CN106571240B - A kind of preparation method and its usage of hollow silica/titanium dioxide microballoon sphere of original position carbon doped layer time structure - Google Patents
A kind of preparation method and its usage of hollow silica/titanium dioxide microballoon sphere of original position carbon doped layer time structure Download PDFInfo
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- CN106571240B CN106571240B CN201611004596.8A CN201611004596A CN106571240B CN 106571240 B CN106571240 B CN 106571240B CN 201611004596 A CN201611004596 A CN 201611004596A CN 106571240 B CN106571240 B CN 106571240B
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- Y02E60/13—Energy storage using capacitors
Abstract
The present invention provides a kind of preparation method and its usage of hollow silica/titanium dioxide microballoon sphere of carbon doped layer time structure in situ, preparation method includes：Step 1, the cationic sub-micron polystyrene core-shell structure microballoon for preparing monodispersity；Step 2 prepares functional CPS/SiO2Nucleocapsid microballoon；Step 3 prepares CPS/SiO2/ CPS microballoons；Step 4 prepares CPS/SiO2/CPS/TiO2Presoma；Step 5, the hollow silica/titanium dioxide microballoon sphere for preparing carbon doped layer time structure in situ.The present invention is by controlling monodispersity, TEOS and the TBT sedimentations of two layers of cationic template and catalyzing hydrolysis speed, it realizes the uniform self assembly in cationic template surface, prepares hollow silica/titanium dioxide microballoon sphere of high degree of monodispersity original position carbon doped layer time structure.
Description
Technical field
The present invention relates to a kind of simple technologies of preparing of novel electrode material for super capacitor, refer in particular to a kind of in-situ carbon
Adulterate the preparation method and its usage of hollow silica/titanium dioxide microballoon sphere of hierarchical structure.
Background technology
Ultracapacitor is as energy storage device of new generation, because of for example high storing up electricity performance of its series of advantages, good
Charge and discharge process and fabulous service life cycle, and extensively send out applied to the composite electric vehicles, mobile device and storage
Deposit back-up system (X.Lu, M.Yu, G.Wang, T.Zhai, S.Xie, Y.Ling, Y.Tong, Y.Li.H-TiO2@MnO2/H-
TiO2@C Core–Shell Nanowires for High Performance and Flexible Asymmetric
Supercapacitors.Adv.Mater.2013,25,267–272).In order to meet to next-generation portable and dexterous energy
The growing demand of source storage device, substantial amounts of scientific worker concentrate on the new high performance electrochemical energy storage of research
Cryopreservation device (X.Xia, D.Chao, Z.Fan, C.Guan, X.Cao, H.Zhang, H.J.Fan.A New Type of Porous
Graphite Foams and Their Integrated Composites with Oxide/Polymer Core/Shell
Nanowires for Supercapacitors:Structural Design,Fabrication,and Full
Supercapacitor Demonstrations.Nano Lett.2014,14,1651-1658).Obviously, electrode material is to determine
Determine the key of ultracapacitor chemical property.Therefore, how to design and prepare the electrode material of high quality and it is tied
Structure, which is realized, controllably just becomes the target that energy science and technology worker makes great efforts.
Titanium dioxide because a series of its charming performance is for example nontoxic, inexpensive, high stability, high energy density and and
The advantages that substantial amounts of current electrode compatibility, become a kind of preferable double layer electrodes material (A.Ramadoss,
S.J.Kim.Improved activity of a graphene–TiO2hybrid electrode in an
electrochemical supercapacitor.Carbon,2013,434-445).However, pure titanium dioxide nano-particle
Because of its poor electricity and ionic conductivity, the solar energy that especially wide band gap causes its relatively low adsorbs and high impedance is
The shortcomings of its high resistance brought as electrode material (X.Chen, L.Liu, P.Y.Yu, S.S.Mao, Increasing
solar absorption for photocatalysis with black hydrogenated titanium dioxide
Nanocrystals.Science, 2011,331,746), and seriously hinder its further applying in ultracapacitor.For
This, by adulterating extraneous element such as metal or the nonmetallic chemical property that can significantly improve titanium dioxide.It is metal-doped because
Its low thermal stability, photoetch and easily become electron-hole complex centre, and be subject to certain restrictions.It is in contrast, non-
The doping of metal-doped especially carbon because have the conductive performance similar to metal, big electron storage capacity, raising photoelectron-
The a series of advantage such as hole separation and wide solar absorption, and it is hot as the research for improving titanium-dioxide photo electrical property
Point.(W.Li,F.Wang,Y.Liu,J.Wang,J.Yang,L.Zhang,A.A.Elzatahry,D.Al-Dahyan,Y.Xia,
D.Y.Zhao.General Strategy to Synthesize Uniform Mesoporous TiO2/Graphene/
Mesoporous TiO2Sandwich-Like Nanosheets for Highly Reversible Lithium
Storage.Nano Lett.,2015,15,2186).However, the existing titania-doped method of carbon for preparing still has very
Big deficiency, if desired for the shortcomings of carbon component of additional carbon matrix precursor and doping is added easily to assemble (L.Quan, Y.Jang,
K.Stoerzinger,K.May,Y.Jang,S.Kochuveedu,Y.S.Horn,D.H.Kim.Soft-template-
carbonization route to highly textured mesoporous carbon–TiO2inverse opals
for efficient photocatalytic and photoelectrochemical
applications.Phys.Chem.Chem.Phys.,2014,16,9023).For this purpose, applicant once invented it is a kind of simple
, the method (application number of the low-cost in-situ preparation of carbon doping efficient visible light catalyst of hollow titanium dioxide：
201510095295.X)。
The advantages that silica is because of its high surface area, chemical inertness and good translucency, is often used as titanium dioxide
The carrier of nano-particle, with improve its surface area and photocatalysis efficiency (C.Kapridaki, L.Pinho, M.J.Mosquera,
P.Maravelaki-Kalaitzaki.Producing photoactive,transparent and hydrophobic
SiO2-crystalline TiO2nanocomposites at ambient conditions with application as
Self-cleaning coatings.Appl.Catal.B-environ, 2014,156-157,416-427), meanwhile, titanium dioxide
Silicon/composite titania material also has wide answer in terms of the high-tech areas such as optics, electricity, medicine, solar cell
Use prospect.However, existing the methods of being condensed by collosol and gel and cohydrolysis, prepares earth silicon/titanic oxide composite wood
Material still has its limitation that can only such as excite under ultraviolet light and poor photoelectric properties.Therefore, development it is a kind of easy,
The low-cost preparation method with the earth silicon/titanic oxide composite material for protruding photoelectric properties, not only with important
Theory meaning, more have great application value.
