CN103014829B - { 001}/{ 010}/{ 101} crystal face anatase octahedrite TiO is rich in preparation 2the method of monocrystalline - Google Patents
{ 001}/{ 010}/{ 101} crystal face anatase octahedrite TiO is rich in preparation 2the method of monocrystalline Download PDFInfo
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 138
- 239000013078 crystal Substances 0.000 title claims abstract description 75
- 238000000034 method Methods 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000002245 particle Substances 0.000 claims abstract description 28
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 13
- 239000002243 precursor Substances 0.000 claims abstract description 9
- 230000009257 reactivity Effects 0.000 claims abstract description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 10
- 238000000151 deposition Methods 0.000 claims description 9
- 230000008021 deposition Effects 0.000 claims description 9
- 238000007789 sealing Methods 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 8
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 2
- 230000001699 photocatalysis Effects 0.000 abstract description 15
- 150000002500 ions Chemical class 0.000 abstract description 8
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 239000001257 hydrogen Substances 0.000 abstract description 5
- 238000006303 photolysis reaction Methods 0.000 abstract description 4
- 230000015843 photosynthesis, light reaction Effects 0.000 abstract description 4
- 229910010413 TiO 2 Inorganic materials 0.000 abstract description 3
- 239000000975 dye Substances 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 238000010189 synthetic method Methods 0.000 abstract description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 2
- 235000011089 carbon dioxide Nutrition 0.000 abstract description 2
- 230000015556 catabolic process Effects 0.000 abstract description 2
- 238000006731 degradation reaction Methods 0.000 abstract description 2
- 238000009826 distribution Methods 0.000 abstract description 2
- 239000003344 environmental pollutant Substances 0.000 abstract description 2
- 238000007540 photo-reduction reaction Methods 0.000 abstract description 2
- 231100000719 pollutant Toxicity 0.000 abstract description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 8
- 229910001220 stainless steel Inorganic materials 0.000 description 7
- 239000010935 stainless steel Substances 0.000 description 7
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 7
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- -1 alkali metal titanate Chemical class 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000012876 topography Methods 0.000 description 3
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- XTEGARKTQYYJKE-UHFFFAOYSA-M chlorate Inorganic materials [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052730 francium Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- ICIWUVCWSCSTAQ-UHFFFAOYSA-M iodate Chemical compound [O-]I(=O)=O ICIWUVCWSCSTAQ-UHFFFAOYSA-M 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000002055 nanoplate Substances 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- YPJKMVATUPSWOH-UHFFFAOYSA-N nitrooxidanyl Chemical compound [O][N+]([O-])=O YPJKMVATUPSWOH-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000007704 wet chemistry method Methods 0.000 description 1
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- Inorganic Compounds Of Heavy Metals (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to anatase titania monocrystalline field, be specially one and prepare and be rich in { 001}/{ 010}/{ 101} crystal face anatase octahedrite TiO
2the method of monocrystalline.The method opens and brand-new is rich in { 001}/{ 010}/{ synthetic method of one or more crystal face anatase octahedrites of 101}, high reactivity crystal face can more simply obtained under the condition of gentleness in a large number, solve the problem of preparation difficulty, thus the anatase titania single crystal product article being rich in high reactivity crystal face can be widely used in the application of photocatalytic pollutant degradation, photolysis water hydrogen, the quick magnificent solar cell of dyestuff and photoreduction carbonic acid gas.Precursor loads in the solution containing specific reactive solute ion by the method, through 50 ~ 300 DEG C of heat treated 2h ~ 240h, the titanium dioxide single crystalline particle that above-mentioned three kinds of crystal faces that can obtain different-grain diameter distribution are dominant respectively, this product has the advantages such as surface-area is large, high reaction activity, high reaction preference, is expected extensively and to be effectively applied in the middle of various photocatalytic applications.
Description
Technical field
The present invention relates to anatase titania monocrystalline field, be specially one and be rich in { 001}/{ 010}/{ method of one or more crystal face anatase titania single crystal particles of 101} by Hydrothermal Growth, utilize the laminate structure alkali metal titanate of heterogeneity as precursor, prepare the anatase titania single crystal particle being rich in particular crystal plane of different-grain diameter.
