CN103159257A - Biomimetic preparation method of hollow titanium dioxide nanospheres in sepharose gel - Google Patents
Biomimetic preparation method of hollow titanium dioxide nanospheres in sepharose gel Download PDFInfo
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Abstract
The invention relates to a biomimetic preparation method of hollow titanium dioxide nanospheres in sepharose gel. The method comprises the following steps: (1) preparing a precursor of titanium, namely a dihydroxybis(ammonium lactato)titanium solution; and (2) soaking gel blocks containing sepharose and protamine in the solution obtained in step (1) to react at room temperature, heating products after reaction to remove the gel, freeze drying to obtain hollow titanium dioxide nanospheres with a mesoporous structure. According to the invention, the preparation conditions are mild, the preparation method is simple, the size and shape of particles are controllable, the applicable range is wide, and no template is required, so that the trouble caused by removing the template in subsequent process and the defect of irregular prepared hollow nanospheres are avoided.
Description
Technical field
The present invention relates to a kind of preparation method of titanium dioxide hollow nano-sphere, be specifically related to a kind of in Ago-Gel medium the method for bionic preparation titanium dioxide hollow nano-sphere.
Background technology
Hollow micro-/ nano ball is that a class kernel is the core-shell particles of the special construction of air or other gases, compare with its block materials have larger specific surface area, the physical properties such as less density and special mechanics, light, electricity, and shell structure is constructed according to people's wish, make hollow nanostructured performance abundanter, thereby cause chemist and material scholar's very big interest, become one of noticeable research direction in the nano material chemical field.The special structure of titanium dioxide hollow ball reaches has excellent properties at aspects such as photoelectricity, catalysis, air-sensitives, therefore has potential using value in fields such as solar cell, photochemical catalysis, environmental purification, gas sensors.At present, the preparation of titanium dioxide hollow ball is generally adopted template and without template.Template is divided into again hard template method and soft template method; Hard template method is the most direct effective means of preparation hollow ball structure, generally comprises following 4 steps: the 1) preparation of hard template; 2) surface property of modification template; 3) adopt the whole bag of tricks that precursor is covered on template, and adopt various processing that the structure that forms is adsorbed on template surface tightly; 4) remove selectively template to obtain required hollow structure.Hard template is a kind of very simple and direct and practical method for preparing hollow structure, but some hard template need the multistep preparation, and program is loaded down with trivial details, removes hard template by often causing the unstable of shell.Soft template method is to be self-assembled into globular micelle by the surfactant molecule in solution, take this globular micelle as template, show absorption one deck inorganic substance by electrostatic interaction or hydrogen bond action in template, then by means stonings such as organic solvent or oxidations, obtain micro-nano hollow ball structure.Than hard template method, the synthetic hollow structure experimental technique of soft template method is simple, and therefore mild condition can avoid the multistep operation in hard template.But the wayward pattern of soft template preparation method, homogeneity is bad, unsuitable a large amount of production applications.By controlling the conditions such as temperature, pressure without template, grow up to macrocrystal through secondary nucleation after making crystal in kernel be dissolved in solution, thereby produce the space in solid interior, need not introduce template in the preparation process of hollow granule, avoid removing the trouble of template, can greatly reduce operation steps.But than template, can not prepare many shell hollow spheres without template, and the hollow ball of preparation surface is regular not as template.
Summary of the invention
For overcoming the above-mentioned deficiency of prior art, the purpose of this invention is to provide a kind of in Ago-Gel medium the method for bionic preparation titanium dioxide hollow nano-sphere, the preparation method is simple, product pattern size is controlled.
The technical solution adopted in the present invention is: a kind of in Ago-Gel medium the method for bionic preparation titanium dioxide hollow nano-sphere, comprise the following steps: presoma two (2 hydroxy propanoic acid) two hydroxide two ammoniums of (1) preparation titanium close titanium solution; The gel piece that (2) will contain agarose and protamine is soaked at room temperature reaction in the solution of step (1), and reacted product obtains having the titanium dioxide hollow nano-sphere of meso-hole structure through adding the heat extraction gel after lyophilize.
Gel piece preparation process in described step (2) can for: a. prepares agarose solution; B. protamine added in described agarose solution and stir; C. with the solution of step b preparation standing cooling formation gel at room temperature, with the described gel formation gel piece that is cut into small pieces.
Beneficial effect of the present invention: the preparation condition of hollow nano-sphere of the present invention is gentle, the preparation method is simple, the granular size pattern is controlled, applied widely, and do not need to use template, avoid thus need removing in subsequent technique trouble that template causes and the irregular defective of hollow nano-sphere of preparation.