The purpose of the present invention is exactly hollow silica/titanium dioxide that design synthesizes the hierarchical structure of in-situ carbon doping
(SiO2/C-TiO2) composite material.C-SiO prepared by the present invention2/TiO2Material not only effectively can overcome titanium dioxide to utilize
The shortcomings that visible ray is poor, and prominent photoelectric properties can be shown, be prepare double electric layers supercapacitor one kind it is splendid
Electrode material.In order to realize this target, the present invention uses a kind of cation polystyrene (CPS) that inventor creates as mould
Plate (Chinese invention patent：ZL 200910234354.1), using ethyl alcohol as polymerization system, using tetraethoxysilane as silicon source, with alkene
Propyl-triethoxysilicane is functional condensation monomer, and functionalized silica nucleocapsid is prepared under ammonia-catalyzed effect
Composite material (CPS/SiO2)；Again with CPS/SiO2For template, the CPS/SiO of sandwich style is prepared by surface aggregate2/CPS
Material then using butyl titanate as titanium precursors, under the catalytic action of minor amount of water, prepares CPS/SiO2/CPS/TiO2Material
Material, the segmented program heating (application number finally invented in the present inventor：201510095295.X) effect under, be prepared in situ out
The hollow C-SiO of the hierarchical structure of carbon doping2/TiO2Composite material.
The content of the invention
It is an object of the invention to provide hollow the two of a kind of carbon doped layer in situ with superior photoelectric properties time structure
Silica/titanium dioxide (SiO2/C-TiO2) new electrode material simple method for preparing, it is therefore intended that not only can effectively gram
Take existing preparation SiO2/TiO2The shortcomings that composite material, and TiO 2 visible light catalytic efficiency and photoelectricity can also be greatly improved
Performance.
Target to realize the present invention, the present invention is first using the monodisperse cation polystyrene microsphere (CPS) prepared
As template；Second step promotes tetraethoxysilane and allyltriethoxysilane in template table by ammonia-catalyzed hydrolysis
Face carries out uniform self assembly, prepares functional monodispersity nucleocapsid microballoon (CPS/SiO2)；3rd step, with CPS/
SiO2For template, second layer cationic polyvinyl template (CPS/SiO is prepared by surface aggregate2/CPS)；4th step, then with
CPS/SiO2/ CPS is template, using electrostatic attraction, accelerates butyl titanate and realizes uniform self assembly on its surface, prepare
The CPS/SiO of hierarchical structure2/CPS/TiO2It is micro- to calcine two layers of cation polystyrene of removing finally by segmented program for presoma
Ball template successfully prepares hollow silica/titanium dioxide (SiO of the hierarchical structure of in-situ carbon doping2/C-TiO2) green wood
Material.
Here is technical scheme：
A kind of preparation method of hollow silica/titanium dioxide microballoon sphere of original position carbon doped layer time structure, including as follows
Step：
Step 1, the cationic sub-micron polystyrene microsphere (CPS) for preparing monodispersity；
Step 2 prepares functional CPS/SiO2Nucleocapsid microballoon：CPS prepared by step 1 is scattered in ethyl alcohol,
The temperature of control system adds in ammonium hydroxide, is slowly added to tetraethoxysilane (TEOS) under mechanical stirring and is reacted at 50 DEG C,
Allyltriethoxysilane is added under inert gas shielding to be reacted, and is cooled to room temperature, is centrifuged, washs, dries,
The cationic sub-micron polystyrene/silica dioxide nucleocapsid microballoon of monodispersity is obtained, is denoted as CPS/SiO2；
Step 3 prepares CPS/SiO2/ CPS microballoons：CPS/SiO prepared by step 22It is scattered in ethyl alcohol, in indifferent gas
Body is protected under mechanical agitation, reacting and being warming up to 50 DEG C, add styrene monomer and azodiisobutyronitrile (AIBN), be warming up to
It 70 DEG C, is reacted；Then cationic benzyl vinyl trimethyl ammonium chloride (VTC)/deionized water mixed liquor is added dropwise, then constant temperature is held
Continuous reaction, reaction are finished, are cooled to room temperature, centrifuge, wash, dry, obtain product, be denoted as CPS/SiO2/ CPS microballoons；
Step 4 prepares CPS/SiO2/CPS/TiO2Presoma：CPS/SiO prepared by step 32/ CPS is scattered in ethyl alcohol
In, under ice-water bath and mechanical agitation, positive four butyl ester (TBT) ethanol solution of metatitanic acid is slowly dropped to reaction system, is settled
After reacting a period of time, then deionized water/alcohol mixeding liquid is slowly added dropwise, reaction is hydrolyzed；After reaction, by sample into
Row centrifugation is alternately washed with deionized water and ethyl alcohol, dry, is obtained product, is denoted as CPS/SiO2/CPS/TiO2Presoma；
Step 5, the hollow silica/titanium dioxide microballoon sphere (SiO for preparing carbon doped layer time structure in situ2/C-TiO2)：
By the CPS/SiO of preparation2/CPS/TiO2Presoma is placed in chamber type electric resistance furnace, is carried out temperature-gradient method calcining, after calcining, is obtained
To hollow silica/titanium dioxide microballoon sphere of carbon doped layer in situ time structure, SiO is denoted as2/C-TiO2。
In step 2, functional CPS/SiO is prepared2During nucleocapsid microballoon, used CPS, ethyl alcohol, ammonium hydroxide, tetrem
Oxysilane, the amount ratio of allyltriethoxysilane are 1~5g：40mL：3mL：0.8g：0.2mL；Used ammonium hydroxide
Mass fraction is 25%, adds in the reaction time after tetraethoxysilane as 4~6h, and the inert gas is nitrogen, is added in
Reaction time after allyltriethoxysilane is 6h.
