CN104556217B - A kind of method preparing divalent metal titanate microballoon - Google Patents
A kind of method preparing divalent metal titanate microballoon Download PDFInfo
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- CN104556217B CN104556217B CN201410834881.7A CN201410834881A CN104556217B CN 104556217 B CN104556217 B CN 104556217B CN 201410834881 A CN201410834881 A CN 201410834881A CN 104556217 B CN104556217 B CN 104556217B
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Abstract
Prepare a method for divalent metal titanate microballoon, it relates to a kind of preparation method preparing metal titanate.The object of the invention is to solve titanate prepared by existing method and there is the microballoon pattern that cannot obtain size uniform, thermal treatment temp is high, heat treatment time is long and the unequal problem of scale topography.Preparation method: one, prepare divalent metal acetate alcoholic solution; Two, part is added; Three, titanium source is added; Four, solvent thermal reaction; Five, centrifugation and washing, drying; Six, roasting, obtains divalent metal titanate microballoon.Divalent metal titanate microballoon prepared by the present invention has uniform microballoon pattern; Divalent metal titanate Microsphere Size prepared by the present invention is even, and be of a size of 2 μm ~ 5 μm, monodispersity is good; Divalent metal titanate microballoon thermal treatment temp prepared by the present invention is low, and roasting time is short.The present invention can obtain a kind of method preparing divalent metal titanate microballoon.
Description
Technical field
The present invention relates to a kind of preparation method preparing metal titanate.
Background technology
The development of human society is maked rapid progress, and along with the continuous lifting of Science and Technology, product innovation and new technology continue to bring out, and these provide convenience not only to the productive life of people, also facilitate the development of social productive forces better.Type material is more and more subject to people's attention as the core component of product, device.Scientist and material scholars try every means to attempt to obtain cheapness, stable, efficient function novel material.Improving the practicality of product, reduce product price, is people's service better.In the past few decades, ultracapacitor, lithium ion battery, solar cell, the new technologies such as semiconductor light-catalyst serve huge pushing effect at the energy and environmental area.As the agent structure unit of these new technologies and new unit, the research of inorganic nanometer functional material receives much attention.Transition metal oxide, titanium dioxide, zinc oxide, the nanometer novel material of a collection of efficient stables such as sulfide sosoloid is found out, and has played huge effect in association area.By contrast, titanate function is due to its stable structure, and the cost of rational energy band structure and cheapness, receives much concern in recent years.Existing such as potassium titanate at present, barium titanate, the titanate material such as strontium titanate and lanthanium titanate is synthesized and prepares, for photodissociation aquatic products hydrogen, photocatalysis degradation organic contaminant, solar cell, piezoelectric ceramics and microelectronic device.
Titanate is generally ABO
3type perovskite structure or A
2bO
4spinel structure, its preparation method is comparatively complicated.Main method is solid phase method and alkaline process, and namely solid phase method obtains titanate product by the method for high temperature sintering; Alkaline process by add in inorganic precursor alkali obtain hydroxide tungsten presoma then thermal treatment obtain titanate.But the titanate prepared of these traditional methods often particle diameter is comparatively large, impurity (phase) is more, specific surface area is less, activity is poor, and solid phase method generally needs higher thermal treatment temp and longer reaction times, and energy consumption is very large.Alkaline process etc. are unfavorable for cleaner production owing to producing alkaline byproduct, have greater environmental impacts, and need High Temperature High Pressure and equipment is complicated.These methods generally all obtain nanoparticle simultaneously, and do not have specific morphology, size differs, and impurity is more, and these are all unfavorable for the photoelectricity of material, the performances such as piezoelectricity.
Microballoon pattern material due to its uniform pattern, good dispersing property, the attention of unique optical property extremely people.Find that the material that occurring in nature has counter opal structure as butterfly's wing etc. is all assembled by microballoon especially by research.Therefore micro-sphere material will in photochemical catalysis, photocatalytic water, and there is very important application in the fields such as dye sensitization of solar.So, develop a kind of simple, general synthetic method prepare titanate microballoon be one very meaningful and there is the work of challenge.
Summary of the invention
The object of the invention is to solve titanate prepared by existing method and there is the microballoon pattern that cannot obtain size uniform, thermal treatment temp is high, heat treatment time is long and the unequal problem of scale topography, and provides a kind of method preparing divalent metal titanate microballoon.