Gel is a kind of special dispersion system, generally is comprised of polymer the resilient, crosslinked network structure that consists of and the fluid that is full of its internal space.The hole dimension of gel network structure can be regulated by changing cross-linking density: the hole dimension of high crosslink density gel is in several nanometer range; And may have very large hole in the gel of lower crosslink density, and with the solution phase ratio, in gel media, convection current is suppressed, and rate of diffusion is also lower, and this makes the mineral nucleation rate reduce.Of the present invention in gel media the process of biomimetic mineralization also can be applied in the preparation engineering of other multiple inorganic materials, avoided the use of acid base catalysator, organic solvent, and preparation condition is gentle, the granular size pattern is controlled, the scope of application is wider.
Description of drawings
Fig. 1 is schema of the present invention;
Fig. 2 is the nitrogen adsorption desorption graphic representation of the titanium dioxide hollow nano-sphere of the embodiment of the present invention 1 preparation;
Fig. 3 is the pore size distribution curve figure of the titanium dioxide hollow nano-sphere of the embodiment of the present invention 1 preparation;
Fig. 4 is transmission electron microscope (TEM) photo of the titanium dioxide hollow nano-sphere of the embodiment of the present invention 2 preparations;
Fig. 5 is that the titanium dioxide hollow nano-sphere of the embodiment of the present invention 3 preparation is at scanning electron microscope (SEM) photo of 200 ℃ of calcinings after 1 hour;
Fig. 6 is transmission electron microscope (TEM) photo of the titanium dioxide hollow nano-sphere of Comparative Examples 1 preparation of the present invention.
Embodiment
Referring to Fig. 1, the invention provides a kind of in Ago-Gel medium the method for bionic preparation titanium dioxide hollow nano-sphere, comprise the following steps: presoma two (2 hydroxy propanoic acid) two hydroxide two ammoniums of (1) preparation titanium close titanium solution; The gel piece that (2) will contain agarose and protamine is soaked at room temperature reaction in the solution of step (1), and reacted product obtains having the titanium dioxide hollow nano-sphere of meso-hole structure through adding the heat extraction gel after lyophilize.
Gel piece preparation process in described step (2) can for: a. prepares agarose solution; B. protamine added in described agarose solution and stir; C. with the solution of step b preparation standing cooling formation gel at room temperature, with the described gel formation gel piece that is cut into small pieces.
The mass percent concentration of the agarose of the agarose solution in described step a is preferably 0.5-4%, as 0.5%, 1%, 2%, 3% or 4%.
In described step a, the temperature of the described agarose solution of configuration is preferably 90-95 ℃, as 90 ℃, 92 ℃, 93 ℃, 94 ℃ or 95 ℃.
The solvent that the agarose solution that configures in described step a adopts is deionized water, prevents from introducing impurity in the process of configuration solution.
The concentration of the protamine in the solution that described step b makes is preferably 1-10g/L, as 1 g/L, 2 g/L, 4 g/L, 6 g/L, 8 g/L or 10 g/L.
The volume of the gel piece in described step c can be 1 cm
3, it is immersed in when reacting in solution, each surface all can be immersed in solution and fully contact with solution, guarantees carrying out smoothly of reaction.
In described step (1), the volumetric molar concentration of the precursor solution of the titanium of configuration is preferably 0.1-0.5mol/L, as 0.1 mol/L, 0.2 mol/L, 0.25 mol/L, 0.3 mol/L or 0.5 mol/L.The precursor solution of described titanium can directly configure, and the precursor solution that also can pass through the titanium of dilution higher concentration obtains, and solvent or the diluent of employing are preferably deionized water, prevent from introducing impurity in the process of configuration solution.
Reaction times in described step (2) can be 1-12h, as 1h, 3h, 6h, 8h or 12h.
The temperature that adds the heat extraction gel in described step (2) is preferably 95-100 ℃, removes clean to guarantee gel.
Described room temperature can be 18-25 ℃, as 18 ℃, 20 ℃, 22 ℃, 24 ℃ or 25 ℃.
The titanium dioxide hollow nano-sphere that adopts the inventive method to obtain is the titanium dioxide hollow nano-sphere with meso-hole structure.
