CN104043390B - A kind of nano-heterogeneous structure hollow ball of small size high-specific surface area and preparation method thereof - Google Patents
A kind of nano-heterogeneous structure hollow ball of small size high-specific surface area and preparation method thereof Download PDFInfo
- Publication number
- CN104043390B CN104043390B CN201410278209.4A CN201410278209A CN104043390B CN 104043390 B CN104043390 B CN 104043390B CN 201410278209 A CN201410278209 A CN 201410278209A CN 104043390 B CN104043390 B CN 104043390B
- Authority
- CN
- China
- Prior art keywords
- ball
- hollow ball
- nano
- nanometers
- hollow
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
The invention discloses a kind of nano-heterogeneous structure hollow balls of small size high-specific surface area and preparation method thereof.The present invention its spherical shell of hollow ball for two or more metal oxides form, different metal oxides crystal grain spherical shell surface formed hetero-junctions, shell thickness at 20 nanometers hereinafter, single hetero-junctions size be 2~20 nanometers, a diameter of 80~800 nanometers of hollow ball.Nano-heterogeneous structure hollow ball is prepared by the way that more metal ion solutions and subsequent annealing are configured using template adsorption method in the present invention.The hollow ball specific surface area of the present invention is generally higher than 200 m2.g‑1, and its hetero-junctions size, in 10 rans, heterojunction boundary crystalline quality is high, the defects of eliminating the surface state and electron trap generated at interface；Method of the invention is simple, cost is relatively low, and the selection of selection and semiconductor quantity to semiconductor material category all has great range, is conducive to the application of industrialization.
Description
Technical field
The present invention relates to a kind of nano-heterogeneous structure hollow ball and preparation method thereof more particularly to a kind of small size Gao Bibiao
Nano-heterogeneous structure hollow ball of area and preparation method thereof.
Background technology
Along with the development of world civilization, the energy of human needs' consumption is more and more, and corresponding, the ring of discharge
Border pollutant is also more and more.Due to the resource of the earth be it is limited, thus energy and environment problem oneself must as contemporary development
The huge challenge that must be faced.In recent years, the severe situation increasingly to warm in face of traditional energy increasingly imbalance of supply and demand, global climate,
Countries in the world increase the dynamics of the development and utilization to new technology of energy and green technology one after another.Solar energy resources potentiality are big, ring
Low, sustainable use is polluted in border, is the important energy source for being conducive to harmony between man and nature development.And Photocatalitic Technique of Semiconductor is because of it
Can reaction directly be driven using solar energy, have important application prospect in the energy and environmental area.It is urged in semi-conducting material light
In change system, realize that efficiently separating for photo-generate electron-hole is in the necessary approach of energy and environmental problem by photocatalytic applications.
Common single compound photochemical catalyst is metal oxide or sulfide semiconductor material.Such as TiO2、WO3Deng,（Nowotny,
J., Energy & Environmental Science 2008, 1 (5), 565-572. Xi, G.; Ouyang, S.;
Li, P.; Ye, J.; Ma, Q.; Su, N.; Bai, H.; Wang, C., Angewandte Chemie
International Edition 2012, 51 (10), 2395-2399.）They all have very wide in photocatalysis field
General application.But they also have an intrinsic imperfect part, and single semi-conducting material is because of internal flaw and intrinsic compound
Reason so that photo-generate electron-hole after generation, has the photo-generate electron-hole close to 90% directly inside semiconductor and surface is matched
To compound rather than act on water and pollutant.Which results in the waste of most of photo-generate electron-hole, the days of one's doom
The utilization to solar energy is made.Therefore, promote the separation in light induced electron and hole, inhibit its compound, so as to improve quantum efficiency,
To make full use of solar energy, the stability for improving photochemical catalyst is the key problem of modern photocatalysis field.At present, have several
The modification technology of common semiconductor light-catalyst, mainly including doped transition metal ions（Liu, B.; Liu, L.-M.;
Lang, X.-F.; Wang, H.-Y.; Lou, X. W.; Aydil, E. S., Energy & Environmental
Science 2014.）, noble metal loading（Xi, G.; Ye, J.; Ma, Q.; Su, N.; Bai, H.; Wang, C.,
Journal of the American Chemical Society 2012, 134 (15), 6508-6511）, semiconductor light
Catalyst it is compound（Tong, H.; Ouyang, S.; Bi, Y.; Umezawa, N.; Oshikiri, M.; Ye, J.,
Advanced Materials 2012, 24 (2), 229-251.）Deng.First two is due to the use of many rare gold among this
Belong to element, so receiving the limitation of cost and resource reserve.Since general semiconductor catalyst cost is very low and resourceful,
So composite photocatalyst material, because these advantages cause extensive concern, particularly heterojunction material, hetero-junctions is usually by two
The different semi-conducting material of kind is combined by heteroepitaxial growth, because its internal generation can promote what electron hole detached
Built in field, so there is unique physicochemical property on photo-generate electron-hole separation is promoted.Due to nanometer size effect so that
The diffusion length of electron hole greatly reduces, so the heterojunction semiconductor of nanoscale is than corresponding bulk semiconductor hetero-junctions
With more obvious photoelectric properties advantage.Nano semiconductor heterojunction material is prepared and studied, its application is explored, is in recent years
One of research frontier of international nano material has very big challenge and important scientific meaning.