Prepare a method for divalent metal titanate microballoon, complete according to the following steps:
One, divalent metal acetate alcoholic solution is prepared: be dissolved in alcoholic solvent by divalent metal acetate under the condition of 25 DEG C ~ 35 DEG C in temperature, obtain the alcoholic solution that metal ion volumetric molar concentration is the divalent metal acetate of 0.0025mol/L ~ 0.01mol/L;
Two, part is added: be that part to be joined metal ion volumetric molar concentration under the condition of 25 DEG C ~ 35 DEG C be in the alcoholic solution of divalent metal acetate of 0.0025mol/L ~ 0.01mol/L in temperature, low whipping speed is stir 30min under the condition of 100r/min ~ 300r/min again, obtains the alcohol mixture solution of divalent metal acetate and part;
Part described in step 2 and metal ion volumetric molar concentration are that the amount of substance of divalent metal acetate in the alcoholic solution of the divalent metal acetate of 0.0025mol/L ~ 0.01mol/L is than being 1:(0.5 ~ 2);
Three, titanium source is added: be joined in the alcohol mixture solution of divalent metal acetate and part in titanium source under the condition of 25 DEG C ~ 35 DEG C in temperature, then low whipping speed is stir 1h ~ 3h under the condition of 100r/min ~ 300r/min, namely obtains reaction soln;
In the alcohol mixture solution of the titanium source described in step 3 and divalent metal acetate and part, the amount of substance of divalent metal acetate is than being 1:(0.5 ~ 2);
Four, solvent thermal reaction: be under the condition of 25 DEG C ~ 35 DEG C, reaction soln is joined in tetrafluoroethylene reactor in temperature, again tetrafluoroethylene reactor is sealed, the tetrafluoroethylene reactor of sealing being put into temperature is heat 10h ~ 24h in the loft drier of 140 DEG C ~ 200 DEG C again, obtains the mixed solution containing divalent metal titanate microballoon presoma;
Five, centrifugation and washing, drying: the mixed solution containing divalent metal titanate microballoon presoma is carried out centrifugation, obtains divalent metal titanate microballoon presoma; Use dehydrated alcohol to wash 2 times ~ 5 times to divalent metal titanate microballoon presoma, be then centrifugation 5min ~ 30min under the condition of 3000r/min ~ 4000r/min in centrifugal speed, obtain wet divalent metal titanate microballoon presoma; Wet divalent metal titanate microballoon presoma is put into vacuum drying oven, is dry 5h ~ 24h under the condition of 30 DEG C ~ 70 DEG C in temperature, obtains divalent metal titanate microballoon presoma;
Six, roasting: be sinter 1h ~ 4h in the retort furnace of 400 DEG C ~ 1000 DEG C in temperature by divalent metal titanate microballoon presoma, obtain divalent metal titanate microballoon.
Advantage of the present invention: the divalent metal titanate microballoon that, prepared by the present invention has uniform microballoon pattern;
Two, the divalent metal titanate Microsphere Size prepared of the present invention is even, and be of a size of 2 μm ~ 5 μm, monodispersity is good; Three, the divalent metal titanate microballoon thermal treatment temp prepared of the present invention is low, and roasting time is short; Four, the divalent metal titanate microballoon that prepared by the present invention has good stability; Five, the metallic divalent metal titanate microballoon that prepared by the present invention is suitable for being used as photocatalysis Decomposition aquatic products hydrogen catalyst, dye sensitization solar battery, the full water of decomposition of photochemical catalysis and photocatalytic reduction of carbon oxide.
The present invention can obtain a kind of method preparing divalent metal titanate microballoon.
Accompanying drawing explanation
Fig. 1 is the X-ray diffractogram of zinc titanate microballoon prepared by test one;
Fig. 2 is the SEM figure that the zinc titanate microballoon of test one preparation amplifies 25000 times;
Fig. 3 is the X-ray diffractogram of magnesium titanate microballoon prepared by test two;
Fig. 4 is the SEM figure that magnesium titanate microballoon that test two obtains amplifies 5000 times;
Fig. 5 is the X-ray diffractogram of cobalt titanate microballoon prepared by test three;
Fig. 6 is the SEM figure that the cobalt titanate microballoon of test three preparation is put into 25000 times;
Fig. 7 is the SEM figure that zinc titanate nanoparticle prepared by the control group of test one amplifies 100000 times;
Fig. 8 is the SEM figure that magnesium titanate nanoparticle prepared by the control group of test two amplifies 50000 times;
Fig. 9 is the SEM figure that cobalt titanate nanoparticle prepared by the control group of test three amplifies 300000 times.