Embodiment 1
Accurately take the 1g agarose, add the 100mL deionized water, be heated to 90-95 ℃ and obtain agarose solution; Accurately take the 200mg protamine, join in above-mentioned agarose solution; Stir, pour watch-glass into, after standing cooling formation gel, gel is cut into 1cm under room temperature
3The fritter of left and right.Get the Ti-BALDH of 25mL 1mol/L, with the deionized water dilution, be settled to 100mL, obtain the Ti-BALDH solution of 0.25 mol/L.Gel piece is immersed in Ti-BALDH solution, reacts 1h under room temperature.Remove unreacted Ti-BALDH solution completely, then use washed with de-ionized water, reheat washing and remove gel, repeatedly clean 2-3 time.Lyophilize obtains having the titanium dioxide hollow nano-sphere of meso-hole structure.
Fig. 2 and Fig. 3 are respectively nitrogen adsorption desorption graphic representation and the pore size distribution curve figure of the titanium dioxide hollow nano-sphere of embodiment 1 preparation.
Embodiment 2
Accurately take the 1g agarose, add the 100mL deionized water, be heated to 90-95 ℃ and obtain agarose solution; Accurately take the 200mg protamine, join in above-mentioned agarose solution; Stir, pour watch-glass into, after standing cooling formation gel, gel is cut into 1cm under room temperature
3The fritter of left and right.Get the Ti-BALDH of 25mL 1mol/L, with the deionized water dilution, be settled to 100mL, obtain the Ti-BALDH solution of 0.25 mol/L.Gel piece is immersed in Ti-BALDH solution, reacts 3h under room temperature.Remove unreacted Ti-BALDH solution completely, then use washed with de-ionized water, reheat washing and remove gel, repeatedly clean 2-3 time.Lyophilize obtains having the titanium dioxide hollow nano-sphere of meso-hole structure.
As shown in Figure 4, transmission electron microscope (TEM) photo for the titanium dioxide hollow nano-sphere of embodiment 2 preparation as seen from the figure, adopt the titanium dioxide hollow nano-sphere of the method preparation of embodiment 2 to have meso-hole structure, and microballoon is hollow housing.
Embodiment 3
Accurately take the 1g agarose, add the 100mL deionized water, be heated to 90-95 ℃ and obtain agarose solution; Accurately take the 200mg protamine, join in above-mentioned agarose solution; Stir, pour watch-glass into, after standing cooling formation gel, gel is cut into 1cm under room temperature
3The fritter of left and right.Get the Ti-BALDH of 25mL 1mol/L, with the deionized water dilution, be settled to 100mL, obtain the Ti-BALDH solution of 0.25 mol/L.Gel piece is immersed in Ti-BALDH solution, reacts 12h under room temperature.Remove unreacted Ti-BALDH solution completely, then use washed with de-ionized water, reheat washing and remove gel, repeatedly clean 2-3 time.Lyophilize obtains having the titanium dioxide hollow nano-sphere of meso-hole structure.
As shown in Figure 5, for the titanium dioxide hollow nano-sphere of embodiment 3 preparation at scanning electron microscope (SEM) photo of 200 ℃ of calcinings after 1 hour, as seen from the figure, after the titanium dioxide hollow Nano ball warp calcining of the method preparation of employing embodiment 3, titanium dioxide still keeps hollow structure.
Embodiment 4:
Accurately take the 0.5g agarose, add the 100mL deionized water, be heated to 90-95 ℃ and obtain agarose solution; Accurately take the 100mg protamine, join in above-mentioned agarose solution; Stir, pour watch-glass into, after standing cooling formation gel, gel is cut into 1cm under room temperature
3The fritter of left and right.Get the Ti-BALDH of 10mL 1mol/L, with the deionized water dilution, be settled to 100mL, obtain the Ti-BALDH solution of 0.1 mol/L.Gel piece is immersed in Ti-BALDH solution, reacts 1h under room temperature.Remove unreacted Ti-BALDH solution completely, then use washed with de-ionized water, reheat washing and remove gel, repeatedly clean 2-3 time.Lyophilize obtains having the titanium dioxide hollow nano-sphere of meso-hole structure.
Embodiment 5:
Accurately take the 4g agarose, add the 100mL deionized water, be heated to 90-95 ℃ and obtain agarose solution; Accurately take the 1000mg protamine, join in above-mentioned agarose solution; Stir, pour watch-glass into, after standing cooling formation gel, gel is cut into 1cm under room temperature
3The fritter of left and right.Get the Ti-BALDH of 50mL 1mol/L, with the deionized water dilution, be settled to 100mL, obtain the Ti-BALDH solution of 0.5 mol/L.Gel piece is immersed in Ti-BALDH solution, reacts 12h under room temperature.Remove unreacted Ti-BALDH solution completely, then use washed with de-ionized water, reheat washing and remove gel, repeatedly clean 2-3 time.Lyophilize obtains having the titanium dioxide hollow nano-sphere of meso-hole structure.