The chemical preparation process of modern nano heterojunction is usually coprecipitation method（Xie, Q.; Guo, H.; Zhang,
X.; Lu, A.; Zeng, D.; Chen, Y.; Peng, D.-L., RSC Advances 2013,3 (46), 24430-
24439）, single separation method（Zheng, L.; Zheng, Y.; Chen, C.; Zhan, Y.; Lin, X.; Zheng,
Q.; Wei, K.; Zhu, J., Inorganic Chemistry 2009,48(5), 1819-1825.）Or it is eutectoid out
Method（Lü, X.; Huang, F.; Mou, X.; Wang, Y.; Xu, F.,Advanced Materials 2010,22
(33), 3719-3722.）.Coprecipitation method due to reacting violent and without surfactant protection, acquisition it is single different
Matter knot size is generally all in 10 micron orders.Single separation method is that another is precipitated in existing semiconductor material structures partly to lead
Body material it is nanocrystalline.This method is sufficiently complex and due to being typically all micro materials as the semi-conducting material of matrix,
So to be obtained nor single hetero-junctions size 100 nanometer scales nano heterojunction.Hetero-junctions can be obtained now
Overall dimensions are to be eutectoid out method in the method for 100 nanometer scales.This method is made using surfactant and metal organic salt
For raw material, precision control experiment parameter can obtain nano heterojunction of the minimum dimension at 20 nanometers.This method in itself for
The requirement of raw material and experimental precision is just very harsh, however most significant problems are hetero-junctions in itself.It is this nano heterogeneous first
Melting becomes block materials between tying single nano heterojunction in order to prevent, and annealing process is not allow to appear in preparation process
's；The heterogeneous interface crystalline quality for thus directly resulting in two kinds of semi-conducting materials is not high excessive with contact stress, so as on boundary
Face produces the defects of surface state and electron trap of flood tide.These defects can directly result in photo-generate electron-hole and be answered in interface
It closes.And since the reunion characteristic in chemical reaction process causes these nano heterojunctions that can be arranged in the form of stacking.In this way
Allow for the photo-generate electron-hole separated in nano heterojunction can occur between nano heterojunction again it is secondary compound.
The specific surface area for having these nano heterojunctions again is generally not more than 100m2·g-1, surface is resulted in this way to be exposed for being catalyzed
The quantity of the active site of reaction is not high, directly results in the degraded performance of heterojunction composite.These composite factors result in existing
The performance of some nano heterojunctions can not be applied to actual production and live.
Invention content
Nano-heterogeneous structure hollow ball and its preparation side the object of the present invention is to provide a kind of small size high-specific surface area
Method.
The nano-heterogeneous structure hollow ball of the small size high-specific surface area of the present invention, the spherical shell of hollow ball is two or more gold
Belong to oxide to form, different metal oxides crystal grain forms hetero-junctions on spherical shell surface, and shell thickness is at 20 nanometers hereinafter, single
Hetero-junctions size is 2~20 nanometers, a diameter of 80~800 nanometers of hollow ball.
The metal oxide be selected from Al, B, Ba, Bi, Ca, Ce, Co, Cr, Cu, Ni, La, Fe, Zn, Sn, Rh, Ta, W,
The oxide of Ti, V, Mn, In, Ge, Zr, Se, Mg, Li, Ga or Si.
The method for preparing the nano-heterogeneous structure hollow ball of above-mentioned small size high-specific surface area, step are as follows：
1）Adsorbent solution is configured：At least two metal salts by arbitrary molar ratio are mixed and are dissolved in solvent, and be configured to gold
Belong to the adsorbent solution that ion total mol concentration is 0.001~10M, the metal salt is Al, B, Ba, Bi, Ca, Ce, Co, Cr,
Acetate, chlorate, the nitric acid of Cu, Ni, La, Fe, Zn, Sn, Rh, Ta, W, Ti, V, Mn, In, Ge, Zr, Se, Mg, Li, Ga, Si
Salt, sulfate or ester salt, the solvent are water, ethyl alcohol, formamide or ethylene glycol；
2）Absorption：There is the spherical template of carboxyl and hydroxyl to immerse step 1 surface）Adsorbent solution in, make its content
For 1g/L ~ 100g/L, ultrasound makes spherical template fully dispersed, centrifuges or filters after 2 ~ 48h of stirring and adsorbing after isolating absorption
Spherical template is placed in 40~100 DEG C, dry 2~48h；The spherical template is carbon ball, PS balls or SiO2Ball；
3）Removing template：By step 2）In dried carbon ball or PS balls 3~60h is heat-treated in air at 300~800 DEG C
It removes carbon ball or PS ball templates obtains hollow ball housing；Or by step 2）In dried SiO2Ball is empty at 300~800 DEG C
After 3~60h being heat-treated in gas, then immerse at 20~100 DEG C in the NaOH solution of a concentration of 1~20M and keep 0.5~for 24 hours, it goes
Except SiO2Ball template obtains hollow ball housing；
4）Annealing：By step 3）In hollow ball housing be placed at 400~800 DEG C and anneal in air 2~20 hours, obtain
Obtain the nano-heterogeneous structure hollow ball with small size high-specific surface area.