Embodiment
Embodiment one: present embodiment is a kind of method preparing divalent metal titanate microballoon, completes according to the following steps:
One, divalent metal acetate alcoholic solution is prepared: be dissolved in alcoholic solvent by divalent metal acetate under the condition of 25 DEG C ~ 35 DEG C in temperature, obtain the alcoholic solution that metal ion volumetric molar concentration is the divalent metal acetate of 0.0025mol/L ~ 0.01mol/L;
Two, part is added: be that part to be joined metal ion volumetric molar concentration under the condition of 25 DEG C ~ 35 DEG C be in the alcoholic solution of divalent metal acetate of 0.0025mol/L ~ 0.01mol/L in temperature, low whipping speed is stir 30min under the condition of 100r/min ~ 300r/min again, obtains the alcohol mixture solution of divalent metal acetate and part;
Part described in step 2 and metal ion volumetric molar concentration are that the amount of substance of divalent metal acetate in the alcoholic solution of the divalent metal acetate of 0.0025mol/L ~ 0.01mol/L is than being 1:(0.5 ~ 2);
Three, titanium source is added: be joined in the alcohol mixture solution of divalent metal acetate and part in titanium source under the condition of 25 DEG C ~ 35 DEG C in temperature, then low whipping speed is stir 1h ~ 3h under the condition of 100r/min ~ 300r/min, namely obtains reaction soln;
In the alcohol mixture solution of the titanium source described in step 3 and divalent metal acetate and part, the amount of substance of divalent metal acetate is than being 1:(0.5 ~ 2);
Four, solvent thermal reaction: be under the condition of 25 DEG C ~ 35 DEG C, reaction soln is joined in tetrafluoroethylene reactor in temperature, again tetrafluoroethylene reactor is sealed, the tetrafluoroethylene reactor of sealing being put into temperature is heat 10h ~ 24h in the loft drier of 140 DEG C ~ 200 DEG C again, obtains the mixed solution containing divalent metal titanate microballoon presoma;
Five, centrifugation and washing, drying: the mixed solution containing divalent metal titanate microballoon presoma is carried out centrifugation, obtains divalent metal titanate microballoon presoma; Use dehydrated alcohol to wash 2 times ~ 5 times to divalent metal titanate microballoon presoma, be then centrifugation 5min ~ 30min under the condition of 3000r/min ~ 4000r/min in centrifugal speed, obtain wet divalent metal titanate microballoon presoma; Wet divalent metal titanate microballoon presoma is put into vacuum drying oven, is dry 5h ~ 24h under the condition of 30 DEG C ~ 70 DEG C in temperature, obtains divalent metal titanate microballoon presoma;
Six, roasting: be sinter 1h ~ 4h in the retort furnace of 400 DEG C ~ 1000 DEG C in temperature by divalent metal titanate microballoon presoma, obtain divalent metal titanate microballoon.
The advantage of present embodiment: the divalent metal titanate microballoon that, prepared by present embodiment has uniform microballoon pattern; Two, the divalent metal titanate Microsphere Size prepared of present embodiment is even, and be of a size of 2 μm ~ 5 μm, monodispersity is good; Three, the divalent metal titanate microballoon thermal treatment temp prepared of present embodiment is low, and roasting time is short; Four, the divalent metal titanate microballoon that prepared by present embodiment has good stability; Five, the metallic divalent metal titanate microballoon that prepared by present embodiment is suitable for being used as photocatalysis Decomposition aquatic products hydrogen catalyst, dye sensitization solar battery, the full water of decomposition of photochemical catalysis and photocatalytic reduction of carbon oxide.
Present embodiment can obtain a kind of method preparing divalent metal titanate microballoon.
Embodiment two: present embodiment and embodiment one difference are: the divalent metal acetate described in step one is a kind of or wherein several mixture in magnesium acetate, strontium acetate, barium acetate, cobaltous acetate, nickelous acetate, ironic acetate, venus crystals, zinc acetate, cadmium acetate, lime acetate, lead acetate and manganous acetate.Other steps are identical with embodiment one.