In step 3, CPS/SiO is prepared2During/CPS microballoons, used CPS/SiO2, ethyl alcohol, styrene monomer, azo two
Isobutyronitrile, the amount ratio of cationic benzyl vinyl trimethyl ammonium chloride/deionized water mixed liquor are 2g：40mL：2g：0.02g：
1.5g；In used cation benzyl vinyl trimethyl ammonium chloride/deionized water mixed liquor, cationic benzyl vinyl trimethyl
Ammonium chloride and the mass ratio of deionized water are 1：1；The reaction time being warming up to after 70 DEG C is 1.5h；Drip cationic benzyl
After vinyl trimethyl ammonium chloride/deionized water mixed liquor, then constant temperature sustained response time for 12 it is small when；The inert gas
For nitrogen.
In step 4, CPS/SiO is prepared2/CPS/TiO2During presoma, used CPS/SiO2/ CPS, ethyl alcohol, metatitanic acid are just
Four butyl ester ethanol solutions, the amount ratio of deionized water/alcohol mixeding liquid are 1g：40mL：20mL：10mL；Positive four fourth of metatitanic acid
The concentration of ester ethanol solution is 0.1~0.25g/mL；In the deionized water/alcohol mixeding liquid, the body of deionized water and ethyl alcohol
Product is than being 3：7；The time of the sedimentation reaction is more than or equal to for 24 hours, and the time of the hydrolysis is more than or equal to for 24 hours.
In step 5, the mode of the temperature-gradient method calcining is：By room temperature to 250 DEG C, used time 250min, at 250 DEG C
Keep 60min；250 DEG C are warming up to 300 DEG C, used time 100min, and 30min is kept at 300 DEG C；300 DEG C are warming up to 350 DEG C, the used time
200min keeps 120min at 350 DEG C；350 DEG C are warming up to 400 DEG C, used time 200min, and 60min is kept at 400 DEG C；400 DEG C rise
Temperature keeps 120min to 450 DEG C, used time 200min, at 450 DEG C.
Hollow silica/titanium dioxide microballoon sphere of prepared carbon doped layer in situ time structure, grain size for 600~
800nm。
Hollow silica/titanium dioxide microballoon sphere of prepared carbon doped layer in situ time structure is used in ultraviolet light or can
See the lower rhodamine B degradation of light excitation.
Hollow silica/titanium dioxide microballoon sphere of prepared carbon doped layer in situ time structure is used to prepare super capacitor
Device electrode material.
In the present invention, CPS/SiO2/CPS/TiO2During presoma, it is added in catalyst (deionized water/alcohol mixeding liquid)
Before, it is necessary to TBT is allowed to have the sufficient sedimentation time (at least for 24 hours) in cationic template.The purpose is to enable TBT template surface into
The uniform sedimentation of row can realize " original position " hydrolysis self assembly, if the sedimentation time is too short, TBT when water adds in template surface
It is uneven in template surface sedimentation, and TBT hydrolysis rates are exceedingly fast, and finally result in the dispersiveness of hollow titanium dioxide of preparation too
Difference.
In the present invention, the catalyst of TBT is hydrolyzed, it is necessary under stirring and add in the mixture (3 of water and ethyl alcohol:7,
v/v).Water is such as directly added into, local hydrolysis rate can be caused too fast, microballoon is caused largely to be reunited.
In the present invention, to CPS/SiO2/CPS/TiO2The method for calcinating of presoma is calcined for segmented program, due to cation
Template at 200 DEG C or so with regard to that can start to decompose, and TiO2From amorphous to about 300 DEG C or so of anatase crystal phase transition temperature, and
And be possible to transformation completely to 500 DEG C.In order to ensure TiO2Before anatase crystal is completely converted into, template cannot be complete
It is removed entirely, and the calcining system preferably relatively closed at one, to ensure TiO2Carbon during crystal phase transition it is a large amount of
In the presence of.
Advantageous effect：
(1) it is a kind of monodispersity, TEOS and TBT sedimentations by controlling two layers of cationic template and catalyzing hydrolysis
Speed realizes the uniform self assembly in cationic template surface, prepares high degree of monodispersity original position carbon doped layer time structure
The method of hollow silica/titanium dioxide microballoon sphere.
(2) it is a kind of hollow silica/titanium dioxide microballoon sphere of carbon doped layer time structure in situ, because it combines two
The two-fold advantage of silica and titanium dioxide, can improve titanium dioxide photocatalysis contact rate and absorption be more catalyzed it is low
Object, and cause the preparation method of higher photocatalysis efficiency.
(3) it is the complex microsphere that a kind of combination carbon, silica and titanium dioxide Multiple components are integrated, not only
The photocatalysis efficiency of titanium dioxide can be improved, even more prepares a kind of method of preferable double electric layers supercapacitor electrode material.
(4) it is a kind of addition time and mode that styrene and cationic monomer are added in by the accuracy controlling second layer,
To obtain " sandwich " formula cation template of monodispersity, and prevent styrene monomer from forming the preparation method of new core.
(5) it be it is a kind of by the sedimentation time of accuracy controlling TBT, catalyst system and catalyzing and temperature of reaction system etc. it is crucial because
Element, to control the method for quick, uniform self assemblies of the TBT in template surface.
