CN104843779B - A kind of hollow ball-shape rutile titanium dioxide is mesomorphic and preparation method thereof - Google Patents
A kind of hollow ball-shape rutile titanium dioxide is mesomorphic and preparation method thereof Download PDFInfo
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- CN104843779B CN104843779B CN201510210633.XA CN201510210633A CN104843779B CN 104843779 B CN104843779 B CN 104843779B CN 201510210633 A CN201510210633 A CN 201510210633A CN 104843779 B CN104843779 B CN 104843779B
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 14
- HHDOORYZQSEMGM-UHFFFAOYSA-L potassium;oxalate;titanium(4+) Chemical compound [K+].[Ti+4].[O-]C(=O)C([O-])=O HHDOORYZQSEMGM-UHFFFAOYSA-L 0.000 claims abstract description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 11
- 238000002425 crystallisation Methods 0.000 claims abstract description 5
- 230000008025 crystallization Effects 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 14
- 239000004408 titanium dioxide Substances 0.000 claims description 6
- 238000005119 centrifugation Methods 0.000 claims description 5
- 230000010355 oscillation Effects 0.000 claims description 5
- 238000007789 sealing Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 2
- KYNKUCOQLYEJPH-UHFFFAOYSA-N [K][Ti] Chemical compound [K][Ti] KYNKUCOQLYEJPH-UHFFFAOYSA-N 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 239000000843 powder Substances 0.000 abstract description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 3
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 3
- 230000001699 photocatalysis Effects 0.000 abstract description 3
- 238000007146 photocatalysis Methods 0.000 abstract description 3
- 239000000376 reactant Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- 239000002073 nanorod Substances 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- 239000002070 nanowire Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002057 nanoflower Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000011426 transformation method Methods 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
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- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
Hollow ball-shape rutile titanium dioxide disclosed by the invention is mesomorphic, is the hollow ball-shape structure being assembled by rutile crystallization nanometer rods, and the diameter of hollow ball is 3.0 ~ 6.0 μ m, and the length of nanometer rods is 200 ~ 500nm, and width is 100 ~ 250nm. Its preparation process is: titanium potassium oxalate is dissolved in the hydrogen peroxide reactant liquor that is added with nitric acid, 80oUnder C, be incubated 48 ~ 72 hours. The present invention is without the thermal and hydric environment of HTHP, and next step acquisition hollow ball-shape rutile titanium dioxide of low temperature is mesomorphic, and syntheti c route is simple and easy to do, and cost is low, and powder productive rate is high, can be applicable to the field such as photocatalysis, lithium ion battery.
Description
Technical field
The present invention relates to a kind of hollow ball-shape rutile titanium dioxide mesomorphic and preparation method thereof, belong to the preparation field of metal oxide functional material.
Background technology
Titanium dioxide be a few acid or under alkali condition one of highly stable inorganic material all, owing to thering is excellent biocompatibility, and itself is nontoxic, resource abundance simultaneously, with low cost, aspect photocatalysis, electrochromism, DSSC and lithium ion battery, having broad application prospects, day by day becoming a kind of critical material that solves global environment and energy problem. Mesomorphic structure material has abundant mesoporous, and its atomic arrangement is orientated close to mono-crystalline structures, thus its physicochemical properties and monocrystalline similar, and specific area is significantly higher than monocrystalline, becomes one of Recent study focus. The mesomorphic preparation method of titanium dioxide mainly contains the hot method of hydrothermal/solvent at present, and the topology transformation of predecessor etc. Wherein the hot method of hydrothermal/solvent needs high temperature and high pressure environment, and energy consumption is large, and environment friendly is poor, has larger potential safety hazard, and industrialization cost is higher; And topological transformation method need to be prepared suitable predecessor, obtain titanium dioxide by the subsequent processes of predecessor mesomorphic. The pattern of the titanium dioxide crystallization having obtained at present has nanometer rods, nano flower hollow Nano brick, dumbbell shape and laminated structure, but also do not have low temperature directly to prepare by the stacking hollow ball-shape structure forming of rutile crystallization nanometer rods.
Summary of the invention
The object of this invention is to provide a kind of process simple, without template, hollow ball-shape rutile titanium dioxide that cheaply prepared by one-step method is mesomorphic and preparation method thereof.
Hollow ball-shape rutile titanium dioxide of the present invention is mesomorphic, is the hollow ball-shape structure being assembled by rutile crystallization nanometer rods, and the diameter of hollow ball is 3.0 ~ 6.0 μ m, and the length of nanometer rods is 200 ~ 500nm, and width is 100 ~ 250nm.