In the present invention, the preparation method that the surface has the spherical template of carboxyl and hydroxyl can refer to Sun, X.;
Li, Y., Angewandte Chemie International Edition 2004,43 (29), 3827-3831、Lou,
X. W.; Archer, L. A.; Yang, Z., Advanced Materials 2008,20(21), 3987-4019 with
And Wang, D.; Hisatomi, T.; Takata, T.; Pan, C.; Katayama, M.; Kubota, J.;
Domen, K., Angewandte Chemie International Edition 2013,52 (43), 11252-11256.
In the present invention, the spherical template of anionic group is rich in using surface, passes through the stirring and adsorbing gold in adsorbent solution
Belong to ion.Since the zeta current potentials of template of the surface rich in anionic group are very low, while adsorbing metal ions, these
Because the principle of electrostatic repulsion, can't occur agglomeration, also avoid the reunion of final product between template.Also,
The anionic group integrated distribution of template surface causes shell thickness generally on 10 nanometers of left sides in one layer of active layer on surface
The right side, nano heterojunction are in the state for being similar to monolayer distribution, this has just thoroughly broken away from the hetero-junctions of pervious nano heterojunction
Between stacking it is serious, secondary compound violent essential problem.Additionally due to anionic group adsorbing metal ions are a kind of pure
Potential behavior, so template is no species selectivity in adsorbing metal ions, as long as sun is presented in adsorbent solution
The metallic element of ionic state can be adsorbed.Template spherical in this way can be adsorbed simultaneously in adsorbent solution various metals from
Son.This method can be not only prepared containing only there are two types of the nano heterojunctions of semi-conducting material, can also be prepared containing more kinds of half
The nano heterojunction of conductor material, the pervasive degree for species of metal ion and nano heterojunction type are method for distinguishing hardly possiblies
With what is reached.
The beneficial effects of the present invention are：The nano-heterogeneous structure hollow ball of the present invention, due to unique hollow knot
Structure, specific surface area are generally higher than 200 m2.g-1, and its hetero-junctions size is minimum, generally in 10 rans, hetero-junctions circle
Face crystalline quality is high, the defects of eliminating the surface state and electron trap generated at interface, and product of the invention is not in
Reunion stacking phenomenon；Method of the invention is simple, cost is relatively low, the choosing of selection and semiconductor quantity to semiconductor material category
Selecting all has great range, is conducive to the application of industrialization.
Description of the drawings
Fig. 1 is TiO2/SnO2The SEM pictures of nano-heterogeneous structure hollow ball.
Fig. 2 is TiO2/SnO2The XRD diffraction pictures of nano-heterogeneous structure hollow ball.
Fig. 3 is TiO2/SnO2The transmission picture of nano-heterogeneous structure hollow ball spherical shell.
Fig. 4 is TiO2/SnO2The high-resolution transmission picture of nano-heterogeneous structure hollow ball spherical shell.
Fig. 5 TiO2/SnO2The N of nano-heterogeneous structure hollow ball2Adsorption-desorption curve.
Fig. 6 is TiO2/SnO2Nano-heterogeneous structure hollow ball and pure SnO2、TiO2The photoexcitation spectrum comparison of hollow ball
Figure.
Fig. 7 is TiO2/SnO2Nano-heterogeneous structure hollow ball and pure SnO2、TiO2The photocatalysis performance comparison diagram of hollow ball.
Fig. 8 is Al2O3The SEM figures of/ZnO nano heterojunction structure hollow ball.
Specific embodiment
Embodiment 1
TiO2/SnO2Nano-heterogeneous structure hollow ball：
(1) by 0.3g SnCl2It is placed in 100mL ethyl alcohol and dissolves with 0.31g butyl titanates, it is molten to obtain more metal ions
Liquid, 1g surfaces are then added in into more metal ion solutions has a carbon ball template of carboxyl and hydroxyl, ultrasonic 30min, then
It adsorbs, while stirs 12 hours at room temperature, obtain mixed solution；
(2) mixed solution with the filter membrane that aperture is 450 nanometers is filtered, obtains the carbon ball adsorbed, be placed in 40 DEG C,
Dry 48h；
(3) the heat treatment 6h being put into dried carbon ball in carrying out air environment at a temperature of 350 DEG C in tube furnace,
Heating control is per minute at 1 DEG C, then obtains hollow nanostructured containing Sn, Ti component oxide；
(4) Sn, Ti component oxide obtained using step (3) is hollow nanostructured by the obtained TiO of annealing2/SnO2It receives
Rice heterojunction structure hollow ball, annealing temperature are 500 DEG C, and annealing time is 6 hours.
TiO2/SnO2The SEM pictures of hollow ball are as shown in Figure 1, clearly display it as hollow-core construction.