(6) it be it is a kind of it is accurate heated up using segmented program prepare the hollow silica of carbon doped layer time structure in situ/
The method of titanium dioxide microballoon sphere.
(7) it is a kind of method for providing carbon doping hollow titanium dioxide carbon source using cationic template itself.
(8) it is a kind of with high storing up electricity performance, durable charge and discharge process and fabulous service life cycle in-situ carbon
Adulterate the preparation method of hollow silica/titanium dioxide microballoon sphere of hierarchical structure.
(9) method provided by the present invention is that the carbon source of carbon doping hollow titanium dioxide comes from two layers of cation and gathers
It styrene template namely is not required to additionally add in any carbon source, so as to be prepared in situ out hollow the two of carbon doped layer in situ time structure
Silica/titanium dioxide microballoon sphere.
(10) hollow silica/titanium dioxide microballoon sphere for the carbon doped layer in situ time structure that prepared by the present invention, Ke Yichong
Divide the negative electrical charge performance using internal layer silica surface, adsorb various metal cations, prepare diversified functional gold
Belong to-hollow silica/titanic oxide material of carbon co-doped hierarchical structure.
(11) hollow silica/titanium dioxide microballoon sphere for the carbon doped layer in situ time structure that prepared by the present invention, outer layer two
The shell thickness of titanium oxide can be easy to adjust by the addition of TBT.
(12) SiO prepared by the present invention2/C-TiO2Catalyst has the ability of very strong light degradation pollutant, either
Under ultraviolet or excited by visible light, the ability of rhodamine B degradation is all than commercial P25TiO2Powder is eager to excel.
(13) SiO prepared by the present invention2/C-TiO2Material can be as the electrode material of ultracapacitor, due to titanium dioxide
The dielectric of silicon is often relatively low, is commonly referred to be and is not suitable for that electrode material can be used as, and therefore, this is that a kind of novelty invented for the first time is super
Grade capacitor material.
SiO prepared by the present invention2/C-TiO2Material can be as the working electrode of ultracapacitor, in 1M KOH electrolyte
In, using saturated calomel electrode as reference electrode, using platinum electrode as anode, present extremely strong charge and discharge time, high capacitance
And recycle number.
Description of the drawings
Fig. 1 is the SEM photograph of the cationic sub-micron polystyrene microsphere of monodispersity in embodiment 1.
Fig. 2 is using the cationic sub-micron polystyrene microsphere of the monodispersity in embodiment one as template in embodiment 2
Prepared CPS/SiO2The SEM photograph of structure.
Fig. 3 is CPS/SiO prepared in embodiment 22/ CPS structure SEM photographs.
Fig. 4 is the CPS/SiO prepared in embodiment 22/CPS/TiO2Structure SEM photograph.
Fig. 5 is the hollow SiO of the hierarchical structure prepared in embodiment 22/C-TiO2SEM photograph.
Fig. 6 is the TEM photos of the hollow SiO2/C-TiO2 of the hierarchical structure prepared in embodiment 2.
Fig. 7 is respectively with SiO in embodiment 72/C-TiO2It is catalyst with P25, rhodamine B degradation under ultraviolet light
(RHB) result figure.
Fig. 8 is respectively with SiO in embodiment 82/C-TiO2It is catalyst with P25, rhodamine B degradation under visible light
(RHB) result figure.
Fig. 9 is respectively with SiO in embodiment 92/C-TiO2It is the capacitance that electrode material prepares ultracapacitor with P25
Value.
Specific embodiment
With reference to specific embodiment, the present invention will be further described.
Embodiment 1
The potassium peroxydisulfate of the deionized water of 72g, 8g styrene and 0.16g is put into the four-necked bottle of 150mL, is being stirred
In the state of speed 350rpm, lead to nitrogen removal air about after twenty minutes, be placed in 70 DEG C of waters bath with thermostatic control.When reaction 1.5 is small
Afterwards, under nitrogen protection, with microsyringe by the mixed liquor (volume ratio of VTC and deionized water of 1.2g VTC/ deionized waters
1：1) inject in reaction bulb, first three pin per one pin of half an hour (per pin 10 μ L), after inject two pins, each one pin of hour, per pin again
For (50 μ L).Subsequent surplus solution injects a pin in every 3 minutes again, is (10 μ L) per pin, until having injected all remaining VTC
Amount, after the completion of to be injected, then make polymerization extend about 12 it is small when, it is made fully to polymerize.After the completion of polymerization, with aqueous miillpore filter
(0.22 μm) filters polymer, washed and is separated, and finally prepares the cationic sub-micro of the monodispersity of VTC about 15%
Rice polystyrene microsphere, referred to as CPS, grain size 600-800nm, as shown in Figure 1.