Embodiment 6:
Accurately take the 2g agarose, add the 100mL deionized water, be heated to 90-95 ℃ and obtain agarose solution; Accurately take the 550mg protamine, join in above-mentioned agarose solution; Stir, pour watch-glass into, after standing cooling formation gel, gel is cut into 1cm under room temperature
3The fritter of left and right.Get the Ti-BALDH of 30mL 1mol/L, with the deionized water dilution, be settled to 100mL, obtain the Ti-BALDH solution of 0.3 mol/L.Gel piece is immersed in Ti-BALDH solution, reacts 6h under room temperature.Remove unreacted Ti-BALDH solution completely, then use washed with de-ionized water, reheat washing and remove gel, repeatedly clean 2-3 time.Lyophilize obtains having the titanium dioxide hollow nano-sphere of meso-hole structure.
Embodiment 7:
Accurately take the 0.8g agarose, add the 100mL deionized water, be heated to 90-95 ℃ and obtain agarose solution; Accurately take the 200mg protamine, join in above-mentioned agarose solution; Stir, pour watch-glass into, after standing cooling formation gel, gel is cut into 1cm under room temperature
3The fritter of left and right.Get the Ti-BALDH of 15mL 1mol/L, with the deionized water dilution, be settled to 100mL, obtain the Ti-BALDH solution of 0.15 mol/L.Gel piece is immersed in Ti-BALDH solution, reacts 5h under room temperature.Remove unreacted Ti-BALDH solution completely, then use washed with de-ionized water, reheat washing and remove gel, repeatedly clean 2-3 time.Lyophilize obtains having the titanium dioxide hollow nano-sphere of meso-hole structure.
Embodiment 8:
Accurately take the 1.5g agarose, add the 100mL deionized water, be heated to 90-95 ℃ and obtain agarose solution; Accurately take the 300mg protamine, join in above-mentioned agarose solution; Stir, pour watch-glass into, after standing cooling formation gel, gel is cut into 1cm under room temperature
3The fritter of left and right.Get the Ti-BALDH of 20mL 1mol/L, with the deionized water dilution, be settled to 100mL, obtain the Ti-BALDH solution of 0.2 mol/L.Gel piece is immersed in Ti-BALDH solution, reacts 7h under room temperature.Remove unreacted Ti-BALDH solution completely, then use washed with de-ionized water, reheat washing and remove gel, repeatedly clean 2-3 time.Lyophilize obtains having the titanium dioxide hollow nano-sphere of meso-hole structure.
Embodiment 9:
Accurately take the 3.5g agarose, add the 100mL deionized water, be heated to 90-95 ℃ and obtain agarose solution; Accurately take the 800mg protamine, join in above-mentioned agarose solution; Stir, pour watch-glass into, after standing cooling formation gel, gel is cut into 1cm under room temperature
3The fritter of left and right.Get the Ti-BALDH of 40mL 2mol/L, with the deionized water dilution, be settled to 100mL, obtain the Ti-BALDH solution of 0.4 mol/L.Gel piece is immersed in Ti-BALDH solution, reacts 10h under room temperature.Remove unreacted Ti-BALDH solution completely, then use washed with de-ionized water, reheat washing and remove gel, repeatedly clean 2-3 time.Lyophilize obtains having the titanium dioxide hollow nano-sphere of meso-hole structure.
Embodiment 10:
Accurately take the 2.5g agarose, add the 100mL deionized water, be heated to 90-95 ℃ and obtain agarose solution; Accurately take the 600mg protamine, join in above-mentioned agarose solution; Stir, pour watch-glass into, after standing cooling formation gel, gel is cut into 1cm under room temperature
3The fritter of left and right.Get the Ti-BALDH of 33mL 1mol/L, with the deionized water dilution, be settled to 100mL, obtain the Ti-BALDH solution of 0.33 mol/L.Gel piece is immersed in Ti-BALDH solution, reacts 8h under room temperature.Remove unreacted Ti-BALDH solution completely, then use washed with de-ionized water, reheat washing and remove gel, repeatedly clean 2-3 time.Lyophilize obtains having the titanium dioxide hollow nano-sphere of meso-hole structure.
The various embodiments described above because the amount of substance that participates in reaction is different with the reaction times, can obtain median size titanium dioxide hollow nano-sphere with meso-hole structure of (as: 100nm, 200nm, 300nm or 400nm) between 100nm-400nm.
