 12h, uniform grinding, obtain cobalt acetate modifying titanium dioxide powder.
Embodiment 11
The step of with embodiment 10, is similar to, embodiment 11 be particle diameter respectively 3mm in only set-up procedure S21,5mm, 8mm,
The mill ball particle diameter ratio of 10mm realizes that remaining condition is constant.Specifically, mill ball particle diameter ratio is the ﹕ 1 of 3 ﹕, 2 ﹕ 1 in embodiment 11.
In conjunction with the embodiments 3,10,11, modifying titanium dioxide powder prepared by embodiment 3,10,11 is carried out SEM, XRD,
BET, UV-Vis-DRS etc. are tested, and each test result is respectively as shown in Figure 17, Figure 11, Figure 18-19.Embodiment 3,10,11 is led to
Crossing the modifying titanium dioxide powder of ball-milling technology preparation is used for the anti-microbial property test of Escherichia coli, and test result is as follows.
With reference to Figure 17,11,18 to Figure 19, make a concrete analysis of as follows：Figure 17 a-c are shown the cobalt acetate after high-energy ball milling 3h
Particle diameter distribution of the titanium dioxide powder of doping in different mill ball particle diameters than under.As can be seen from Figure 21, with 3mm and 5mm balls
The addition of particle diameter, the particle diameter of the titanium dioxide powder of acetic acid cobalt doped gradually increases, and this is probably because when the quality of mill ball
Necessarily, the timing of material one, the smaller mill ball in mechanical milling process of ball grain size is bigger with the contact area of material, so easy
So that material is captured by the interface between ball and ball, so as to cause particle diameter gradually smaller.
Figure 11 shows, when mill ball particle diameter ratio is the ﹕ 1 of 2 ﹕, 1 ﹕ 1, the ﹕ 1 of 2 ﹕, 2 ﹕ 1,3 ﹕, 21 ﹕ 1 of ﹕, the thing of material is mutually main after ball milling
There is Anatase TiO2、CoTiO3、Co(C2H3O2)2And a small amount of Rutile Type TiO2。
Figure 18 shows that the specific surface area of the nano TiO 2 powder of the cobalt acetate doping vario-property of embodiment 3,10,11 is average
In 20-24m2Between/g.
Figure 19 understands, cobalt acetate and titanium dioxide mill ball particle diameter than for the ﹕ 1 of 2 ﹕, 1 ﹕ 1, the ﹕ 1 of 2 ﹕, 2 ﹕ 1, the ﹕ 1 of 3 ﹕, 2 ﹕ 1 material
Its ABSORPTION EDGE is moved to visible region after ball milling 3h.
When mill ball particle diameter ratio is the ﹕ 1 of 2 ﹕, 1 ﹕ 1, the ﹕ 1 of 2 ﹕, 2 ﹕ 1,3 ﹕, 21 ﹕ 1 of ﹕, the titanium dioxide powder of acetic acid cobalt doped is to big
Enterobacteria has bactericidal effect, suppression of the material to Escherichia coli when mill ball particle diameter is than for the ﹕ 1 of 2 ﹕, 1 ﹕ 1, the ﹕ 1 of 2 ﹕, 2 ﹕ 1,3 ﹕, 21 ﹕ 1 of ﹕
Collarium is respectively 3.7cm, 4.2cm, 5.0cm.
Embodiment 1-11 is displayed in material ratio for 10 ﹕ 1, the ﹕ 1, cobalt acetate of 3 ﹕ of mill ball particle diameter, 2 ﹕ 1 and titanium dioxide mol ratio
1 ﹕ 1, through the acetic acid cobalt doped after high-energy ball milling 3h titanium dioxide powder particle diameter between 100-500nm, can generate new
Constituent element CoTiO3, specific surface area is 23.89m2/ g, ABSORPTION EDGE is moved to visible light direction, and good to Escherichia coli bactericidal effect
Good, antibacterial ring size is up to 5.0cm.