Background technology
1972, Japanese Fujishima etc. found that titanium dioxide photoelectrode decomposable asymmetric choice net water under illumination condition produces hydrogen, and titanium dioxide and other conductor photocatalysis material are widely studied subsequently, transform to the sun power realizing based semiconductor photocatalytic process.Titanium dioxide has high stability, nontoxic, environmental friendliness, and the remarkable advantage such as cheap, not only be widely used in photocatalytic hydrogen production by water decomposition process, also be used to the fields such as photolysis pollutent, dye sensitization solar battery, photoelectrochemistry, biological chemistry and automatically cleaning, but the solar conversion efficiency of current titanium dioxide based photocatalytic material is general very low, can not meet the needs of practical application.For improving transformation efficiency, the means such as doping, finishing, morphology control, heterojunction structure compound are widely used in modifying titanium dioxide.
Light-catalyzed reaction occurs in the surface of photocatalyst, different crystal face shows different photocatalytic activities and selectivity due to surface atom arrangement difference and the difference of Electronic Structure that causes thereof, controlling the surperficial crystal face exposed of photocatalyst material is the important means changing photocatalysis performance, receive extensive concern in recent years, particularly Australian Lu in 2008 etc. achieve first and have the high-energy surface { controlled synthesis of the anatase titania monocrystalline of 001} at high proportion.Recently, three low index surface { 101}, { 001} and { the photocatalytic activity obvious difference of 010}, the satisfied { 010}>{101}>{001} of photocatalytic activity order in photolysis water hydrogen application of our research work Late Cambrian anatase titania.Meanwhile, lot of domestic and foreign research work is reached a conclusion again, and in the middle of different light-catalyzed reactions, above-mentioned three kinds of crystal faces activity and selectivity again can be different.Therefore, the anatase titania single crystal particle being rich in above-mentioned crystal face respectively according to the different properties of each crystal face, can use thus obtains optimized performance targetedly in different light-catalyzed reaction.But the titanium body hydrolysis reaction of the overwhelming majority is rapid, nucleation, process of growth are difficult to control, particularly in industrialization, batch production pattern.Therefore, develop low cost, environmental friendliness, be easy to mass-producing synthetic method significant for promoting to be rich in the photocatalysis material of titanium dioxide of different crystal face.
Summary of the invention
The object of the present invention is to provide one with insoluble titanate solid for precursor, { 001}/{ 010}/{ method of the titanium dioxide single crystalline particle of one or more crystal faces of 101} that a large amount of preparation is rich in, solve the difficult problem preparing anatase titania monocrystalline on a large scale, thus { 001}, { 010}, { 101} crystal face can be widely used in different solar energy photocatalytic fields to make highly active anatase octahedrite.
Technical scheme of the present invention is:
One is prepared and is rich in { 001}/{ 010}/{ 101} crystal face anatase octahedrite TiO
2the method of monocrystalline, first, chooses the titanate with laminate structure of heterogeneity, as the precursor of Hydrothermal Synthesis; Then, presoma is evenly spread in the solution containing specific reactive solute ion, the volumetric molar concentration of specific reactive solute ion is 0.5mM ~ 3M, and the ratio between titanate and the mass/volume containing specific reactive solute solion is 2g/20mL ~ 1g/8000mL; By it with after reactor sealing, put into the process of baking oven Hydrothermal Synthesis, Heating temperature is 50 ~ 300 DEG C, heat-up time is 2h ~ 240h, white depositions is collected after cooling, with washed with de-ionized water, centrifugal, oven dry, bake out temperature is 50 ~ 120 DEG C, obtains the anatase titania single crystal particle being rich in high reactivity crystal face; The titanium dioxide single crystalline particle obtained, size is controlled, and particle size is 20nm ~ 6 μm, and { 001}, { 010}, { one or more crystal face ratios of 101} are more than 80%; Wherein, specific reactive solute ion is hydrazine or its hydrate, fluorine-containing acid group salt or oxygen acid root, and oxygen acid root is chlorate anions, sulfate radical, nitrate radical, carbonate, phosphate radical, iodate, borate, oxalate, the Asia of above-mentioned element, secondary or high acid ion or peroxide acid group.