Embodiment three: one of present embodiment and embodiment one or two difference is: the alcoholic solvent described in step one is a kind of or wherein several mixture in methyl alcohol, dehydrated alcohol, Virahol, butanols, isopropylcarbinol, phenylcarbinol and phenylethyl alcohol.Other steps are identical with embodiment one or two.
Embodiment four: one of present embodiment and embodiment one to three difference is: the part described in step 2 is a kind of in Whitfield's ointment, acetylsalicylic acid, 3-aminosallcylic acid, 4-ASA and 5-aminosalicylic acid or the wherein mixture of two kinds.Other steps are identical with embodiment one to three.
Embodiment five: one of present embodiment and embodiment one to four difference is: the titanium source described in step 3 is the mixture of the one or both in tetrabutyl titanate and isopropyl titanate.Other steps are identical with embodiment one to four.
Embodiment six: one of present embodiment and embodiment one to five difference is: the part described in step 2 and metal ion volumetric molar concentration are that the amount of substance of divalent metal acetate in the alcoholic solution of the divalent metal acetate of 0.0025mol/L ~ 0.01mol/L is than being 1:(1 ~ 2).Other steps are identical with embodiment one to five.
Embodiment seven: one of present embodiment and embodiment one to six difference is: the part described in step 2 and metal ion volumetric molar concentration are that the amount of substance of divalent metal acetate in the alcoholic solution of the divalent metal acetate of 0.0025mol/L ~ 0.01mol/L is than being 1:(0.5 ~ 1).Other steps are identical with embodiment one to six.
Embodiment eight: one of present embodiment and embodiment one to seven difference is: in the alcohol mixture solution of the titanium source described in step 3 and divalent metal acetate and part, the amount of substance of divalent metal acetate is than being 1:(0.5 ~ 1).Other steps are identical with embodiment one to seven.
Embodiment nine: one of present embodiment and embodiment one to eight difference is: in the alcohol mixture solution of the titanium source described in step 3 and divalent metal acetate and part, the amount of substance of divalent metal acetate is than being 1:(1 ~ 2).Other steps are identical with embodiment one to eight.
Embodiment ten: one of present embodiment and embodiment one to nine difference is: be sinter 2h ~ 3h in the retort furnace of 400 DEG C ~ 700 DEG C in temperature by divalent metal titanate microballoon presoma in step 6, obtain divalent metal titanate microballoon.Other steps are identical with embodiment one to nine.
Adopt following verification experimental verification beneficial effect of the present invention:
Test one: a kind of method preparing divalent metal titanate microballoon, completes according to the following steps:
One, divalent metal acetate alcoholic solution is prepared: be dissolved in dehydrated alcohol by zinc acetate under the condition of 30 DEG C in temperature, obtain the alcoholic solution that metal ion volumetric molar concentration is the zinc acetate of 0.01mol/L;
Two, part is added: be that Whitfield's ointment to be joined metal ion volumetric molar concentration under the condition of 30 DEG C be in the alcoholic solution of the zinc acetate of 0.01mol/L in temperature, low whipping speed is stir 30min under the condition of 300r/min again, obtains zinc acetate and salicylic alcohol mixture solution;
Whitfield's ointment described in step 2 and metal ion volumetric molar concentration are that the amount of substance of zinc acetate in the alcoholic solution of the zinc acetate of 0.01mol/L is than being 1:1;
Three, titanium source is added: be joined by tetrabutyl titanate in zinc acetate and salicylic alcohol mixture solution under the condition of 30 DEG C in temperature, then low whipping speed is stir 1h under the condition of 300r/min, namely obtains reaction soln;
Tetrabutyl titanate described in step 3 is 1:1 with the amount of substance ratio of zinc acetate in zinc acetate and salicylic alcohol mixture solution;
Four, solvent thermal reaction: be under the condition of 30 DEG C, reaction soln is joined in tetrafluoroethylene reactor in temperature, again tetrafluoroethylene reactor is sealed, the tetrafluoroethylene reactor of sealing being put into temperature is again heat 12h in the loft drier of 160 DEG C, obtains the mixed solution containing zinc titanate presoma microballoon;
Five, centrifugation and washing, drying: the mixed solution containing divalent metal titanate microballoon presoma is carried out centrifugation, obtains divalent metal titanate microballoon presoma; Use dehydrated alcohol to wash 3 times to divalent metal titanate microballoon presoma, be then centrifugation 5min under the condition of 4000r/min in centrifugal speed, obtain wet zinc titanate microballoon presoma; Wet zinc titanate microballoon presoma is put into vacuum drying oven, is dry 8h under the condition of 40 DEG C in temperature, obtains zinc titanate microballoon presoma;
Six, roasting: be sinter 2h in the retort furnace of 600 DEG C in temperature by zinc titanate microballoon presoma, obtain zinc titanate microballoon.