Embodiment 2
Prepare carbon doping hollow silica/titanium dioxide (SiO of hierarchical structure2/C-TiO2)。
CPS/SiO2It prepares：In the four-hole boiling flask of 100mL, add in 3.2g CPS templates and be scattered in 40mL ethyl alcohol,
At 50 DEG C, the 3mL ammonium hydroxide that addition mass fraction is 25% slowly adds the temperature of control system under mechanical stirring as catalyst
Enter the TEOS of 0.8g, after reacting 4h, add in 0.2mL allyltriethoxysilanes under nitrogen protection, react 6h, be cooled to room
Temperature centrifuges, washs, is dry, preparing functional CPS/SiO2Nucleocapsid microballoon；Such as Fig. 2；
CPS/SiO2/ CPS is synthesized：In the four-hole boiling flask of 100mL, 2g CPS/SiO are added in2And it is scattered in 40mL ethyl alcohol
In, in nitrogen protection under mechanical agitation, reacting and being warming up to 50 DEG C, add styrene monomer 2g and initiator A IBN
0.02g is warming up to 70 DEG C.After reacting 1.5h, the mixed liquor (m/m=1) of DMC 0.75g and deionized water 0.75g is added dropwise, then it is permanent
When warm sustained response 12 is small, it is cooled to room temperature, centrifuges, washs, dries, prepare the CPS/SiO of " sandwich " formula2/CPS
Microballoon, such as Fig. 3；
CPS/SiO2/CPS/TiO2It is prepared by presoma：In the four-hole boiling flask of 100mL, 1g CPS/SiO are added in2/ CPS is simultaneously
It is scattered in 40mL ethyl alcohol, under ice-water bath and mechanical agitation, adds in prepared 20mL in advance, the metatitanic acid of 0.1g/mL is just
Four butyl ester ethanol solutions, and be slowly dropped to reaction system, sedimentation reaction at least for 24 hours after, then 10mL volume ratios are slowly added dropwise and are
3:Reaction is hydrolyzed at least for 24 hours in 7 deionized water/alcohol mixeding liquid.Reaction terminates, and sample is centrifuged, and uses deionization
Alternately washing for several times, in 60 DEG C of oven drying 15h, obtains CPS/SiO for water and ethyl alcohol2/CPS/TiO2Presoma, such as Fig. 4；
SiO2/C-TiO2It prepares：By the CPS/SiO of preparation2/CPS/TiO2Presoma is placed in chamber type electric resistance furnace, is carried out special
It is calcined in fixed temperature-gradient method program：25 DEG C are warming up to 250 DEG C, used time 250min, keep 60min；250 DEG C are warming up to 300 DEG C,
Used time 100min keeps 30min；300 DEG C are warming up to 350 DEG C, used time 200min, keep 120min；350 DEG C are warming up to 400 DEG C,
Used time 200min keeps 60min；400 DEG C are warming up to 450 DEG C, used time 200min, keep 120min.So as to what is be prepared in situ out
Carbon doping hollow silica/titanium dioxide microballoon sphere of hierarchical structure, such as Fig. 5 and Fig. 6.
Embodiment 3
Prepare carbon doping hollow silica/titanium dioxide (SiO of hierarchical structure2/C-TiO2)。
CPS/SiO2It prepares：In the four-hole boiling flask of 100mL, add in 3.2g CPS templates and be scattered in 40mL ethyl alcohol,
At 50 DEG C, the 3mL ammonium hydroxide that addition mass fraction is 25% slowly adds the temperature of control system under mechanical stirring as catalyst
Enter the TEOS of 0.8g, after reacting 5h, add in 0.2mL allyltriethoxysilanes under nitrogen protection, react 6h, be cooled to room
Temperature centrifuges, washs, is dry, preparing functional CPS/SiO2Nucleocapsid microballoon；
CPS/SiO2/ CPS is synthesized：In the four-hole boiling flask of 100mL, 2g CPS/SiO are added in2And it is scattered in 40mL ethyl alcohol
In, in nitrogen protection under mechanical agitation, reacting and being warming up to 50 DEG C, add styrene monomer 2g and initiator A IBN
0.02g is warming up to 70 DEG C.After reacting 1.5h, the mixed liquor (m/m=1) of DMC 0.75g and deionized water 0.75g is added dropwise, then it is permanent
When warm sustained response 12 is small, it is cooled to room temperature, centrifuges, washs, dries, prepare the CPS/SiO of " sandwich " formula2/CPS
Microballoon；
CPS/SiO2/CPS/TiO2It is prepared by presoma：In the four-hole boiling flask of 100mL, 1g CPS/SiO are added in2/ CPS is simultaneously
It is scattered in 40mL ethyl alcohol, under ice-water bath and mechanical agitation, adds in prepared 20mL in advance, the metatitanic acid of 0.2g/mL is just
Four butyl ester ethanol solutions, and be slowly dropped to reaction system, sedimentation reaction at least for 24 hours after, then 10mL volume ratios are slowly added dropwise and are
3:Reaction is hydrolyzed at least for 24 hours in 7 deionized water/alcohol mixeding liquid.Reaction terminates, and sample is centrifuged, and uses deionization
Alternately washing for several times, in 60 DEG C of oven drying 15h, obtains CPS/SiO for water and ethyl alcohol2/CPS/TiO2Presoma；
SiO2/C-TiO2It prepares：By the CPS/SiO of preparation2/CPS/TiO2Presoma is placed in chamber type electric resistance furnace, is carried out special
It is calcined in fixed temperature-gradient method program：25 DEG C are warming up to 250 DEG C, used time 250min, keep 60min；250 DEG C are warming up to 300 DEG C,
Used time 100min keeps 30min；300 DEG C are warming up to 350 DEG C, used time 200min, keep 120min；350 DEG C are warming up to 400 DEG C,
Used time 200min keeps 60min；400 DEG C are warming up to 450 DEG C, used time 200min, keep 120min.So as to what is be prepared in situ out
Carbon doping hollow silica/titanium dioxide microballoon sphere of hierarchical structure.