Embodiment 12
Embodiment 12 provides a kind of modifying titanium dioxide raw powder's production technology, comprises the following steps：
S1, mol ratio is taken for 1 ﹕ 1, gross mass is lithium sulfate and the titania powder mixing of 100g, and sequentially adds 2g
Stearic acid and 50g absolute ethyl alcohol (concentration is 99.7%), mixing and stirring obtains ball milling material；
S21, the zirconium oxide abrasive ball that mass ratio is the ﹕ 1, particle diameter of 3 ﹕, 2 ﹕ 1 respectively 3mm, 5mm, 8mm, 10mm is taken, by size
It is descending to be sequentially placed into the alumina balls grinding jar that volume is 500ml；
S22, it is that the ball milling material of 10 ﹕ 1 is laid on mill ball by ratio of grinding media to material, will be equipped with the ball of mill ball and ball milling material
Grinding jar is put into planetary high-energy ball mill and carries out ball milling together with the ball grinder equipped with fine sand equal quality, wherein, the public affairs of ball mill
Speed walk around for 300r/min, revolution rotational velocity ratio is 1：1.5, Ball-milling Time is 3h；
S3, the reactant after ball milling is cooled to room temperature, is 220V in voltage, frequency is 50Hz, the bar that temperature is 30 DEG C
Ultrasound 20min under part, 100 DEG C dry 24h, uniform grinding, obtain lithium sulfate modifying titanium dioxide powder.
SEM, XRD, UV-Vis-DRS etc. are carried out to the modified titanium dioxide doped powder of lithium sulfate prepared by embodiment 12 to survey
Examination, each test result difference is as illustrated in figs 20-22.Embodiment 12 is used by modifying titanium dioxide powder prepared by ball-milling technology
In the anti-microbial property test of Escherichia coli, test result is as follows.
Figure 20 shows that the particle diameter distribution of the titanium dioxide powder of sulfuric acid lithium doping is in 100-500nm after high-energy ball milling 3h
Between.Figure 21 shows that the product of the present embodiment is anatase phase titanium dioxide, Li2TiO3And Li2SO4.Figure 22 shows, ball milling 3h
Material ABSORPTION EDGE afterwards is moved to visible region.The titanium dioxide powder of the present embodiment sulfuric acid lithium doping is to the antibacterial of Escherichia coli
Ring is 5.0cm.
Embodiment 13
Embodiment 13 provides a kind of modifying titanium dioxide raw powder's production technology, comprises the following steps：
S1, mol ratio is taken for 1 ﹕ 1, gross mass is zinc nitrate and the titania powder mixing of 100g, and sequentially adds 2g
Stearic acid and 50g absolute ethyl alcohol (concentration is 99.7%), mixing and stirring obtains ball milling material；
S21, the zirconium oxide abrasive ball that mass ratio is the ﹕ 1, particle diameter of 3 ﹕, 2 ﹕ 1 respectively 3mm, 5mm, 8mm, 10mm is taken, by size
It is descending to be sequentially placed into the alumina balls grinding jar that volume is 500ml；
S22, it is that the ball milling material of 10 ﹕ 1 is laid on mill ball by ratio of grinding media to material, will be equipped with the ball of mill ball and ball milling material
Grinding jar is put into planetary high-energy ball mill and carries out ball milling together with the ball grinder equipped with fine sand equal quality, wherein, the public affairs of ball mill
Speed walk around for 300r/min, revolution rotational velocity ratio is 1：1.5, Ball-milling Time is 3h；
S3, the reactant after ball milling is cooled to room temperature, is 220V in voltage, frequency is 50Hz, the bar that temperature is 30 DEG C
Ultrasound 20min under part, 105 DEG C dry 18h, uniform grinding, obtain lithium sulfate modifying titanium dioxide powder.
SEM, XRD, UV-Vis-DRS etc. are carried out to the modified titanium dioxide doped powder of zinc nitrate prepared by embodiment 13 to survey
Examination, each test result difference is as shown in figs. 23-25.Embodiment 13 is used by modifying titanium dioxide powder prepared by ball-milling technology
In the anti-microbial property test of Escherichia coli, test result is as follows.
Figure 23 shows that the particle diameter distribution of the titanium dioxide powder of nitric acid zinc doping is in 100-500nm after high-energy ball milling 3h
Between.Figure 24 shows that the product of the present embodiment is anatase phase titanium dioxide, ZnTiO3.Figure 25 shows, the material after ball milling 3h
ABSORPTION EDGE is moved to visible region.The titanium dioxide powder of the present embodiment nitric acid zinc doping is to the antibacterial ring size of Escherichia coli
5.5cm。
In sum, the present invention uses high-energy-milling, by material titania powder and metal ion compound
Grinding and shock between mill ball, so as to reduce the particle diameter of material, make titanium dioxide and metal ion compound mutual
Diffusion is penetrated into, two-phase or multiphase heterojunction structure of the tissue and distributed components based on titanium dioxide is formed, in this way, both
The advantage in terms of the intrinsic physicochemical properties of pure phase titanium dioxide is remained, again using the second newly-increased phase or other phase constituent elements
It is carried out assisted and strengthened.