Its XRD diffraction picture is as shown in Fig. 2, surface TiO2/SnO2Hollow ball is TiO2And SnO2The common presence of phase.
TiO2/SnO2The transmission picture of hollow ball spherical shell is as shown in figure 3, it can be seen that its shell thickness is only 7 nanometers.
Its high-resolution transmits picture as shown in figure 4, showing TiO2、SnO2It is nanocrystalline coexist to form heterojunction structure, it is brilliant
Grain is generally at 3~10 nanometers, and hetero-junctions is nearly monolayer alignment on surface.
Fig. 5 is TiO2/SnO2The N of nano-heterogeneous structure hollow ball2Adsorption-desorption curve, it is from curve it can be seen that this
The specific surface area of heterojunction structure hollow ball is more than 200 m2.g-1
Fig. 6 is TiO2/SnO2Nano-heterogeneous structure hollow ball and the pure SnO prepared using the method2、TiO2Hollow ball
Photoexcitation spectrum comparison diagram, it can be seen that TiO2/SnO2Photo-generate electron-hole is kept completely separate by nano-heterogeneous structure hollow ball；
Its photocatalysis performance comparison diagram is as shown in fig. 7, show TiO2/SnO2Nano-heterogeneous structure hollow ball has excellent photocatalytic
Energy.
Embodiment 2
Al2O3/ ZnO nano heterojunction structure hollow ball：
(1) by 0.1g Al (Ac)3With 1g Zn (Ac)2It is placed in 100mL water and dissolves, obtain more metal ion solutions, then
1g is added in into more metal ion solutions has the carbon ball template of carboxyl and hydroxyl, then ultrasonic 50min inhales at room temperature
It is attached, while stir 12 hours, obtain mixed solution；
(2) mixed solution with the filter membrane that aperture is 450 nanometers is filtered, obtains the carbon ball adsorbed, be placed in 100
DEG C, dry 2h；
(3) the heat treatment 6h being put into dried carbon ball in carrying out air environment at a temperature of 350 DEG C in tube furnace,
Heating control is per minute at 1 DEG C, then obtains hollow nanostructured containing Al, Zn component oxide；
(4) Al, Zn component oxide obtained using step (3) is hollow nanostructured by the obtained Al of annealing2O3/ ZnO receives
Rice heterojunction structure hollow ball, annealing temperature are 700 DEG C, and annealing time is 6 hours.Its SEM picture is as shown in figure 8, clearly
It is shown as hollow-core construction, hollow bulb diameter is within 800nm.
Embodiment 3
Cr2O3/TiO2Nano-heterogeneous structure hollow ball：
(1) by 0.41g Cr (NO3)3It is placed in 100mL ethyl alcohol and dissolves with 0.27g butyl titanates, obtain more metal ions
Solution, 0.4g surfaces are then added in into more metal ion solutions has the SiO of carboxyl and hydroxyl2Ball template, ultrasound
Then 70min is adsorbed at room temperature, while stir 12 hours, obtains mixed solution；
(2) mixed solution with the filter membrane that aperture is 450 nanometers is filtered, obtains the SiO adsorbed2Ball is placed in 60
DEG C, dry 10h；
(3) by dried SiO2Ball is put into the heat treatment 6h in carrying out air environment at a temperature of 350 DEG C in tube furnace,
Its control that heats up is per minute at 1 DEG C, is then added into the NaOH solution of 5M, and 3h is stirred under room temperature by SiO2Ball template dissolves
Fall, obtain hollow nanostructured containing Cr, Ti component oxide；
(4) Cu, Ti component oxide obtained using step (3) is hollow nanostructured by the obtained Cr of annealing2O3/TiO2
Nano-heterogeneous structure hollow ball, annealing temperature are 400 DEG C, and annealing time is 20 hours.Obtained hollow bulb diameter exists
500nm or so.
Embodiment 4
ZnO/NiO nano-heterogeneous structure hollow balls：
(1) by 0.2g Zn (NO3)2With 0.6g Ni (NO3)2It is placed in 100mL formamides and dissolves, obtain more metal ions
Solution, 1g surfaces are then added in into more metal ion solutions has a carbon ball template of carboxyl and hydroxyl, ultrasonic 30min, so
It adsorbs, while stirs 24 hours at 70 DEG C afterwards, obtain mixed solution；
(2) mixed solution with the filter membrane that aperture is 450 nanometers is filtered, obtains the carbon ball adsorbed, be placed in 80 DEG C,
Dry 20h；
(3) the heat treatment 6h being put into dried carbon ball in carrying out air environment at a temperature of 350 DEG C in tube furnace,
Heating control is per minute at 1 DEG C, then obtains hollow nanostructured containing Zn, Ni component oxide；
(4) Zn, Ni component oxide for being obtained using step (3) is hollow nanostructured to be made ZnO/NiO by annealing and receives
Rice heterojunction structure hollow ball, annealing temperature are 600 DEG C, and annealing time is 10 hours.Obtained hollow bulb diameter is in 700nm
Within.