Embodiment 4
Prepare carbon doping hollow silica/titanium dioxide (SiO of hierarchical structure2/C-TiO2)。
CPS/SiO2It prepares：In the four-hole boiling flask of 100mL, add in 3.2g CPS templates and be scattered in 40mL ethyl alcohol,
At 50 DEG C, the 3mL ammonium hydroxide that addition mass fraction is 25% slowly adds the temperature of control system under mechanical stirring as catalyst
Enter the TEOS of 0.8g, after reacting 6h, add in 0.2mL allyltriethoxysilanes under nitrogen protection, react 6h, be cooled to room
Temperature centrifuges, washs, is dry, preparing functional CPS/SiO2Nucleocapsid microballoon；
CPS/SiO2/ CPS is synthesized：In the four-hole boiling flask of 100mL, 2g CPS/SiO are added in2And it is scattered in 40mL ethyl alcohol
In, in nitrogen protection under mechanical agitation, reacting and being warming up to 50 DEG C, add styrene monomer 2g and initiator A IBN
0.02g is warming up to 70 DEG C.After reacting 1.5h, the mixed liquor (m/m=1) of DMC 0.75g and deionized water 0.75g is added dropwise, then it is permanent
When warm sustained response 12 is small, it is cooled to room temperature, centrifuges, washs, dries, prepare the CPS/SiO of " sandwich " formula2/CPS
Microballoon；
CPS/SiO2/CPS/TiO2It is prepared by presoma：In the four-hole boiling flask of 100mL, 1g CPS/SiO are added in2/ CPS is simultaneously
It is scattered in 40mL ethyl alcohol, under ice-water bath and mechanical agitation, adds in prepared 20mL in advance, the metatitanic acid of 0.25g/mL is just
Four butyl ester ethanol solutions, and be slowly dropped to reaction system, sedimentation reaction at least for 24 hours after, then 10mL volume ratios are slowly added dropwise and are
3:Reaction is hydrolyzed at least for 24 hours in 7 deionized water/alcohol mixeding liquid.Reaction terminates, and sample is centrifuged, and uses deionization
Alternately washing for several times, in 60 DEG C of oven drying 15h, obtains CPS/SiO for water and ethyl alcohol2/CPS/TiO2Presoma；
SiO2/C-TiO2It prepares：By the CPS/SiO of preparation2/CPS/TiO2Presoma is placed in chamber type electric resistance furnace, is carried out special
It is calcined in fixed temperature-gradient method program：25 DEG C are warming up to 250 DEG C, used time 250min, keep 60min；250 DEG C are warming up to 300 DEG C,
Used time 100min keeps 30min；300 DEG C are warming up to 350 DEG C, used time 200min, keep 120min；350 DEG C are warming up to 400 DEG C,
Used time 200min keeps 60min；400 DEG C are warming up to 450 DEG C, used time 200min, keep 120min.So as to what is be prepared in situ out
Carbon doping hollow silica/titanium dioxide microballoon sphere of hierarchical structure.
Embodiment 5
Prepare carbon doping hollow silica/titanium dioxide (SiO of hierarchical structure2/C-TiO2)。
CPS/SiO2It prepares：In the four-hole boiling flask of 100mL, add in 1g CPS templates and be scattered in 40mL ethyl alcohol, control
At 50 DEG C, the 3mL ammonium hydroxide that addition mass fraction is 25% is slowly added to the temperature of system processed under mechanical stirring as catalyst
The TEOS of 0.8g after reacting 4h, adds in 0.2mL allyltriethoxysilanes, reacts 6h, be cooled to room under nitrogen protection
Temperature centrifuges, washs, is dry, preparing functional CPS/SiO2Nucleocapsid microballoon；
CPS/SiO2/ CPS is synthesized：In the four-hole boiling flask of 100mL, 2g CPS/SiO are added in2And it is scattered in 40mL ethyl alcohol
In, in nitrogen protection under mechanical agitation, reacting and being warming up to 50 DEG C, add styrene monomer 2g and initiator A IBN
0.02g is warming up to 70 DEG C.After reacting 1.5h, the mixed liquor (m/m=1) of DMC 0.75g and deionized water 0.75g is added dropwise, then it is permanent
When warm sustained response 12 is small, it is cooled to room temperature, centrifuges, washs, dries, prepare the CPS/SiO of " sandwich " formula2/CPS
Microballoon；
CPS/SiO2/CPS/TiO2It is prepared by presoma：In the four-hole boiling flask of 100mL, 1g CPS/SiO are added in2/ CPS is simultaneously
It is scattered in 40mL ethyl alcohol, under ice-water bath and mechanical agitation, adds in prepared 20mL in advance, the metatitanic acid of 0.1g/mL is just
Four butyl ester ethanol solutions, and be slowly dropped to reaction system, sedimentation reaction at least for 24 hours after, then 10mL volume ratios are slowly added dropwise and are
3:Reaction is hydrolyzed at least for 24 hours in 7 deionized water/alcohol mixeding liquid.Reaction terminates, and sample is centrifuged, and uses deionization
Alternately washing for several times, in 60 DEG C of oven drying 15h, obtains CPS/SiO for water and ethyl alcohol2/CPS/TiO2Presoma；
SiO2/C-TiO2It prepares：By the CPS/SiO of preparation2/CPS/TiO2Presoma is placed in chamber type electric resistance furnace, is carried out special
It is calcined in fixed temperature-gradient method program：25 DEG C are warming up to 250 DEG C, used time 250min, keep 60min；250 DEG C are warming up to 300 DEG C,
Used time 100min keeps 30min；300 DEG C are warming up to 350 DEG C, used time 200min, keep 120min；350 DEG C are warming up to 400 DEG C,
Used time 200min keeps 60min；400 DEG C are warming up to 450 DEG C, used time 200min, keep 120min.So as to what is be prepared in situ out
Carbon doping hollow silica/titanium dioxide microballoon sphere of hierarchical structure.