X-ray diffractometer is adopted to test the zinc titanate microballoon that test one step 6 obtains, as shown in Figure 1; Fig. 1 is the X-ray diffractogram of zinc titanate microballoon prepared by test one, and as shown in Figure 1, the zinc titanate microballoon that test one prepares is pure zinc titanate, and crystallization degree is higher.
Scanning electronic microscope is adopted to test zinc titanate microballoon prepared by test one step 6, as shown in Figure 2.Fig. 2 is the SEM figure that the zinc titanate microballoon of test one preparation amplifies 25000 times; As can be seen from Figure 2, the zinc titanate microballoon of test one preparation is microballoon pattern, and size is approximately 5 microns.
The controlled trial of test one: adopt solid sintering technology to prepare zinc titanate nanoparticle, specifically complete according to the following steps:
Get 0.01mol zinc oxide and 0.01mol titanium dioxide is dispersed in 10mL ethanol, low whipping speed is stir 1h under the condition of 300r/min, obtains suspension liquid, then is dry 12h in the vacuum drying oven of 60 DEG C in temperature, obtains zinc titanate nanoparticle precursor powder; Be roasting 10h in the retort furnace of 1000 DEG C in temperature by the zinc titanate nanoparticle precursor powder obtained, namely obtain zinc titanate zinc titanate nanoparticle.
Test two: a kind of method preparing divalent metal titanate microballoon, completes according to the following steps:
One, divalent metal acetate alcoholic solution is prepared: be dissolved in dehydrated alcohol by magnesium acetate under the condition of 30 DEG C in temperature, obtain the ethanolic soln that metal ion volumetric molar concentration is the magnesium acetate of 0.01mol/L;
Two, part is added: be that Whitfield's ointment to be joined metal ion volumetric molar concentration under the condition of 30 DEG C be in the ethanolic soln of the magnesium acetate of 0.01mol/L in temperature, low whipping speed is stir 30min under the condition of 300r/min again, obtains magnesium acetate and salicylic alcohol mixture solution;
Whitfield's ointment described in step 2 and metal ion volumetric molar concentration are that the amount of substance of magnesium acetate in the ethanolic soln of the magnesium acetate of 0.01mol/L is than being 1:1;
Three, titanium source is added: be joined by tetrabutyl titanate in magnesium acetate and salicylic alcohol mixture solution under the condition of 30 DEG C in temperature, then low whipping speed is stir 1h under the condition of 300r/min, namely obtains reaction soln;
Tetrabutyl titanate described in step 3 is 1:1 with the amount of substance ratio of magnesium acetate in magnesium acetate and salicylic alcohol mixture solution;
Four, solvent thermal reaction: be under the condition of 30 DEG C, reaction soln is joined in tetrafluoroethylene reactor in temperature, again tetrafluoroethylene reactor is sealed, the tetrafluoroethylene reactor of sealing being put into temperature is again heat 12h in the loft drier of 160 DEG C, obtains the mixed solution containing magnesium titanate microballoon presoma;
Five, centrifugation and washing, drying: the mixed solution containing magnesium titanate microballoon presoma is carried out centrifugation, obtains magnesium titanate microballoon presoma; Use dehydrated alcohol to wash 3 times to magnesium titanate microballoon presoma, be then centrifugation 5min under the condition of 4000r/min in centrifugal speed, obtain wet magnesium titanate microballoon presoma; Wet magnesium titanate microballoon presoma is put into vacuum drying oven, is dry 8h under the condition of 40 DEG C in temperature, obtains magnesium titanate microballoon presoma;
Six, roasting: be sinter 2h in the retort furnace of 600 DEG C in temperature by magnesium titanate microballoon presoma, obtain magnesium titanate microballoon.