Embodiment 5
WO3/TiO2Nano-heterogeneous structure hollow ball：
(1) by 0.1g WCl6It is placed in 100mL ethylene glycol and dissolves with 0.8g butyl titanates, it is molten to obtain more metal ions
Liquid, 10g surfaces are then added in into more metal ion solutions has a carbon ball template of carboxyl and hydroxyl, ultrasonic 30min, then
It adsorbs, while stirs 5 hours at room temperature, obtain mixed solution；
(2) carbon ball for having adsorbed mixed solution with centrifuge 3000r/min centrifugation 5 min acquisitions, obtains what is adsorbed
Carbon ball template is placed in 50 DEG C, dry 8h；
(3) the heat treatment 10h being put into dried carbon ball in carrying out air environment at a temperature of 350 DEG C in tube furnace,
Its control that heats up is per minute at 1 DEG C, then obtains hollow nanostructured containing W, Ti component oxide；
(4) W, Ti component oxide obtained using step (3) is hollow nanostructured by the obtained WO of annealing3/TiO2Nanometer
Heterojunction structure hollow ball, annealing temperature are 600 DEG C, and annealing time is 14 hours.Obtained hollow bulb diameter 800nm with
It is interior.
Embodiment 6
Al2O3/ ZnO nano heterojunction structure hollow ball：
(1) by 0.1g Al (NO3)3With 1g Zn (NO3)2It is placed in 100mL water and dissolves, obtain more metal ion solutions, so
Adding in 1g surfaces in backward more metal ion solutions has the carbon ball template of carboxyl and hydroxyl, ultrasonic 20min, then in room temperature
Lower absorption, while stir 12 hours, obtain mixed solution；
(2) mixed solution with the filter membrane that aperture is 450 nanometers is filtered, obtains the carbon ball adsorbed, be placed in 40 DEG C,
Dry 30h；
(3) the heat treatment 6h being put into dried carbon ball in carrying out air environment at a temperature of 350 DEG C in tube furnace,
Heating control is per minute at 1 DEG C, then obtains hollow nanostructured containing Al, Zn component oxide；
(4) Al, Zn component oxide obtained using step (3) is hollow nanostructured by the obtained Al of annealing2O3/ ZnO receives
Rice heterojunction structure hollow ball, annealing temperature are 700 DEG C, and annealing time is 6 hours.Obtained hollow bulb diameter is in 500nm
Left and right.
Embodiment 7
CuO/TiO2The different heterojunction structure hollow ball of nanometer：
(1) by 0.2g CuSO4It is placed in 100mL ethyl alcohol and dissolves with 0.25g butyl titanates, it is molten to obtain more metal ions
Liquid, 0.3g surfaces are then added in into more metal ion solutions has a PS ball templates of carboxyl and hydroxyl, ultrasonic 30min, so
It adsorbs, while stirs 12 hours at 40 DEG C afterwards, obtain mixed solution；
(2) mixed solution with the filter membrane that aperture is 450 nanometers is filtered, obtains the PS balls adsorbed, be placed in 100
DEG C, dry 2h；
(3) the heat treatment 6h being put into dried PS balls in carrying out air environment at a temperature of 350 DEG C in tube furnace,
Heating control is per minute at 1 DEG C, then obtains hollow nanostructured containing Cu, Ti component oxide；
(4) Cu, Ti component oxide obtained using step (3) is hollow nanostructured by the obtained CuO/TiO of annealing2It receives
Rice heterojunction structure hollow ball, annealing temperature are 800 DEG C, and annealing time is 2 hours.Obtained hollow bulb diameter is in 150nm
Left and right.
Embodiment 8
La2O3/ZrO2Nano-heterogeneous structure hollow ball：
(1) by 0.8g La2(NO3)3With 0.1g Zr (NO3)4It is placed in 100mL ethyl alcohol and dissolves, it is molten to obtain more metal ions
Liquid, 1g surfaces are then added in into more metal ion solutions has a carbon ball template of carboxyl and hydroxyl, ultrasonic 30min, then
It adsorbs, while stirs 17 hours at room temperature, obtain mixed solution；
(2) mixed solution with the filter membrane that aperture is 450 nanometers is filtered, obtains the carbon ball adsorbed, be placed in 40 DEG C,
Dry 18h；
(3) the heat treatment 60h being put into dried carbon ball in carrying out air environment at a temperature of 300 DEG C in tube furnace,
Its control that heats up is per minute at 1 DEG C, then obtains hollow nanostructured containing La, Zr component oxide；
(4) La, Zr component oxide obtained using step (3) is hollow nanostructured by the obtained La of annealing2O3/ZrO2
Nano-heterogeneous structure hollow ball, annealing temperature are 700 DEG C, and annealing time is 8 hours.Obtained hollow bulb diameter exists
400nm or so.