Embodiment 6
Prepare carbon doping hollow silica/titanium dioxide (SiO of hierarchical structure2/C-TiO2)。
CPS/SiO2It prepares：In the four-hole boiling flask of 100mL, add in 5g CPS templates and be scattered in 40mL ethyl alcohol, control
At 50 DEG C, the 3mL ammonium hydroxide that addition mass fraction is 25% is slowly added to the temperature of system processed under mechanical stirring as catalyst
The TEOS of 0.8g after reacting 6h, adds in 0.2mL allyltriethoxysilanes, reacts 6h, be cooled to room under nitrogen protection
Temperature centrifuges, washs, is dry, preparing functional CPS/SiO2Nucleocapsid microballoon；
CPS/SiO2/ CPS is synthesized：In the four-hole boiling flask of 100mL, 2g CPS/SiO are added in2And it is scattered in 40mL ethyl alcohol
In, in nitrogen protection under mechanical agitation, reacting and being warming up to 50 DEG C, add styrene monomer 2g and initiator A IBN
0.02g is warming up to 70 DEG C.After reacting 1.5h, the mixed liquor (m/m=1) of DMC 0.75g and deionized water 0.75g is added dropwise, then it is permanent
When warm sustained response 12 is small, it is cooled to room temperature, centrifuges, washs, dries, prepare the CPS/SiO of " sandwich " formula2/CPS
Microballoon；
CPS/SiO2/CPS/TiO2It is prepared by presoma：In the four-hole boiling flask of 100mL, 1g CPS/SiO are added in2/ CPS is simultaneously
It is scattered in 40mL ethyl alcohol, under ice-water bath and mechanical agitation, adds in prepared 20mL in advance, the metatitanic acid of 0.15g/mL is just
Four butyl ester ethanol solutions, and be slowly dropped to reaction system, sedimentation reaction at least for 24 hours after, then 10mL volume ratios are slowly added dropwise and are
3:Reaction is hydrolyzed at least for 24 hours in 7 deionized water/alcohol mixeding liquid.Reaction terminates, and sample is centrifuged, and uses deionization
Alternately washing for several times, in 60 DEG C of oven drying 15h, obtains CPS/SiO for water and ethyl alcohol2/CPS/TiO2Presoma；
SiO2/C-TiO2It prepares：By the CPS/SiO of preparation2/CPS/TiO2Presoma is placed in chamber type electric resistance furnace, is carried out special
It is calcined in fixed temperature-gradient method program：25 DEG C are warming up to 250 DEG C, used time 250min, keep 60min；250 DEG C are warming up to 300 DEG C,
Used time 100min keeps 30min；300 DEG C are warming up to 350 DEG C, used time 200min, keep 120min；350 DEG C are warming up to 400 DEG C,
Used time 200min keeps 60min；400 DEG C are warming up to 450 DEG C, used time 200min, keep 120min.So as to what is be prepared in situ out
Carbon doping hollow silica/titanium dioxide microballoon sphere of hierarchical structure.
Embodiment 7
The SiO prepared by 10mg (1mg/mL)2/C-TiO2With rhodamine B 5mL (RHB：2mol/l) pour into small beaker
In, it stirs 60 minutes in the dark, the absorption-desorption of rhodamine B is balanced with reaching catalyst, is then irradiated under ultraviolet light
The different time.It was sampled every 20 minutes, (λ=553nm) is tested using UV, visible light spectrophotometer, to obtain difference
The RHB concentration variation of degradation time, such as Fig. 7, finally according to the value of the degraded RHB of the positive curve acquisition of core.Recycle business P25
As a comparison, the RHB degradation values under its same terms are measured, the results showed that hierarchical structure SiO of the invention2/C-TiO2It presents
The performance of higher UV degradation pollutant.
Embodiment 8
The SiO prepared by 10mg (1mg/mL)2/C-TiO2With rhodamine B 5mL (RHB：2mol/l) pour into small beaker
In, it stirs 60 minutes in the dark, the absorption-desorption of rhodamine B is balanced with reaching catalyst, is then irradiated under visible light
The different time.It was sampled every 10 minutes, (λ=553nm) is tested using UV, visible light spectrophotometer, to obtain difference
The RHB concentration variation of degradation time, such as Fig. 8, finally according to the value of the degraded RHB of the positive curve acquisition of core.Recycle business P25
As a comparison, the RHB degradation values under its same terms are measured, the results showed that hierarchical structure SiO of the invention2/C-TiO2It presents
The performance of higher Visible Light Induced Photocatalytic pollutant.
Embodiment 9
SiO2/C-TiO2(14mg) and acetylene black (6mg) are fallen under polytetrafluoroethylene (PTFE) bonding agent and the effect of a small amount of ethyl alcohol
Enter nickel bubble on piece, then the working electrode of ultracapacitor is prepared through calendering, finally in 1M KOH electrolyte, with saturation calomel
Electrode is reference electrode, using platinum electrode as anode, measures its capacitance.Again on this basis, with P25 under the same conditions, into
Row capacitance compares, such as Fig. 9, the results showed that hierarchical structure SiO of the invention2/C-TiO2It is demonstrated by out higher specific capacitance.
Claims (8)
1. a kind of preparation method of hollow silica/titanium dioxide microballoon sphere of original position carbon doped layer time structure, which is characterized in that
Include the following steps：
Step 1, the cationic sub-micron polystyrene microsphere CPS for preparing monodispersity；
Step 2 prepares functional CPS/SiO2Nucleocapsid microballoon：CPS prepared by step 1 is scattered in ethyl alcohol, control volume
The temperature of system adds in ammonium hydroxide, is slowly added to tetraethoxysilane under mechanical stirring and is reacted at 50 DEG C, is protected in inert gas
The lower addition allyltriethoxysilane of shield is reacted, and is cooled to room temperature, is centrifuged, washs, dries, obtains monodispersity
Cationic sub-micron polystyrene/silica dioxide nucleocapsid microballoon, be denoted as CPS/SiO2；
Step 3 prepares CPS/SiO2/ CPS microballoons：CPS/SiO prepared by step 22It is scattered in ethyl alcohol, is protected in inert gas
Shield is warming up to 70 DEG C, carries out under mechanical agitation, reacting and being warming up to 50 DEG C, add styrene monomer and azodiisobutyronitrile
Reaction；Then cationic benzyl vinyl trimethyl ammonium chloride/deionized water mixed liquor, then constant temperature sustained response is added dropwise, has reacted
Finish, be cooled to room temperature, centrifuge, wash, dry, obtain product, be denoted as CPS/SiO2/ CPS microballoons；
Step 4 prepares CPS/SiO2/CPS/TiO2Presoma：CPS/SiO prepared by step 32/ CPS is scattered in ethyl alcohol,
Under ice-water bath and mechanical agitation, the positive four butyl esters ethanol solution of metatitanic acid is slowly dropped to reaction system, during one section of sedimentation reaction
Between after, then deionized water/alcohol mixeding liquid is slowly added dropwise, reaction is hydrolyzed；After reaction, sample is centrifuged, spent
Ionized water and ethyl alcohol alternately wash, dry, obtain product, are denoted as CPS/SiO2/CPS/TiO2Presoma；
Step 5, the hollow silica/titanium dioxide microballoon sphere SiO for preparing carbon doped layer time structure in situ2/C-TiO2：It will prepare
CPS/SiO2/CPS/TiO2Presoma is placed in chamber type electric resistance furnace, is carried out temperature-gradient method calcining, after calcining, is obtained original position
Hollow silica/titanium dioxide microballoon sphere of carbon doped layer time structure, is denoted as SiO2/C-TiO2。
2. a kind of hollow silica/titanium dioxide microballoon sphere of carbon doped layer time structure in situ according to claim 1
Preparation method, which is characterized in that in step 2, prepare functional CPS/SiO2During nucleocapsid microballoon, used CPS, second
Alcohol, ammonium hydroxide, tetraethoxysilane, the amount ratio of allyltriethoxysilane are 1 ~ 5g：40mL：3mL：0.8g：0.2mL；Institute
The mass fraction of the ammonium hydroxide used is 25%, adds in the reaction time after tetraethoxysilane as 4 ~ 6h, the inert gas is
Nitrogen, the reaction time added in after allyltriethoxysilane are 6h.