The selected titanate as precursor has good laminate structure, and the chemical formula of titanate is M
xti
yo
z, M=H, Li, Na, K, Rb, Cs or Fr; 0 < x, y, z≤15.
Described containing in the solution of specific reactive solute ion, the concentration of ammoniacal liquor is 0 ~ 60wt%, and the volume fraction of ethanol is 0% ~ 95%.
Described containing in the solution of specific reactive solute ion, the volumetric molar concentration of specific reactive solute ion is preferably 2mM ~ 100mM, and the concentration of ammoniacal liquor is preferably 10 ~ 30wt%, and the volume fraction of ethanol is preferably 20% ~ 40%.
In described Hydrothermal Synthesis process, Heating temperature is preferably 100 ~ 200 DEG C, and heat-up time is preferably 10h ~ 50h.
Described preparation is rich in { 001}/{ 010}/{ 101} crystal face anatase octahedrite TiO
2the method of monocrystalline, the titanium dioxide single crystalline particle size obtained is preferably 80nm ~ 1 μm.
The inventive method proposes using the titanate of insoluble as precursor, need not any morphology control agent, and { 001}/{ 010}/{ anatase octahedrite TiO of one or more crystal faces of 101} is rich in preparation
2single crystal particle, its advantage and beneficial effect are:
1, precursor used in the present invention be easy to preparation, store, with low cost.
2, the inventive method synthesis window is wide, and equipment is simple, can accomplish scale production.
3, the inventive method synthesis high reactivity crystal face gained ratio is large, and quality product is high, and product can be used widely.
4, product of the present invention has the advantages such as surface-area is large, high reaction activity, high reaction preference, is expected extensively and to be effectively applied in the middle of various photocatalytic applications.
Accompanying drawing explanation
Fig. 1. particle diameter 2 ~ 3 microns be rich in { SEM, TEM and HRTEM photo of the anatase titania monocrystalline of 010} crystal face; Wherein, (a) figure is SEM photo; B () figure is TEM photo.
Fig. 2. particle diameter is rich in { SEM, TEM and HRTEM photo of the anatase titania monocrystalline of 010} crystal face in 100 ~ 300 nanometers; Wherein, (a) figure is SEM photo; B () figure is TEM photo.
Fig. 3. particle diameter is rich in { the SEM photo of the anatase titania monocrystalline of 101} crystal face in 100-300 nanometer.
Fig. 4. particle diameter is at being rich in of 100-300 nanometer { 101} and { the SEM photo of the anatase titania monocrystalline of 010} crystal face.
Fig. 5. particle diameter is rich in { the TEM photo of the anatase titania monocrystalline of 101} crystal face in 30-50 nanometer.
Fig. 6. particle diameter is rich in { the SEM photo of the anatase titania monocrystalline of 001} crystal face in 50 nanometers.
Fig. 7. particle diameter is rich in { the TEM photo of the anatase titania monocrystalline of 101} crystal face in 200 nanometers.
Embodiment
The present invention is described in detail below in conjunction with embodiment.
Embodiment 1
By 100mg layered titanic acid sodium (Na
2ti
6o
13) put into 80mL stainless steel cauldron that 40mL deionized water is housed, that take tetrafluoroethylene as liner.After reactor sealing, put into the process of baking oven Hydrothermal Synthesis, at 160 DEG C of heat treated 24h, collect white depositions, centrifugal and 80 DEG C of oven dry, be rich in { the anatase titania monocrystalline micron bar of 010} crystal face by washed with de-ionized water, crystal face ratio is higher than 90%, the specification of micron bar is as follows: be about 3 microns, and wide about 100-200 nanometer, is shown in Fig. 1.
As can be seen from Fig. 1 a, gained sample is bar-shaped product, and size is homogeneous; Can analyze from the high-resolution-ration transmission electric-lens photo of Fig. 1 b, the radial side of this rod is { 010} crystal face.