The mesomorphic preparation method of hollow ball-shape rutile titanium dioxide of the present invention, its concrete steps are as follows:
1) nitric acid of mass concentration 63% is joined in the hydrogen peroxide solution of mass concentration 10%, the volume ratio of nitric acid and hydrogen peroxide solution is 0.02-0.06;
2) in the nitric acid of step 1) and hydrogen peroxide mixed solution, add titanium potassium oxalate, making the concentration of titanium potassium oxalate in solution is 100 ~ 200 mM/ls, and sonic oscillation fully mixes, and then sealing, 80oUnder C, be incubated 48 ~ 72 hours, through centrifugation, washing, dry, obtain hollow ball-shape rutile titanium dioxide mesomorphic.
The present invention has realized the mesomorphic low temperature preparation of hollow ball-shape structure rutile titanium dioxide first. Utilize titanium potassium oxalate for titanium source, utilize the hydrolysis-dissolving-again deposition process of titanium potassium oxalate in the hydrogen peroxide solution that is dissolved with nitric acid, 80oThe hollow ball-shape rutile titanium dioxide for preparing high-crystallinity under the low temperature of C is mesomorphic. This hollow ball-shape structure is to be the secondary structure that basic composition unit assembles by nanometer rods, and the SEAD of individual nanorod shows that synthesis of nano rod has the structure of single crystal-like, distributes mesoporous in monocrystal nano rod. Synthetic hollow ball-shape titania is mesomorphic to have a wide range of applications in various fields such as photocatalysis, photoelectrocatalysis, solar cell, gas sensor, biomaterial, lithium ion batteries.
Brief description of the drawings
Fig. 1 is the mesomorphic low power SEM photo of hollow ball-shape titania prepared by embodiment 1;
Fig. 2 is the mesomorphic high power SEM photo of hollow ball-shape titania prepared by embodiment 1;
Fig. 3 is the mesomorphic XRD collection of illustrative plates of hollow ball-shape titania prepared by embodiment 1;
Fig. 4 is the TEM photo of the mesomorphic basic composition unit nanometer rods of the hollow ball-shape titania prepared of embodiment 1;
Fig. 5 is HRTEM figure and the FFT Transformation Graphs of the mesomorphic basic composition unit nanometer rods of the hollow ball-shape titania prepared of embodiment 1; Wherein scheming a is HRTEM figure, and figure b is FFT Transformation Graphs.
Fig. 6 is the mesomorphic nitrogen adsorption curve of hollow ball-shape titania prepared by embodiment 1;
Fig. 7 is the SEM figure that embodiment 1 reacts 12 hours product; Wherein scheming a is low power SEM photo, and figure b is high power SEM photo.
Fig. 8 is the SEM figure that embodiment 1 reacts 24 hours product; Wherein scheming a is low power SEM photo, and figure b is high power SEM photo.
Fig. 9 is the SEM figure that embodiment 1 reacts 36 hours product; Wherein scheming a is low power SEM photo, and figure b is high power SEM photo.
Figure 10 is the SEM figure that embodiment 1 reacts 48 hours product; Wherein scheming a is low power SEM photo, and figure b is high power SEM photo.
Figure 11 is the SEM figure that embodiment 1 reacts 60 hours product; Wherein scheming a is low power SEM photo, and figure b is high power SEM photo.
Figure 12 is 12 hours product XRD collection of illustrative plates;
Figure 13 is the mesomorphic SEM photo of hollow ball-shape titania prepared by embodiment 2;
Figure 14 is the mesomorphic SEM photo of hollow ball-shape titania prepared by embodiment 3.
Detailed description of the invention
Further set forth the present invention below in conjunction with embodiment, but the present invention is not only confined to following embodiment.
Embodiment 1
1) getting 3mL mass percent is that to join 50mL mass percent be in 10% hydrogen peroxide solution for 63% nitric acid;
2) in the solution obtaining in step 1), add titanium potassium oxalate, making the concentration of titanium potassium oxalate in solution is 100 mM/ls, and sonic oscillation fully mixes, and obtains kermesinus clear solution;
3) by step 2) sealing of the kermesinus clear solution that obtains, be placed on 80oIn C baking oven, be incubated 72 hours, through centrifugation, washing, dry, obtain white powder, be hollow ball-shape rutile titanium dioxide mesomorphic.
The hollow ball-shape rutile titanium dioxide that this example makes is as shown in Figure 1, 2 mesomorphic, approximately 100 ~ 250nm of the width of nanometer rods, and length is about 200 ~ 500nm, and the hollow ball diameter being assembled by nanometer rods is 3.0 ~ 6.0 μ m. The XRD results verification gained powder of Fig. 3 is well-crystallized's rutile structure titanium dioxide. Fig. 4,5 TEM characterization result show, the basic structural unit of composition hollow ball-shape is the mesoporous rutile titanium dioxide monocrystalline (mesomorphic) that distributes in it. The low temperature nitrogen adsorption curve of Fig. 6 shows, the sample specific area of preparation is 32.19m2/ g, average pore size is 11.3nm, further confirms mesoporous existence.