X-ray diffractometer is adopted to test the magnesium titanate microballoon that test two obtains, as shown in Figure 3; Fig. 3 is the X-ray diffractogram of magnesium titanate microballoon prepared by test two; As shown in Figure 3, the magnesium titanate microballoon that test two is prepared is the mixed phase of positive magnesium titanate and two magnesium titanates, high and sharp-pointed diffraction peak describes gained magnesium titanate microballoon has higher degree of crystallinity, theoretical and experiment proves that the material of this mixed phase is favourable to photocatalytic hydrogen production by water decomposition.
Scanning electronic microscope is adopted to test the magnesium titanate microballoon that test two obtains, as shown in Figure 4; Fig. 4 is the SEM figure that magnesium titanate microballoon that test two obtains amplifies 5000 times; As shown in Figure 4, test the two magnesium titanate microballoon structures spherical in shape prepared and surface irregularity, can find out that from the sample photo of fragmentation microballoon is piled up by less nanoparticle to form.
The control group of test two: adopt solid sintering technology to prepare magnesium titanate nanoparticle, specifically complete according to the following steps:
Get 0.01mol magnesium oxide and 0.01mol titanium dioxide is dispersed in 10mL ethanol, low whipping speed is stir 1h under the condition of 300r/min to obtain suspension liquid, is dry 12h in the vacuum drying oven of 60 DEG C, obtains magnesium titanate nanoparticle precursor powder in temperature; By the magnesium titanate nanoparticle precursor powder 1000 DEG C of roasting 10h in retort furnace obtained, namely obtain magnesium titanate nanoparticle.
Test three: a kind of method preparing divalent metal titanate microballoon, completes according to the following steps:
One, divalent metal acetate alcoholic solution is prepared: be dissolved in dehydrated alcohol by cobaltous acetate under the condition of 30 DEG C in temperature, obtain the ethanolic soln that metal ion volumetric molar concentration is the cobaltous acetate of 0.01mol/L;
Two, part is added: be that Whitfield's ointment to be joined metal ion volumetric molar concentration under the condition of 30 DEG C be in the ethanolic soln of the cobaltous acetate of 0.01mol/L in temperature, low whipping speed is stir 30min under the condition of 300r/min again, obtains cobaltous acetate and salicylic alcohol mixture solution;
Whitfield's ointment described in step 2 and metal ion volumetric molar concentration are that the amount of substance of cobaltous acetate in the ethanolic soln of the cobaltous acetate of 0.01mol/L is than being 1:1;
Three, titanium source is added: be joined by tetrabutyl titanate in cobaltous acetate and salicylic alcohol mixture solution under the condition of 30 DEG C in temperature, then low whipping speed is stir 1h under the condition of 300r/min, namely obtains reaction soln;
Tetrabutyl titanate described in step 3 is 1:1 with the amount of substance ratio of cobaltous acetate in cobaltous acetate and salicylic alcohol mixture solution;
Four, solvent thermal reaction: be under the condition of 30 DEG C, reaction soln is joined in tetrafluoroethylene reactor in temperature, again tetrafluoroethylene reactor is sealed, the tetrafluoroethylene reactor of sealing being put into temperature is again heat 12h in the loft drier of 160 DEG C, obtains the mixed solution containing cobalt titanate microballoon presoma;
Five, centrifugation and washing, drying: the mixed solution containing cobalt titanate microballoon presoma is carried out centrifugation, obtains cobalt titanate microballoon presoma; Use dehydrated alcohol to wash 3 times to cobalt titanate microballoon presoma, be then centrifugation 5min under the condition of 4000r/min in centrifugal speed, obtain wet cobalt titanate microballoon presoma; Wet cobalt titanate microballoon presoma is put into vacuum drying oven, is dry 8h under the condition of 40 DEG C in temperature, obtains cobalt titanate microballoon presoma;
Six, roasting: be sinter 2h in the retort furnace of 600 DEG C in temperature by cobalt titanate microballoon presoma, obtain cobalt titanate microballoon.