Embodiment 9
CuO/ZrO2Nano-heterogeneous structure hollow ball：
(1) by 0.5g Cu (Ac)2With 0.2g Zr (NO3)4It is placed in 100mL ethyl alcohol and dissolves, it is molten to obtain more metal ions
Liquid, 5g surfaces are then added in into more metal ion solutions has a carbon ball template of carboxyl and hydroxyl, ultrasonic 30min, then
It adsorbs, while stirs 48 hours at room temperature, obtain mixed solution；
(2) mixed solution with the filter membrane that aperture is 450 nanometers is filtered, obtains the carbon ball adsorbed, be placed in 40 DEG C,
Dry 48h；
(3) the heat treatment 3h being put into dried carbon ball in carrying out air environment at a temperature of 800 DEG C in tube furnace,
Heating control is per minute at 1 DEG C, then obtains hollow nanostructured containing Cu, Zr component oxide；
(4) Cu, Zr component oxide obtained using step (3) is hollow nanostructured by the obtained CuO/ZrO of annealing2It receives
Rice heterojunction structure hollow ball, annealing temperature are 700 DEG C, and annealing time is 4 hours.Obtained hollow bulb diameter is in 600nm
Left and right.
Embodiment 10
B2O3/SiO2Nano-heterogeneous structure hollow ball：
(1) by 0.3g SiCl4With 0.31g B (NO3)3It is placed in 100mL ethyl alcohol and dissolves, obtain more metal ion solutions,
Then 1g surfaces are added in into more metal ion solutions has the carbon ball template of carboxyl and hydroxyl, ultrasonic 30min, then in room
Temperature is lower to be adsorbed, while stir 12 hours, obtains mixed solution；
(2) mixed solution with the filter membrane that aperture is 450 nanometers is filtered, obtains the carbon ball adsorbed, be placed in 40 DEG C,
Dry 48h；
(3) the heat treatment 6h being put into dried carbon ball in carrying out air environment at a temperature of 350 DEG C in tube furnace,
Heating control is per minute at 1 DEG C, then obtains hollow nanostructured containing Si, B component oxide；
(4) Si, the B component oxide obtained using step (3) is hollow nanostructured by the obtained B of annealing2O3/SiO2It receives
Rice heterojunction structure hollow ball, annealing temperature are 500 DEG C, and annealing time is 6 hours.Obtained hollow bulb diameter is in 500nm
Left and right.
Embodiment 11
In2O3/MgO/Ga2O3Nano-heterogeneous structure hollow ball：
(1) by 0.3g InCl3、0.31g MgSO4With 0.2g GaCl3It is placed in 100mL ethyl alcohol and dissolves, obtain more metals
Solion, 1g surfaces are then added in into more metal ion solutions has the carbon ball template of carboxyl and hydroxyl, ultrasound
Then 30min is adsorbed at room temperature, while stir 12 hours, obtains mixed solution；
(2) mixed solution with the filter membrane that aperture is 450 nanometers is filtered, obtains the carbon ball adsorbed, be placed in 40 DEG C,
Dry 48h；
(3) the heat treatment 6h being put into dried carbon ball in carrying out air environment at a temperature of 350 DEG C in tube furnace,
Heating control is per minute at 1 DEG C, then obtains hollow nanostructured containing In, Mg, Ga component oxide；
(4) In, Mg, Ga component oxide obtained using step (3) is hollow nanostructured by the obtained In of annealing2O3/
MgO/Ga2O3Nano-heterogeneous structure hollow ball, annealing temperature are 550 DEG C, and annealing time is 6 hours.Obtained hollow ball is straight
Diameter is within 800nm.
Embodiment 12
Co3O4/CuO/TiO2The different heterojunction structure hollow ball of nanometer：
(1) by 0.2g CoCl2、0.2g CuCl2It is placed in 100mL ethyl alcohol and dissolves with 0.25g butyl titanates, obtain more
Metal ion solution, 0.3g surfaces are then added in into more metal ion solutions has the PS ball templates of carboxyl and hydroxyl, surpasses
Then sound 30min is adsorbed at 40 DEG C, while stir 12 hours, obtains mixed solution；
(2) mixed solution with the filter membrane that aperture is 450 nanometers is filtered, obtains the PS balls adsorbed, be placed in 70 DEG C,
Dry 40h；
(3) the heat treatment 6h being put into dried PS balls in carrying out air environment at a temperature of 350 DEG C in tube furnace,
Its control that heats up is per minute at 1 DEG C, then obtains hollow nanostructured containing Co, Cu, Ti component oxide；
(4) Co, Cu, Ti component oxide obtained using step (3) is hollow nanostructured by the obtained Co of annealing3O4/
CuO/TiO2Nano-heterogeneous structure hollow ball, annealing temperature are 450 DEG C, and annealing time is 8 hours.Obtained hollow ball is straight
Diameter is in 300nm or so.