The time series test of Fig. 7 shows, is 12 hours when the reaction time, and product is the sphere that set of nanowires is dressed up, known in conjunction with Figure 12, and this product is hydrogen metatitanic acid. Reaction time is 24 hours, and as shown in Figure 8, nano wire disappears, and occurs the solid sphere that club shaped structure is stacking. Along with the carrying out of reaction, form gradually by nanometer rods and assemble the hollow ball-shape structure forming, as shown in Fig. 9,10,11.
Embodiment 2
1) getting 1mL mass percent is that to join 50mL mass percent be in 10% hydrogen peroxide solution for 63% nitric acid;
2) in the solution obtaining in step 1), add titanium potassium oxalate, making the concentration of titanium potassium oxalate in solution is 100 mM/ls, and sonic oscillation fully mixes, and obtains kermesinus clear solution;
3) by step 2) sealing of the kermesinus clear solution that obtains, be placed on 80oIn C baking oven, be incubated 72 hours, through centrifugation, washing, dry, obtain white powder.
The mesomorphic SEM photo of hollow ball-shape rutile titanium dioxide that this example makes is as Figure 13, and the length of its construction unit nanometer rods is 150 ~ 250nm, and width is 70 ~ 150nm.
Embodiment 3
1) getting 3mL mass percent is that to join 50mL mass percent be in 10% hydrogen peroxide solution for 63% nitric acid;
2) in the solution obtaining in step 1), add titanium potassium oxalate, making the concentration of titanium potassium oxalate in solution is 200 mM/ls, and sonic oscillation fully mixes, and obtains kermesinus clear solution;
3) by step 2) sealing of the kermesinus clear solution that obtains, be placed on 80oIn C baking oven, be incubated 72 hours, through centrifugation, washing, dry, obtain white powder.
The mesomorphic SEM photo of hollow ball-shape rutile titanium dioxide that this example makes is as Figure 14, and the length of its construction unit nanometer rods is about 150 ~ 200nm, and width is about 50 ~ 100nm.
Claims (1)
1. the mesomorphic preparation method of hollow ball-shape rutile titanium dioxide, this titanium dioxide is situated betweenCrystalline substance is the hollow ball-shape structure being assembled by rutile crystallization nanometer rods, the diameter of hollow ballBe 3.0～6.0 μ m, the length of nanometer rods is 200～500nm, and width is 100～250nm,Its preparation comprises that step is as follows:
1) nitric acid of mass concentration 63% is joined in the hydrogen peroxide solution of mass concentration 10%,The volume ratio of nitric acid and hydrogen peroxide solution is 0.02-0.06;
2) to step 1) nitric acid and hydrogen peroxide mixed solution in add titanium potassium oxalate, make oxalic acidThe concentration of titanium potassium in solution is 100～200 mM/ls, and sonic oscillation fully mixes, soRear sealing is incubated 48～72 hours at 80 DEG C, through centrifugation, washing, dry,Mesomorphic to hollow ball-shape rutile titanium dioxide.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105540657B (en) * | 2016-01-14 | 2017-04-12 | 浙江大学 | Nanosheet-assembling core-shell structure anatase titanium dioxide microsphere and preparation method thereof |
| CN105600822A (en) * | 2016-03-31 | 2016-05-25 | 天津城建大学 | Preparation method of litchi-like hierarchical-structure {001}-surface-exposed TiO2 powder |
| CN106238097B (en) * | 2016-07-28 | 2018-10-16 | 安徽师范大学 | A kind of TiO of butoxy modification2Single crystal hollow four directions nanocone materials, preparation method and applications |
| CN106370858B (en) * | 2016-08-20 | 2017-11-07 | 福建师范大学 | A kind of photoelectric detecting method of double tumor markerses based on current potential addressing mode |
| CN106466604A (en) * | 2016-11-22 | 2017-03-01 | 安徽理工大学 | A kind of Cu2O/TiO2Composite photocatalyst material and preparation method thereof |
| CN112266242A (en) * | 2020-11-19 | 2021-01-26 | 张希君 | Method for preparing spherical rutile particles by using rutile with size less than 200 meshes as main raw material |
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| CN102336435A (en) * | 2011-09-13 | 2012-02-01 | 福州大学 | Porous rutile TiO2 mesomorphase and preparation method and application thereof |
| CN102583525A (en) * | 2012-01-31 | 2012-07-18 | 桂林理工大学 | Preparation method of rutile titanium dioxide mesomorphic crystal |
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| CN102583525A (en) * | 2012-01-31 | 2012-07-18 | 桂林理工大学 | Preparation method of rutile titanium dioxide mesomorphic crystal |
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