Embodiment 2
By 50mg layered titanic acid (H
2ti
6o
13) put into the 0.6mM Cs that 40mL is housed
2cO
3the aqueous solution, in the 80mL stainless steel cauldron that take tetrafluoroethylene as liner.After reactor sealing, put into the process of baking oven Hydrothermal Synthesis, at 180 DEG C of heat treated 36h, collect white depositions, centrifugal and 80 DEG C of oven dry, be rich in { the anatase titania monocrystal nano rod of 010} crystal face by washed with de-ionized water, crystal face ratio is higher than 90%, the specification of nanometer rod is as follows: be about 500 nanometers, and wide about 20-35 nanometer, is shown in Fig. 2.
As can be seen from Fig. 2 a, gained sample is bar-shaped product, and size is homogeneous; The radial side that can analyze this rod from the high-resolution-ration transmission electric-lens photo of Fig. 2 b is { 010} crystal face.
Embodiment 3
By 100mg layered titanic acid (H
2ti
6o
13) put into the 2.5mM Na that 40mL is housed
3pO
4the aqueous solution, in the 80mL stainless steel cauldron that take tetrafluoroethylene as liner.After reactor sealing, put into the process of baking oven Hydrothermal Synthesis, at 180 DEG C of heat treated 36h, collect white depositions, centrifugal and 80 DEG C of oven dry, be rich in that { the anatase titania nanometer monocrystalline of 101} crystal face is octahedra, and crystal face ratio is more than 90% by washed with de-ionized water, the octahedral specification of nanometer is as follows: be about 400-700 nanometer, see Fig. 3.
As can be seen from Figure 3, sample topography and particle size more homogeneous, long axis direction size 400-700 nanometer, is { 101} crystal face by the known octahedral exposure of anatase titania crystal symmetry.
Embodiment 4
By 200mg layered titanic acid (H
2ti
6o
13) put into the Na that 40mL is housed
2sO
4-ammoniacal liquor-ethanol-water solution (Na
2sO
4volumetric molar concentration be 10mM, ammoniacal liquor is 20w%, and ethanol is 25vol%), in the 80mL stainless steel cauldron that take tetrafluoroethylene as liner.After reactor sealing, put into the process of baking oven Hydrothermal Synthesis, at 180 DEG C of heat treated 20h, collect white depositions, centrifugal and 80 DEG C of oven dry, be rich in { 101} and { nanometer that the anatase titania monocrystalline of 010} crystal face elongates is octahedra, and { 101}, { 010} crystal face ratio is about 70% and 30% respectively by washed with de-ionized water, the octahedral specification of nanometer is as follows: be about 200-400 nanometer, see Fig. 4.
As can be seen from Figure 4, sample topography and particle size more homogeneous, long axis direction size 200-400 nanometer is { 101} and { 010} crystal face by the exposure of the known monocrystalline of anatase titania crystal symmetry.
Embodiment 5
By 500mg layered titanic acid (H
2ti
6o
13) put into the 20mM N that 40mL is housed
2h
4the aqueous solution, in the 80mL stainless steel cauldron that take tetrafluoroethylene as liner.After reactor sealing, put into the process of baking oven Hydrothermal Synthesis, at 180 DEG C of heat treated 20h, collect white depositions, centrifugal and 80 DEG C of oven dry, be rich in that { the anatase titania monocrystalline of 101} crystal face is octahedra, and { 101} crystal face ratio is about 90% by washed with de-ionized water, the octahedral specification of nanometer is as follows: be about 30-50 nanometer, see Fig. 5.
As can be seen from Figure 5, sample topography and particle size more homogeneous, long axis direction size 30-50 nanometer is { 101} crystal face by the exposure of the known monocrystalline of anatase titania crystal symmetry.
Embodiment 6
By 500mg layered titanic acid (H
2ti
6o
13) put into 80mL stainless steel cauldron that the 30mM HF aqueous solution of 40mL is housed, that take tetrafluoroethylene as liner.After reactor sealing, put into the process of baking oven Hydrothermal Synthesis, at 180 DEG C of heat treated 20h, collect white depositions, centrifugal and 80 DEG C of oven dry, be rich in { the anatase titania single crystal nanoplate of 001} crystal face by washed with de-ionized water, { 001} crystal face ratio is about 90%, the nanometer sheet length of side is about 30-50 nanometer, and thickness is less than 20nm, sees Fig. 6.
As can be seen from Figure 6, sample become square flake, the length of side is about 30-50nm, and thickness is less than 20nm.Its main exposure is { 001} crystal face.