Comparative Examples 1
Accurately take the 5mg protamine, be dissolved in deionized water, be settled to 10mL.Get the Ti-BALDH of 1mL 2mol/L, with the deionized water dilution, be settled to 8mL, obtain the Ti-BALDH solution of 0.25 mol/L.
Get respectively each 1mL of Ti-BALDH of 2mg/mL protamine solution and 0.25mol/L, hybrid reaction stirs 5min, and centrifugation 5min(centrifugal speed is 3000r/min).Remove supernatant liquor, then use washed with de-ionized water, more centrifugal 5min, remove supernatant liquor.Repeatedly clean 2-3 time.Lyophilize obtains the reunion titania nanoparticles together of median size 40nm.
As shown in Figure 6, be transmission electron microscope (TEM) photo of the titanium dioxide hollow nano-sphere of Comparative Examples 1 preparation, as seen from the figure, the titanium dioxide for preparing in the aqueous solution does not possess hollow structure.
The present invention adopts the biomimetic mineralization in gel media to prepare the titanium dioxide hollow nano-sphere, preparation condition is gentle, the preparation method is simple, the granular size pattern is controlled, the scope of application is wider, and do not need to use template, avoid thus need removing in subsequent technique trouble that template causes and the irregular defective of hollow nano-sphere of preparation.
Claims (10)
1. the method for a bionic preparation titanium dioxide hollow nano-sphere in Ago-Gel medium is characterized in that comprising the following steps: presoma two (2 hydroxy propanoic acid) two hydroxide two ammoniums of (1) preparation titanium close titanium solution; The gel piece that (2) will contain agarose and protamine is soaked at room temperature reaction in the solution of step (1), and reacted product obtains having the titanium dioxide hollow nano-sphere of meso-hole structure through adding the heat extraction gel after lyophilize.
As claimed in claim 1 in Ago-Gel medium the method for bionic preparation titanium dioxide hollow nano-sphere, it is characterized in that the gel piece preparation process in described step (2) is: a. prepares agarose solution; B. protamine added in described agarose solution and stir; C. with the solution of step b preparation standing cooling formation gel at room temperature, with the described gel formation gel piece that is cut into small pieces.
As claimed in claim 2 in Ago-Gel medium the method for bionic preparation titanium dioxide hollow nano-sphere, the mass percent concentration that it is characterized in that the agarose of the agarose solution in described step a is 0.5-4%.
As claimed in claim 3 in Ago-Gel medium the method for bionic preparation titanium dioxide hollow nano-sphere, it is characterized in that the temperature of the described agarose solution of preparation in described step a is 90-95 ℃.
As claimed in claim 4 in Ago-Gel medium the method for bionic preparation titanium dioxide hollow nano-sphere, it is characterized in that the concentration of the protamine in solution that described step b makes is 1-10g/L.
As claimed in claim 5 in Ago-Gel medium the method for bionic preparation titanium dioxide hollow nano-sphere, the volumetric molar concentration that it is characterized in that the precursor solution of the titanium of configuration in described step (1) is 0.1-0.5mol/L, and the solvent of employing is deionized water.
As claimed in claim 6 in Ago-Gel medium the method for bionic preparation titanium dioxide hollow nano-sphere, it is characterized in that the reaction times in described step (2) is 1-12h.
As claimed in claim 7 in Ago-Gel medium the method for bionic preparation titanium dioxide hollow nano-sphere, it is characterized in that the temperature that adds the heat extraction gel in described step (2) is 95-100 ℃.
As claimed in claim 8 in Ago-Gel medium the method for bionic preparation titanium dioxide hollow nano-sphere, the solvent that the agarose solution that it is characterized in that configuring in described step a adopts is deionized water.
As claimed in claim 9 in Ago-Gel medium the method for bionic preparation titanium dioxide hollow nano-sphere, it is characterized in that described room temperature is 18-25 ℃.
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| CN109967064A (en) * | 2019-04-25 | 2019-07-05 | 陕西科技大学 | It is a kind of using natural casein as the porous spherical TiO of template2The preparation method of nanocatalyst |
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| CN106629835B (en) * | 2016-11-18 | 2018-03-23 | 浙江理工大学 | A kind of controllable method for preparing of titania nanoparticles |
| CN109967064A (en) * | 2019-04-25 | 2019-07-05 | 陕西科技大学 | It is a kind of using natural casein as the porous spherical TiO of template2The preparation method of nanocatalyst |
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Application publication date: 20130619 |