X-ray diffractometer is adopted to test the cobalt titanate microballoon that test three obtains, as shown in Figure 5; Fig. 5 is the X-ray diffractogram of cobalt titanate microballoon prepared by test three; As can be seen from Figure 5, the cobalt titanate microballoons of test three preparation are pure cobalt titanate, high and sharp-pointed diffraction peak describes gained cobalt titanate microballoon has higher degree of crystallinity.
Scanning electronic microscope is adopted to test cobalt titanate microballoon prepared by test three, as shown in Figure 6; Fig. 6 is the SEM figure that the cobalt titanate microballoon of test three preparation is put into 25000 times; As can be seen from Figure 6, the cobalt titanate microballoon testing three preparations is globosity and surface irregularity.
The control group of test three: adopt solid sintering technology to prepare cobalt titanate nanoparticle, specifically complete according to the following steps:
Get 0.01mol tricobalt tetroxide and 0.01mol titanium dioxide is dispersed in 10mL ethanol, low whipping speed is stir 1h under the condition of 300r/min to obtain suspension liquid again, be dry 12h in the vacuum drying oven of 60 DEG C in temperature, obtain cobalt titanate nanoparticle precursor powder; By the cobalt titanate nanoparticle precursor powder 1000 DEG C of roasting 10h in retort furnace obtained, namely obtain cobalt titanate nanoparticle.
Cobalt titanate nanoparticle prepared by the control group of the zinc titanate nanoparticle adopting the control group of scanning electronic microscope to test one to prepare, magnesium titanate nanoparticle prepared by the control group of test two and test three is tested, as shown in Fig. 7, Fig. 8 and Fig. 9; Fig. 7 is the SEM figure that zinc titanate nanoparticle prepared by the control group of test one amplifies 100000 times; Fig. 8 is the SEM figure that magnesium titanate nanoparticle prepared by the control group of test two amplifies 50000 times; Fig. 9 is the SEM figure that cobalt titanate nanoparticle prepared by the control group of test three amplifies 300000 times;
Comparison diagram 2, Fig. 4, Fig. 6 and Fig. 7, Fig. 8, Fig. 9 known, test one, test two and the products that obtain of test three are as globosity, the size uniform of ball, and pattern is homogeneous; And sized particles is comparatively large in product nanometer prepared by corresponding controlled trial, homogeneity is poor, and agglomeration is obvious; From synthetic method, test one, the maturing temperature that microballoon is prepared in test two and test three is 600 DEG C, and the time is 2 hours, and nanoparticle prepared by control group then needs the high temperature of 1000 DEG C and reaches the roasting time of 10 hours.Therefore, test one, this Liqand Precursor method that test two and test three use more easily can prepare the divalent metal titanate functional materials with spherical morphology.
Claims (8)
1. prepare a method for divalent metal titanate microballoon, it is characterized in that a kind of method preparing divalent metal titanate microballoon completes according to the following steps:
One, divalent metal acetate alcoholic solution is prepared: be dissolved in alcoholic solvent by divalent metal acetate under the condition of 25 DEG C ~ 35 DEG C in temperature, obtain the alcoholic solution that metal ion volumetric molar concentration is the divalent metal acetate of 0.0025mol/L ~ 0.01mol/L;
Two, part is added: be that part to be joined metal ion volumetric molar concentration under the condition of 25 DEG C ~ 35 DEG C be in the alcoholic solution of divalent metal acetate of 0.0025mol/L ~ 0.01mol/L in temperature, low whipping speed is stir 30min under the condition of 100r/min ~ 300r/min again, obtains the alcohol mixture solution of divalent metal acetate and part;
Part described in step 2 is a kind of in Whitfield's ointment, acetylsalicylic acid, 3-aminosallcylic acid, 4-ASA and 5-aminosalicylic acid or the wherein mixture of two kinds;
Part described in step 2 and metal ion volumetric molar concentration are that the amount of substance of divalent metal acetate in the alcoholic solution of the divalent metal acetate of 0.0025mol/L ~ 0.01mol/L is than being 1:(0.5 ~ 2);
Three, titanium source is added: be joined in the alcohol mixture solution of divalent metal acetate and part in titanium source under the condition of 25 DEG C ~ 35 DEG C in temperature, then low whipping speed is stir 1h ~ 3h under the condition of 100r/min ~ 300r/min, namely obtains reaction soln;