Embodiment 13
GeO2/V2O3/TiO2The different heterojunction structure hollow ball of nanometer：
(1) by 0.2g GeCl4、0.2g VCl3It is placed in 100mL ethyl alcohol and dissolves with 0.25g butyl titanates, obtain mostly golden
Belong to solion, 0.3g surfaces are then added in into more metal ion solutions has the PS ball templates of carboxyl and hydroxyl, ultrasound
Then 30min is adsorbed at 40 DEG C, while stir 12 hours, obtains mixed solution；
(2) mixed solution with the filter membrane that aperture is 450 nanometers is filtered, obtains the PS balls adsorbed, be placed in 70 DEG C,
Dry 40h；
(3) the heat treatment 6h being put into dried PS balls in carrying out air environment at a temperature of 350 DEG C in tube furnace,
Its control that heats up is per minute at 1 DEG C, then obtains hollow nanostructured containing Ge, V, Ti component oxide；
(4) Ge, V, Ti component oxide obtained using step (3) is hollow nanostructured by the obtained GeO of annealing2/
V2O3/TiO2Nano-heterogeneous structure hollow ball, annealing temperature are 450 DEG C, and annealing time is 8 hours.Obtained hollow ball is straight
Diameter is in 400nm or so.
Embodiment 14
ZnO/MgO2/CuO/TiO2The different heterojunction structure hollow ball of nanometer：
(1) by 0.2g ZnCl2、0.3g MgSO4、0.2g CuCl2It is placed in 100mL ethyl alcohol with 0.25g butyl titanates
Dissolving, obtains more metal ion solutions, and 0.3g surfaces are then added in into more metal ion solutions has carboxyl and hydroxyl
Then PS ball templates, ultrasonic 30min are adsorbed at 40 DEG C, while stir 12 hours, obtain mixed solution；
(2) mixed solution with the filter membrane that aperture is 450 nanometers is filtered, obtains the PS balls adsorbed, be placed in 70 DEG C,
Dry 40h；
(3) the heat treatment 6h being put into dried PS balls in carrying out air environment at a temperature of 350 DEG C in tube furnace,
Its control that heats up is per minute at 1 DEG C, then obtains hollow nanostructured containing Zn, Mg, Cu, Ti component oxide；
(4) Zn, Mg, Cu, Ti component oxide obtained using step (3) is hollow nanostructured by the obtained ZnO/ of annealing
MgO2/CuO/TiO2Nano-heterogeneous structure hollow ball, annealing temperature are 450 DEG C, and annealing time is 8 hours.Obtained is hollow
Bulb diameter is in 500nm or so.
Claims (1)
1. a kind of nano-heterogeneous structure hollow ball of small size high-specific surface area, it is characterised in that the spherical shell of the hollow ball is two
Kind or more metal oxide form, different metal oxides crystal grain spherical shell surface formed hetero-junctions, shell thickness is at 20 nanometers
Hereinafter, single hetero-junctions size is 2~20 nanometers, a diameter of 80~800 nanometers of hollow ball, the composition of the hollow ball is：
In2O3/MgO/Ga2O3Or Co3O4/CuO/TiO2Or GeO2/V2O3/TiO2Or ZnO/MgO/CuO/TiO2；And the hollow ball
It prepares with the following method：
1）Adsorbent solution is configured：By at least three kinds of metal salts by arbitrary molar ratio mix be dissolved in solvent, and be configured to metal from
Sub- total mol concentration is the adsorbent solution of 0.001~10M, and the metal salt is Co, Cu, Zn, Ti, V, In, Ge, Mg, Ga
Chlorate, sulfate or ester salt, the solvent are ethyl alcohol；
2）Absorption：There is the spherical template of carboxyl and hydroxyl to immerse step 1 surface）Adsorbent solution in, make its content be 1g/
L ~ 100g/L, ultrasound make spherical template fully dispersed, and the spherical mould after isolating absorption is centrifuged or filtered after 2 ~ 48h of stirring and adsorbing
Plate is placed in 40~100 DEG C, dry 2~48h；The spherical template is carbon ball, PS balls or SiO2Ball；
3）Removing template：By step 2）In dried carbon ball or PS balls 3~60h removals are heat-treated in air at 300~800 DEG C
Carbon ball or PS ball templates obtain hollow ball housing；Or by step 2）In dried SiO2Ball is at 300~800 DEG C in air
After being heat-treated 3~60h, then immerse at 20~100 DEG C in the NaOH solution of a concentration of 1~20M and keep 0.5~for 24 hours, removal
SiO2Ball template obtains hollow ball housing；
4）Annealing：By step 3）Hollow ball housing obtained is placed at 400~800 DEG C anneals 2~20 hours in air, obtains
Nano-heterogeneous structure hollow ball with small size high-specific surface area.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410278209.4A CN104043390B (en) | 2014-06-20 | 2014-06-20 | A kind of nano-heterogeneous structure hollow ball of small size high-specific surface area and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410278209.4A CN104043390B (en) | 2014-06-20 | 2014-06-20 | A kind of nano-heterogeneous structure hollow ball of small size high-specific surface area and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104043390A CN104043390A (en) | 2014-09-17 |
| CN104043390B true CN104043390B (en) | 2018-07-06 |
Family
ID=51497081