3. a kind of hollow silica/titanium dioxide microballoon sphere of carbon doped layer time structure in situ according to claim 1
Preparation method, which is characterized in that in step 3, prepare CPS/SiO2During/CPS microballoons, used CPS/SiO2, ethyl alcohol, benzene second
Alkene monomer, azodiisobutyronitrile, the amount ratio of cationic benzyl vinyl trimethyl ammonium chloride/deionized water mixed liquor are 2g：
40mL：2g：0.02g：1.5g；In used cation benzyl vinyl trimethyl ammonium chloride/deionized water mixed liquor, cation
Benzyl vinyl trimethyl ammonium chloride and the mass ratio of deionized water are 1：1；The reaction time being warming up to after 70 DEG C is 1.5h；
After dripping cationic benzyl vinyl trimethyl ammonium chloride/deionized water mixed liquor, then the time of constant temperature sustained response is small for 12
When；The inert gas is nitrogen.
4. a kind of hollow silica/titanium dioxide microballoon sphere of carbon doped layer time structure in situ according to claim 1
Preparation method, which is characterized in that in step 4, prepare CPS/SiO2/CPS/TiO2During presoma, used CPS/SiO2/
The positive four butyl esters ethanol solution of CPS, ethyl alcohol, metatitanic acid, the amount ratio of deionized water/alcohol mixeding liquid are 1g：40mL：20mL：10mL；
The concentration of the positive four butyl esters ethanol solution of metatitanic acid is 0.1 ~ 0.25g/mL；In the deionized water/alcohol mixeding liquid, deionization
The volume ratio of water and ethyl alcohol is 3：7；The time of the sedimentation reaction is more than or equal to for 24 hours, and the time of the hydrolysis is big
In equal to for 24 hours.
5. a kind of hollow silica/titanium dioxide microballoon sphere of carbon doped layer time structure in situ according to claim 1
Preparation method, which is characterized in that in step 5, the mode of the temperature-gradient method calcining is：By room temperature to 250 DEG C, the used time
250 min keep 60 min at 250 DEG C；250 DEG C are warming up to 300 DEG C, 100 min of used time, and 30 min are kept at 300 DEG C；
300 DEG C are warming up to 350 DEG C, 200 min of used time, and 120 min are kept at 350 DEG C；350 DEG C are warming up to 400 DEG C, the used time 200
Min keeps 60 min at 400 DEG C；400 DEG C are warming up to 450 DEG C, 200 min of used time, and 120 min are kept at 450 DEG C.
6. hollow silica/titanium dioxide microballoon sphere of carbon doped layer in situ time structure prepared by method described in claim 1,
It is characterized in that, hollow silica/titanium dioxide microballoon sphere of the original position carbon doped layer time structure, grain size are 600 ~ 800nm.
7. hollow silica/bis- of carbon doped layer in situ time structure prepared by the method described in claim 1 ~ 5 any one
The purposes of titania microsphere, which is characterized in that hollow silica/titanium dioxide of prepared carbon doped layer in situ time structure
Microballoon is used for the rhodamine B degradation under ultraviolet light or excited by visible light.
8. hollow silica/bis- of carbon doped layer in situ time structure prepared by the method described in claim 1 ~ 5 any one
The purposes of titania microsphere, which is characterized in that hollow silica/titanium dioxide of prepared carbon doped layer in situ time structure
Microballoon is used to prepare electrode material for super capacitor.
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| CN104759273A (en) * | 2015-03-04 | 2015-07-08 | 江苏大学 | Preparation method for in-situ carbon doped hollow titanium dioxide visible light photocatalyst |
| CN104829265A (en) * | 2015-04-09 | 2015-08-12 | 河北工业大学 | Preparation method of inorganic hierarchical pore structure material |
| CN104843724A (en) * | 2015-04-09 | 2015-08-19 | 河北工业大学 | Preparation method of novel inorganic hierarchical pore structure material |
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| CN102463105A (en) * | 2010-10-29 | 2012-05-23 | 中国科学院理化技术研究所 | Preparation method of silicon-dioxide-coated titanium dioxide hollow core-shell structural material |
| CN104759273A (en) * | 2015-03-04 | 2015-07-08 | 江苏大学 | Preparation method for in-situ carbon doped hollow titanium dioxide visible light photocatalyst |
| CN104829265A (en) * | 2015-04-09 | 2015-08-12 | 河北工业大学 | Preparation method of inorganic hierarchical pore structure material |
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