Titanium source described in step 3 is the mixture of the one or both in tetrabutyl titanate and isopropyl titanate;
In the alcohol mixture solution of the titanium source described in step 3 and divalent metal acetate and part, the amount of substance of divalent metal acetate is than being 1:(0.5 ~ 2);
Four, solvent thermal reaction: be under the condition of 25 DEG C ~ 35 DEG C, reaction soln is joined in tetrafluoroethylene reactor in temperature, again tetrafluoroethylene reactor is sealed, the tetrafluoroethylene reactor of sealing being put into temperature is heat 10h ~ 24h in the loft drier of 140 DEG C ~ 200 DEG C again, obtains the mixed solution containing divalent metal titanate microballoon presoma;
Five, centrifugation and washing, drying: the mixed solution containing divalent metal titanate microballoon presoma is carried out centrifugation, obtains divalent metal titanate microballoon presoma; Use dehydrated alcohol to wash 2 times ~ 5 times to divalent metal titanate microballoon presoma, be then centrifugation 5min ~ 30min under the condition of 3000r/min ~ 4000r/min in centrifugal speed, obtain wet divalent metal titanate microballoon presoma; Wet divalent metal titanate microballoon presoma is put into vacuum drying oven, is dry 5h ~ 24h under the condition of 30 DEG C ~ 70 DEG C in temperature, obtains divalent metal titanate microballoon presoma;
Six, roasting: be sinter 1h ~ 4h in the retort furnace of 400 DEG C ~ 1000 DEG C in temperature by divalent metal titanate microballoon presoma, obtain divalent metal titanate microballoon.
2. a kind of method preparing divalent metal titanate microballoon according to claim 1, is characterized in that the divalent metal acetate described in step one is a kind of or wherein several mixture in magnesium acetate, strontium acetate, barium acetate, cobaltous acetate, nickelous acetate, ironic acetate, venus crystals, zinc acetate, cadmium acetate, lime acetate, lead acetate and manganous acetate.
3. a kind of method preparing divalent metal titanate microballoon according to claim 1, is characterized in that the alcoholic solvent described in step one is a kind of or wherein several mixture in methyl alcohol, dehydrated alcohol, Virahol, butanols, isopropylcarbinol, phenylcarbinol and phenylethyl alcohol.
4. a kind of method preparing divalent metal titanate microballoon according to claim 1, is characterized in that the part described in step 2 and metal ion volumetric molar concentration are that the amount of substance of divalent metal acetate in the alcoholic solution of the divalent metal acetate of 0.0025mol/L ~ 0.01mol/L is than being 1:(1 ~ 2).
5. a kind of method preparing divalent metal titanate microballoon according to claim 1, is characterized in that the part described in step 2 and metal ion volumetric molar concentration are that the amount of substance of divalent metal acetate in the alcoholic solution of the divalent metal acetate of 0.0025mol/L ~ 0.01mol/L is than being 1:(0.5 ~ 1).
6. a kind of method preparing divalent metal titanate microballoon according to claim 1, is characterized in that the amount of substance of divalent metal acetate in the alcohol mixture solution of the titanium source described in step 3 and divalent metal acetate and part than being 1:(0.5 ~ 1).
7. a kind of method preparing divalent metal titanate microballoon according to claim 1, is characterized in that the amount of substance of divalent metal acetate in the alcohol mixture solution of the titanium source described in step 3 and divalent metal acetate and part than being 1:(1 ~ 2).
8. a kind of method preparing divalent metal titanate microballoon according to claim 1, it is characterized in that being sinter 2h ~ 3h in the retort furnace of 400 DEG C ~ 700 DEG C in temperature by divalent metal titanate microballoon presoma in step 6, obtain divalent metal titanate microballoon.
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| US6264912B1 (en) * | 1999-09-10 | 2001-07-24 | Ut-Battelle, Llc | Methods for producing monodispersed particles of barium titanate |
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| US6264912B1 (en) * | 1999-09-10 | 2001-07-24 | Ut-Battelle, Llc | Methods for producing monodispersed particles of barium titanate |
| CN101172646A (en) * | 2007-11-05 | 2008-05-07 | 桂林工学院 | Method of producing spinel structured lithium titanate |
| CN101181682A (en) * | 2007-12-14 | 2008-05-21 | 浙江大学 | Method for preparing ferromagnetic titania cobalt-doped photocatalysis material |
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