Embodiment 7
By 500mg layered titanic acid (H
2ti
6o
13) put into the 5mM H that 40mL is housed
2o
2with the 10mM HCl aqueous solution, in the 80mL stainless steel cauldron that take tetrafluoroethylene as liner.After reactor sealing, put into the process of baking oven Hydrothermal Synthesis, at 180 DEG C of heat treated 20h, collect white depositions, centrifugal and 80 DEG C of oven dry, be rich in that { nanometer that the anatase titania monocrystalline of 101} crystal face elongates is octahedra, and { 101} crystal face ratio is about 95% by washed with de-ionized water, particle diameter about 200 nanometer, is shown in Fig. 7.
As can be seen from Figure 7, sample become square flake, the length of side is about 30-50nm, and thickness is less than 20nm.Its main exposure is { 101} crystal face.
Result shows, the present invention makes layered titanate decompose in the solution by Hydrothermal Synthesis wet-chemical process, again forming core, be grown to serve as { 001}/{ 010}/{ anatase titania single crystal particle that one or more crystal faces of 101} are dominant.The method opens and brand-new is rich in { 001}/{ 010}/{ synthetic method of one or more crystal face anatase octahedrites of 101}, { 001}/{ 010}/{ one or more crystal faces of 101} can obtain in a large number under more simple condition to make high reactivity, solve the problem of preparation difficulty, thus can { 001}/{ 010}/{ the anatase titania single crystal product article of one or more crystal faces of 101} is widely used in the application of photocatalytic pollutant degradation, photolysis water hydrogen, the quick magnificent solar cell of dyestuff and photoreduction carbonic acid gas by being rich in high reactivity.Precursor loads in the reactor containing oxygen acid root solution by the method, through 50 ~ 300 DEG C of heat treated 2h ~ 240h, can obtain { 001}/{ 010}/{ the titanium dioxide single crystalline particle that one or more crystal faces of 101} are dominant of different-grain diameter distribution.Particle size is 50nm ~ 6 μm, and { 001}/{ 010}/{ one or more crystal face ratios of 101} are more than 80%.It is large that this product has surface-area, and reactive behavior advantages of higher, is expected extensively and to be effectively applied in the middle of various photocatalytic applications.
Claims (3)
1. prepare and be rich in { 001} crystal face anatase octahedrite TiO for one kind
2the method of monocrystalline, is characterized in that: first, chooses the metatitanic acid H with laminate structure
2ti
6o
13, as the precursor of Hydrothermal Synthesis; Then, evenly spread to by presoma in the HF aqueous solution, the volumetric molar concentration of the HF aqueous solution is 0.5mM ~ 3M, and the ratio between the mass/volume of metatitanic acid and the HF aqueous solution is 2g/20mL ~ 1g/8000mL; By it with after reactor sealing, put into the process of baking oven Hydrothermal Synthesis, Heating temperature is 50 ~ 300 DEG C, heat-up time is 2h ~ 240h, white depositions is collected after cooling, with washed with de-ionized water, centrifugal, oven dry, bake out temperature is 50 ~ 120 DEG C, obtains the anatase titania single crystal particle being rich in high reactivity crystal face; The titanium dioxide single crystalline particle obtained, size is controlled, and particle size is 20nm ~ 6 μm, and { 001} crystal face ratio is more than 80%.
2. be rich in { 001} crystal face anatase octahedrite TiO according to preparation according to claim 1
2the method of monocrystalline, is characterized in that: in described Hydrothermal Synthesis process, and Heating temperature is 100 ~ 200 DEG C, and heat-up time is 10h ~ 50h.
3. be rich in { 001} crystal face anatase octahedrite TiO according to preparation according to claim 1
2the method of monocrystalline, is characterized in that: the titanium dioxide single crystalline particle size obtained is 80nm ~ 1 μm.
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| CN103626225B (en) * | 2013-10-25 | 2015-08-26 | 河南大学 | A kind of expose that { 001} face anatase titania is nanocrystalline and preparation method thereof containing constraint single electron Lacking oxygen |
| CN104192900B (en) * | 2014-08-20 | 2016-05-11 | 北京师范大学 | A kind of TiO2Nanocrystalline synthetic method |
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