Compared with existing modifying titanium dioxide preparation method, modifying titanium dioxide raw powder's production technology of the invention
It is easy to operate, easily regulate and control the particle diameter of titanium dioxide powder, applied widely, the high income of titanium dioxide powder can be real
Existing industrialized production, low cost.
The average grain diameter of the modifying titanium dioxide powder prepared by the present invention is small, and specific surface area is big, has in visible region
Excellent absorption, its utilization rate to visible ray is high, and around-France large intestine bar is carried out to modifying titanium dioxide powder by using antibacterial
The anti-microbial property test of bacterium, the antibiotic property of modifying titanium dioxide powder is strong.
Know-why of the invention is described above in association with specific embodiment.These descriptions are intended merely to explain the present invention
Principle, and can not by any way be construed to limiting the scope of the invention.Based on explanation herein, art technology
Personnel associate other specific embodiments of the invention by need not paying creative work, these modes fall within this
Within invention protection domain.
Claims (10)
1. a kind of modifying titanium dioxide raw powder's production technology, it is characterised in that comprise the following steps：
S1, metal ion compound and titania powder are mixed first, dispersant and absolute ethyl alcohol are added afterwards, mixing is equal
It is even, obtain ball milling material；
S2, the ball grinder that will be equipped with mill ball and ball milling material are placed in ball milling are carried out in ball mill；
S3, the sample after ball milling is cooled to room temperature, then carry out successively ultrasound, dry, grinding, obtain modifying titanium dioxide powder
Body.
2. modifying titanium dioxide raw powder's production technology as claimed in claim 1, it is characterised in that the metal ion chemical combination
Thing is the one kind in cobalt acetate, lithium sulfate, zinc nitrate, and the metal ion compound is 1 ﹕ with the mol ratio of titania powder
1-1 ﹕ 10.
3. modifying titanium dioxide raw powder's production technology as claimed in claim 2, it is characterised in that the dispersant is tristearin
The mixture of acid, the metal ion compound and titania powder is 50 ﹕ 1 with stearic mass ratio.
4. modifying titanium dioxide raw powder's production technology as claimed in claim 2, it is characterised in that the metal ion chemical combination
The mixture of thing and titania powder is 2 ﹕ 1 with the mass ratio of absolute ethyl alcohol.
5. modifying titanium dioxide raw powder's production technology as claimed in claim 1, it is characterised in that the S2 includes following step
Suddenly：
S21, take particle diameter be 3-10mm zirconium oxide abrasive ball be sequentially placed into alumina balls grinding jar according to size is descending；
S22, ball milling material is laid on mill ball, be placed in carries out ball milling afterwards in ball mill.
6. modifying titanium dioxide raw powder's production technology as claimed in claim 5, it is characterised in that in S21, the grinding
Spherolite footpath is respectively 3mm, 5mm, 8mm, 10mm, and mass ratio is the ﹕ 1 of 1-3 ﹕ 1-2 ﹕ 1.
7. the modifying titanium dioxide raw powder's production technology as described in claim 1 or 5, it is characterised in that the mill ball with
The mass ratio of ball milling material is 10 ﹕ 1-20 ﹕ 1.
8. the preparation method of the modifying titanium dioxide raw powder's production technology as described in claim 1 or 5, it is characterised in that institute
The rotary speed of ball mill is stated for 300r/min, revolution rotational velocity ratio is 1 ﹕ 1.5, and Ball-milling Time is 0.5-10h.
9. modifying titanium dioxide raw powder's production technology as claimed in claim 1, it is characterised in that the drying temperature is
90-105 DEG C, drying time is 12-24h.
10. a kind of modifying titanium dioxide powder, it is characterised in that the modifying titanium dioxide powder is using such as claim 1-9
Modifying titanium dioxide raw powder's production technology described in any one is prepared from.
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| CN108997029A (en) * | 2018-08-31 | 2018-12-14 | 东北大学 | A kind of preparation method for the anti-bacteria ceramic having excellent anti-bacterium capability |
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