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410278209.4A Active CN104043390B (en) | 2014-06-20 | 2014-06-20 | A kind of nano-heterogeneous structure hollow ball of small size high-specific surface area and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104043390B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106268846B (en) * | 2015-06-03 | 2018-07-06 | 浙江大学 | A kind of crystal Cu2O/ amorphous Ta2O5Nano-heterogeneous structure hollow ball and preparation method thereof |
| CN105688889A (en) * | 2016-03-21 | 2016-06-22 | 江苏大学 | Preparation method for bismuth vanadate hollow microspheres |
| CN107946087B (en) * | 2017-11-24 | 2020-07-10 | 云南大学 | Preparation and application of hollow nanospheres composed of manganous-manganic oxide nanoparticles |
| CN110721689A (en) * | 2019-11-12 | 2020-01-24 | 江苏师范大学 | Porous spherical NiO/TiO2Heterostructure nano material and preparation method thereof |
| CN114843106B (en) * | 2022-04-29 | 2024-03-19 | 哈尔滨工业大学 | Preparation method of bismuth oxide heterojunction, bismuth oxide heterojunction broadband photoelectric detector and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101905153A (en) * | 2010-07-21 | 2010-12-08 | 江苏大学 | Preparation method and application of ZnO-doped TiO2 composite hollow sphere |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100464833C (en) * | 2004-11-11 | 2009-03-04 | 中国科学院化学研究所 | Template process of preparing hollow ball and composite hollow ball |
| CN101259401B (en) * | 2004-11-11 | 2010-06-23 | 中国科学院化学研究所 | Method for preparing hollow ball and hollow ball with complex structure by template method |
| CN101890350B (en) * | 2010-07-21 | 2012-07-04 | 江苏大学 | Method for preparing Fe3+doped TiO2 hollow sphere catalyst and application thereof |
-
2014
- 2014-06-20 CN CN201410278209.4A patent/CN104043390B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101905153A (en) * | 2010-07-21 | 2010-12-08 | 江苏大学 | Preparation method and application of ZnO-doped TiO2 composite hollow sphere |
Non-Patent Citations (1)
| Title |
|---|
| Use of Carbonaceous Polysaccharide Microspheres as Templates for Fabricating Metal Oxide Hollow Spheres;Xiaoming Sun等;《Chemistry-A European Journal》;20051223;第12卷;实验部分和结论部分 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104043390A (en) | 2014-09-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104492460B (en) | A kind of metal-oxide/nano metal sulfide hollow ball and its production and use | |
| CN104043390B (en) | A kind of nano-heterogeneous structure hollow ball of small size high-specific surface area and preparation method thereof | |
| US9586191B2 (en) | Magnetic core coated inorganic ion adsorbent for removing Cs ions in radioactive wastewater and preparation method thereof | |
| CN103908972A (en) | Recyclable BiOX/TiO2 composite photocatalyst and preparation method thereof | |
| CN104174415B (en) | A kind of Bi2O3/ BiOX nano-heterogeneous structure hollow ball and preparation method thereof | |
| CN104549526B (en) | Metallic oxide/Cu2O/polypyrrole three-layer-structure hollow nanosphere and preparation method and application thereof | |
| Lei et al. | Microstructure and photocatalytic properties of polyimide/heterostructured NiO–Fe 2 O 3–ZnO nanocomposite films via an ion-exchange technique | |
| CN101302036A (en) | Preparation of doped titanium dioxide nano-tube | |
| CN101116808A (en) | Photocatalysis powder having a negative ion releasing function and method for preparing the same | |
| CN102674451A (en) | Preparation method of {001} face exposed titanium dioxide nanocrystals | |
| CN102941103A (en) | Bismuth ferrite-graphene nanometer composite material for the filed of photocatalysis and preparation method thereof | |
| CN104591301A (en) | Preparation method of porous nano CoFe2O4 | |
| CN108187606A (en) | A kind of electric conductivity titanium based lithium-ion sieve and preparation method thereof | |
| CN103641165A (en) | Method for preparing titanium dioxide nanotube by using natural mineral as formwork | |
| CN105289578A (en) | Metal oxide/carbon nanotube composite photocatalyst, and preparation method and application thereof | |
| CN105056849A (en) | Hollow sphere adopting metal oxide/Pt/C three-layer nano structure and preparation method of hollow sphere | |
| CN105883910B (en) | A kind of perovskite SrTiO3The preparation method and product of porous nano particle | |
| CN101525155B (en) | Method for preparing manganese sesquioxide one dimension nano material | |
| CN102660770A (en) | Preparation method for ZnMn2O4 nanorod by using alpha-MnO2 nanorod template method | |
| CN108793231A (en) | The method that molten-salt growth method synthesizes fusiform germanic acid zinc nanoparticles | |
| CN105817241A (en) | Method for preparing copper phosphotungstate@titanium dioxide core-shell structured nanomaterial | |
| CN108435757A (en) | A method of stablizing cadmium using oxide containing silicon | |
| CN111135838B (en) | Bi 2 MoO 6 And Co (OH) 2 Composite material for forming heterogeneous structure and preparation method thereof | |
| CN101693520B (en) | Industrialized process for preparing cerium oxide nano-rods doped with rare earth elements | |
| CN104483351B (en) | Palladium-doped hollow porous stannic oxide microcubes as well as preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |