CN108946800A - A kind of titanium dioxide and its preparation method and application of crystal face exposure - Google Patents
A kind of titanium dioxide and its preparation method and application of crystal face exposure Download PDFInfo
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- CN108946800A CN108946800A CN201810862501.9A CN201810862501A CN108946800A CN 108946800 A CN108946800 A CN 108946800A CN 201810862501 A CN201810862501 A CN 201810862501A CN 108946800 A CN108946800 A CN 108946800A
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 146
- 239000013078 crystal Substances 0.000 title claims abstract description 106
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 68
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 37
- 239000007788 liquid Substances 0.000 claims abstract description 35
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 33
- 239000013067 intermediate product Substances 0.000 claims abstract description 27
- 239000007787 solid Substances 0.000 claims abstract description 26
- 230000003197 catalytic effect Effects 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000000926 separation method Methods 0.000 claims abstract description 23
- 230000003647 oxidation Effects 0.000 claims abstract description 19
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 19
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000012670 alkaline solution Substances 0.000 claims abstract description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 40
- 239000000243 solution Substances 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 32
- 238000001914 filtration Methods 0.000 claims description 14
- 230000035484 reaction time Effects 0.000 claims description 14
- 238000005119 centrifugation Methods 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000012808 vapor phase Substances 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 16
- 239000002994 raw material Substances 0.000 abstract description 7
- 238000002156 mixing Methods 0.000 abstract description 5
- 230000002349 favourable effect Effects 0.000 abstract description 4
- 235000010215 titanium dioxide Nutrition 0.000 description 51
- 238000006243 chemical reaction Methods 0.000 description 28
- 230000000694 effects Effects 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 9
- 229910010413 TiO 2 Inorganic materials 0.000 description 8
- 238000006555 catalytic reaction Methods 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 6
- 238000010998 test method Methods 0.000 description 6
- 229910052719 titanium Inorganic materials 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 4
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 230000001699 photocatalysis Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 241000790917 Dioxys <bee> Species 0.000 description 2
- 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 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- 230000037237 body shape Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8634—Ammonia
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B01J35/39—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/80—Type of catalytic reaction
- B01D2255/802—Photocatalytic
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/41—Particle morphology extending in three dimensions octahedron-like
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
Abstract
The present invention provides a kind of titanium dioxide and its preparation method and application of crystal face exposure.The preparation method comprises the following steps: (1) mixing Nano titanium dioxide with alkaline solution, carry out first time hydro-thermal reaction, be separated by solid-liquid separation, obtained solid is intermediate product；(2) step (1) described intermediate product is mixed with water, carries out second of hydro-thermal reaction, be separated by solid-liquid separation, obtained solid is the titanium dioxide of crystal face exposure.The crystal face of the titanium dioxide exposure of the crystal face exposure includes { 101 } crystal face and/or { 010 } crystal face.The titanium dioxide of the crystal face exposure is used for photochemical catalytic oxidation ammonia.Preparation method of the invention can efficiently control based on which kind of crystal face of product exposure, and favorable repeatability, and raw material is simple, cheap.The ammonia catalytic activity of the titanium dioxide of crystal face exposure provided by the invention is excellent.
Description
Technical field
The invention belongs to photocatalysis technology fields, and in particular to titanium dioxide of a kind of crystal face exposure and preparation method thereof and
Purposes.
Background technique
Ammonia (NH3) it is the important presoma that gray haze is formed in one of indoor typical pollutant and atmospheric environment, it is right
Human health, which has, to be seriously endangered.Photocatalysis technology is a kind of pollutant process technology novel at present, Anatase titanium dioxide
Titanium (TiO2) it is the photochemical catalyst that photocatalysis field is most widely used, crystal face engineering research is also the most deep.
CN106082321A disclose a kind of anatase titanium dioxide nano material for exposing controllable high activity crystal face and its
Preparation method and application.The program the following steps are included: (1) in molar ratio example be 1~10:5 weigh water and ammonium fluoride, be configured to
Solution A；(2) titanium tetrachloride solution is added into solution A, stirs, obtained solution B；(3) by solution B in 170-210 DEG C, reaction
It is cooled to room temperature after 8-24h；(4) supernatant for the reaction solution that step (3) obtains is outwelled, remaining solidliquid mixture is carried out
Centrifuge washing obtains sediment；(5) above-mentioned sediment is successively washed several times with dehydrated alcohol and deionized water；It (6) will step
Suddenly the anatase titanium dioxide nano material of the controllable high activity crystal face of exposure is made in the drying precipitate after the washing that (5) obtain.
But program process is cumbersome, and it is complicated for operation, it is not suitable for industrialization production.
CN103014829A discloses a kind of prepare rich in { 001 }/{ 010 }/{ 101 } crystal face anatase TiO2The side of monocrystalline
Method, this method choose the titanate with layer structure of heterogeneity, the precursor as hydrothermal synthesis first；Then, will
Presoma is evenly spread in the solution containing specific reactive solute ion, and the molar concentration of specific reactive solute ion is 0.5mM
Ratio between~3M, titanate and mass/volume containing specific reactive solute solion is 2g/20mL~1g/8000mL；
After it is sealed with reaction kettle, be put into baking oven hydrothermal synthesis processing, heating temperature be 50~300 DEG C, heating time be 2h~
240h collects white depositions after cooling, is cleaned, be centrifuged, dried with deionized water, and drying temperature is 50~120 DEG C, obtains richness
The anatase titania single crystal grain of the crystal face containing high activity.But program raw material is complicated, higher cost is not suitable for industry
Metaplasia produces.
Therefore, a kind of favorable repeatability is developed, the raw material used is simple, the cheap titanium dioxide for preparing crystal face exposure
The method of titanium has this field important meaning.
Summary of the invention
Aiming at the above shortcomings existing in the prior art, the purpose of the present invention is to provide a kind of titanium dioxides of crystal face exposure
Titanium and its preparation method and application.Preparation method favorable repeatability provided by the invention, the raw material used is simple, cheap,
Product obtained has ammonia catalytic activity well.
In order to achieve the above object, the invention adopts the following technical scheme:
In a first aspect, the present invention provides a kind of preparation method of the titanium dioxide of crystal face exposure, the method includes following
Step:
(1) Nano titanium dioxide is mixed with alkaline solution, carries out first time hydro-thermal reaction, be separated by solid-liquid separation, obtain
Solid is intermediate product；
(2) step (1) described intermediate product is mixed with water, carries out second of hydro-thermal reaction, be separated by solid-liquid separation, what is obtained consolidates
Body is the titanium dioxide of crystal face exposure.
In preparation method provided by the invention, step (1) described Nano titanium dioxide does not expose any crystal face.
Preparation method provided by the invention realizes having for the exposure crystal face to titanium dioxide by hydro-thermal reaction twice
Effect control.Wherein first time hydro-thermal reaction carries out under alkaline condition, (such as tubulose, rodlike with certain pattern to be formed
Or it is octahedronlike) intermediate product, and second of hydro-thermal reaction uses water as solvent, to crystallize the dioxy to form crystal face exposure
Change titanium, and controls based on which kind of crystal face of exposure.The raw material that preparation method provided by the invention uses is simple and easy to get, and process
It is short, the exposure crystal face of final products can be controlled well.
It is used as currently preferred technical solution below, but not as the limitation to technical solution provided by the invention, leads to
Following preferred technical solution is crossed, can preferably reach and realize technical purpose and beneficial effect of the invention.
As currently preferred technical solution, in step (1), the Nano titanium dioxide is fumed nano grade two
Titanium oxide.For example, the fumed nano grade dioxy of German goldschmidt chemical corporation production can be used in method provided by the invention
Change titanium P25.
Preferably, the average grain diameter of the Nano titanium dioxide be 15nm-30nm, such as 15nm, 16nm, 17nm,
18nm, 19nm, 20nm, 21nm, 22nm, 23nm, 24nm, 25nm, 26nm, 27nm, 28nm, 29nm or 30nm etc., but simultaneously not only
It is limited to cited numerical value, other unlisted numerical value are equally applicable in the numberical range, preferably 25nm.
As currently preferred technical solution, in step (1), the alkaline solution include sodium hydroxide solution and/or
Potassium hydroxide, preferably sodium hydroxide solution.
Preferably, in step (1), in the alkaline solution, concentration hydroxy is 7mol/L-13mol/L, such as
7mol/L, 8mol/L, 9mol/L, 10mol/L, 11mol/L, 12mol/L or 13mol/L etc., it is not limited to cited
Numerical value, other interior unlisted numerical value of the numberical range are equally applicable, preferably 10mol/L.In the present invention, 7mol/L- is used
It is intermediate product octahedronlike and/or rodlike that the hydroxyl concentration of 13mol/L, which is more advantageous to and to form pattern, and 10mol/L
Hydroxyl concentration effect is best.
Preferably, in step (1), the solid-to-liquid ratio of the volume of the quality and alkaline solution of the Nano titanium dioxide is
14.2g/L-28.4g/L, such as 14.2g/L, 15g/L, 18g/L, 20g/L, 22g/L, 24g/L, 26g/L or 28.4g/L etc., but
It is not limited in cited numerical value, other unlisted numerical value are equally applicable in the numberical range.
As currently preferred technical solution, in step (1), the temperature of the first time hydro-thermal reaction is 140 DEG C-
200 DEG C, such as 140 DEG C, 150 DEG C, 160 DEG C, 170 DEG C, 175 DEG C, 180 DEG C, 185 DEG C, 190 DEG C, 195 DEG C or 200 DEG C etc., but simultaneously
It is not limited only to cited numerical value, other unlisted numerical value are equally applicable in the numberical range, and preferably 190 DEG C.
Preferably, in step (1), time of the first time hydro-thermal reaction is 12h-30h, for example, 12h, 13h, 14h,
15h, 16h, 17h, 18h, 19h, 20h, 21h, 22h, 23h, for 24 hours, 25h, 26h, 27h, 28h, 29h or 30h etc., but simultaneously not only limit
It is equally applicable in other unlisted numerical value in cited numerical value, the numberical range, preferably for 24 hours.
Preferably, in step (1), it is described be separated by solid-liquid separation for filtering and/or centrifugation, the present invention in, it is described filtering and/or from
The heart, which refers to, to be filtering, or centrifugation can also be the combination of filtering and centrifugation.
Preferably, in step (1), further includes: the solid obtained to separation of solid and liquid is washed and dried.
As currently preferred technical solution, in step (2), the quality of step (1) described intermediate product and the body of water
Long-pending solid-to-liquid ratio is 0.7g/L-1.4g/L, such as 0.7g/L, 0.9g/L, 1.1g/L, 1.3g/L or 1.4g/L etc., but simultaneously not only
It is limited to cited numerical value, other unlisted numerical value are equally applicable in the numberical range.
Preferably, in step (2), the temperature of second of hydro-thermal reaction is 150 DEG C -220 DEG C, such as 150 DEG C, 160
DEG C, 170 DEG C, 180 DEG C, 190 DEG C, 200 DEG C, 210 DEG C or 220 DEG C etc., it is not limited to cited numerical value, the numberical range
Other interior unlisted numerical value are equally applicable, and preferably 170 DEG C -200 DEG C, further preferably 170 DEG C or 200 DEG C.When second
When the temperature of secondary hydro-thermal reaction is 170 DEG C, the crystal face of obtained product exposure is based on { 101 } crystal face, when second of hydro-thermal is anti-
When the temperature answered is 200 DEG C, the crystal face of obtained product exposure is based on { 010 } crystal face.
Preferably, in step (2), time of second of hydro-thermal reaction is 18h-30h, for example, 18h, 19h, 20h,
21h, 22h, 23h, for 24 hours, 25h, 26h, 27h, 28h, 29h or 30h etc., it is not limited to cited numerical value, the numerical value model
Other unlisted numerical value are equally applicable in enclosing, preferably for 24 hours；
Preferably, in step (2), it is described be separated by solid-liquid separation for filtering and/or centrifugation, the present invention in, it is described filtering and/or from
The heart, which refers to, to be filtering, or centrifugation can also be the combination of filtering and centrifugation.
Preferably, in step (2), further includes: the solid obtained to separation of solid and liquid is washed and dried.
As currently preferred technical solution, step (1) the first time hydro-thermal reaction and step (2) are described for the second time
Hydro-thermal reaction carries out in hydrothermal reactor.
Preferably, the hydrothermal reactor contains polytetrafluoroethylliner liner.
As the further preferred technical solution of the method for the invention, the described method comprises the following steps:
(1) the fumed nano grade titanium dioxide that average grain diameter is 25nm is mixed with 10mol/L sodium hydroxide solution, is set
In the hydrothermal reactor containing polytetrafluoroethylliner liner, at 190 DEG C carry out first time hydro-thermal reaction, the reaction time be for 24 hours,
It is separated by solid-liquid separation, obtained solid is washed and dried, intermediate product is obtained；
Wherein, the solid-to-liquid ratio of the volume of the quality and sodium hydroxide solution of the fumed nano grade titanium dioxide is
14.2g/L-28.4g/L；
(2) step (1) described intermediate product is mixed with water, is placed in the hydrothermal reactor containing polytetrafluoroethylliner liner
In, second of hydro-thermal reaction is carried out at 170 DEG C or 200 DEG C, the reaction time is for 24 hours, to be separated by solid-liquid separation, and is carried out to obtained solid
Washing and drying, obtain the titanium dioxide of crystal face exposure；
Wherein, the solid-to-liquid ratio of the volume of the quality and water of step (1) described intermediate product is 0.7g/L-1.4g/L.
Second aspect, the present invention provide a kind of titanium dioxide of the crystal face exposure of preparation of method as described in relation to the first aspect, institute
The crystal face for stating the titanium dioxide exposure of crystal face exposure includes { 101 } crystal face and/or { 010 } crystal face.It is described { 101 } in the present invention
Crystal face and/or { 010 } crystal face refer to that exposed crystal face can be { 101 } crystal face, are also possible to { 010 } crystal face, can also be
{ 101 } combination of crystal face and { 010 } crystal face.
In the crystal face of the titanium dioxide exposure of crystal face of the present invention exposure, the ratio of { 101 } crystal face up to 90.2%,
{ 010 } ratio of crystal face is up to 83.3%.
As currently preferred technical solution, the pattern of the titanium dioxide of crystal face exposure be it is octahedronlike and/or
It is rodlike.It is described octahedronlike and/or rodlike refer to can be octahedronlike in the present invention, or it is rodlike, it can also be eight
Face body shape and rodlike combination.
Preferably, the specific surface area of the titanium dioxide of the crystal face exposure is 20m2/g-40m2/g。
The third aspect, the present invention provide a kind of purposes of the titanium dioxide of exposure of the crystal face as described in second aspect, the crystalline substance
The titanium dioxide of face exposure is used for photochemical catalytic oxidation ammonia.The titanium dioxide of crystal face exposure provided by the invention is urged as a kind of light
Agent has the effect of excellent removal ammonia.
Compared with the prior art, the invention has the following beneficial effects:
(1) preparation method provided by the invention by the first time hydro-thermal reaction that is carried out in alkaline solution and in water into
Second capable of hydro-thermal reaction can efficiently control based on which kind of crystal face of product exposure, and method provided by the invention can
Reproducible, raw material is simple, cheap；
(2) the ammonia catalytic activity of the titanium dioxide of crystal face exposure provided by the invention is excellent, after light-catalyzed reaction 2h
Ammonia conversion ratio is up to 70%, and the fitting reaction rate constant of catalysis oxidation ammonia is up to 0.004.
Detailed description of the invention
Nothing under the titanium dioxide for the crystal face exposure that Fig. 1 is the embodiment of the present invention 1, embodiment 2 obtains and same test condition
The photochemical catalytic oxidation ammonia activity figure of catalyst control experiment；
Fig. 2 is that the optically catalytic TiO 2 for the crystal face exposure that Example 1 and Example 2 of the present invention obtains aoxidizes the quasi- of ammonia
Close reaction rate constant figure.
Specific embodiment
In order to better illustrate the present invention, it is easy to understand technical solution of the present invention, below further specifically to the present invention
It is bright.But following embodiments is only simple example of the invention, does not represent or limit the scope of the present invention, this
Invention protection scope is subject to claims.
The following are typical but non-limiting embodiments of the invention:
Embodiment 1
The present embodiment provides a kind of crystal face exposure titanium dioxide preparation method, method particularly includes:
(1) hydroxide for being 10mol/L by fumed nano grade titanium dioxide P25 (average grain diameter 25nm) and 70mL concentration
Sodium solution mixing, is placed in the 100mL hydrothermal reactor containing polytetrafluoroethylliner liner, and first time hydro-thermal is carried out at 190 DEG C
Reaction, reaction time are that for 24 hours, centrifuge separation is washed and dried to obtained solid, obtains intermediate product；
Wherein, the solid-to-liquid ratio of the volume of the quality and sodium hydroxide solution of the fumed nano grade titanium dioxide P25 is
14.2g/L；
(2) step (1) described intermediate product is mixed with water, is placed in the hydrothermal reactor containing polytetrafluoroethylliner liner
In, carry out second of hydro-thermal reaction at 170 DEG C, the reaction time is centrifuge separation for 24 hours, to obtained solid carry out washing and
It is dry, obtain the titanium dioxide of crystal face exposure；
Wherein, the solid-to-liquid ratio of the volume of the quality and water of step (1) described intermediate product is 0.7g/L.
The titanium dioxide for the crystal face exposure that the present embodiment is prepared is that nanoscale is octahedronlike, specific surface area 41m2/
G, exposed crystal face are mainly { 101 } crystal face, which is 90.2%.
The active test method of photochemical catalytic oxidation ammonia of the titanium dioxide for the crystal face exposure that the present embodiment obtains is as follows: taking
The titanium dioxide 100mg for the crystal face exposure being prepared is dispersed to ultrasound in water, drops in the disk that diameter is 8cm, naturally dry
It is dry that film is made, it is put into catalyst activity evaluating apparatus, activity rating carries out in homemade reactor.Simulated atmosphere group becomes
(500ppm NH3, 20%O2, N2For Balance Air, flow 100mL/min.) atmosphere is circulated through catalyst surface.
Ammonia conversion ratio is 70% after the optically catalytic TiO 2 reaction 2h for the crystal face exposure that the present embodiment is prepared,
The fitting reaction rate constant of catalysis oxidation ammonia is 0.004.
Embodiment 2
The present embodiment provides a kind of crystal face exposure titanium dioxide preparation method, method particularly includes:
(1) hydroxide for being 10mol/L by fumed nano grade titanium dioxide P25 (average grain diameter 25nm) and 70mL concentration
Sodium solution mixing, is placed in the 100mL hydrothermal reactor containing polytetrafluoroethylliner liner, and first time hydro-thermal is carried out at 190 DEG C
Reaction, reaction time are that for 24 hours, centrifuge separation is washed and dried to obtained solid, obtains intermediate product；
Wherein, the solid-to-liquid ratio of the volume of the quality and sodium hydroxide solution of the fumed nano grade titanium dioxide P25 is
14.2g/L；
(2) step (1) described intermediate product is mixed with water, is placed in the hydrothermal reactor containing polytetrafluoroethylliner liner
In, carry out second of hydro-thermal reaction at 200 DEG C, the reaction time is centrifuge separation for 24 hours, to obtained solid carry out washing and
It is dry, obtain the titanium dioxide of crystal face exposure；
Wherein, the solid-to-liquid ratio of the volume of the quality and water of step (1) described intermediate product is 0.7g/L.
The titanium dioxide for the crystal face exposure that the present embodiment is prepared is that nanoscale is rodlike, specific surface area 27m2/ g, cruelly
The crystal face of dew is mainly { 010 } crystal face, which is 83.3%.
The active test method of photochemical catalytic oxidation ammonia and implementation of the titanium dioxide for the crystal face exposure that the present embodiment obtains
Example 1 is identical.
Ammonia conversion ratio is 20% after the optically catalytic TiO 2 reaction 2h for the crystal face exposure that the present embodiment is prepared,
The fitting reaction rate constant of catalysis oxidation ammonia is 0.001.
The titanium dioxide of crystal face exposure and the light without catalyst control experiment that Fig. 1 is embodiment 1, embodiment 2 obtains are urged
Change oxidation ammonia activity figure, wherein the product test item of the test condition without catalyst control experiment and embodiment 1 and embodiment 2
Part is identical, and difference is that no catalyst control experiment does not use any catalyst.When can be seen that no catalyst by the figure without
Photochemical catalytic oxidation NH3The activity of activity, 1 product of embodiment is substantially better than the activity of 2 product of embodiment.
Fig. 2 is that the optically catalytic TiO 2 for the crystal face exposure that embodiment 1 and embodiment 2 obtain aoxidizes the fitting reaction of ammonia
Rate constant figure can be seen that the reaction rate constant of 1 product of embodiment is 4 times of 2 product of embodiment by the figure.
Embodiment 3
The present embodiment provides a kind of crystal face exposure titanium dioxide preparation method, method particularly includes:
(1) fumed nano grade titanium dioxide (average grain diameter 15nm) is molten for the sodium hydroxide of 7mol/L with 70mL concentration
Liquid mixing, is placed in the 100mL hydrothermal reactor containing polytetrafluoroethylliner liner, and first time hydro-thermal reaction is carried out at 140 DEG C,
Reaction time is 30h, is separated by filtration, and obtained solid is washed and dried, intermediate product is obtained；
Wherein, the solid-to-liquid ratio of the volume of the quality and sodium hydroxide solution of the fumed nano grade titanium dioxide is
20.0g/L；
(2) step (1) described intermediate product is mixed with water, is placed in the hydrothermal reactor containing polytetrafluoroethylliner liner
In, second of hydro-thermal reaction is carried out at 150 DEG C, reaction time 30h is separated by filtration, to obtained solid carry out washing and
It is dry, obtain the titanium dioxide of crystal face exposure；
Wherein, the solid-to-liquid ratio of the volume of the quality and water of step (1) described intermediate product is 1.4g/L.
The titanium dioxide for the crystal face exposure that the present embodiment is prepared is that nanoscale is octahedronlike, specific surface area 37m2/
G, exposed crystal face are mainly { 101 } crystal face, which is 83.2%
The active test method of photochemical catalytic oxidation ammonia and implementation of the titanium dioxide for the crystal face exposure that the present embodiment obtains
Example 1 is identical.
Ammonia conversion ratio is 66% after the optically catalytic TiO 2 reaction 2h for the crystal face exposure that the present embodiment is prepared,
The fitting reaction rate constant of catalysis oxidation ammonia is 0.003.
Embodiment 4
The present embodiment provides a kind of crystal face exposure titanium dioxide preparation method, method particularly includes:
(1) sodium hydroxide for being 13mol/L by fumed nano grade titanium dioxide (average grain diameter 30nm) and 70mL concentration
Solution mixing, is placed in the 100mL hydrothermal reactor containing polytetrafluoroethylliner liner, and it is anti-that first time hydro-thermal is carried out at 200 DEG C
It answers, reaction time 12h is separated by filtration, and obtained solid is washed and dried, intermediate product is obtained；
Wherein, the solid-to-liquid ratio of the volume of the quality and sodium hydroxide solution of the fumed nano grade titanium dioxide is
28.4g/L；
(2) step (1) described intermediate product is mixed with water, is placed in the hydrothermal reactor containing polytetrafluoroethylliner liner
In, second of hydro-thermal reaction is carried out at 220 DEG C, reaction time 18h is separated by filtration, to obtained solid carry out washing and
It is dry, obtain the titanium dioxide of crystal face exposure；
Wherein, the solid-to-liquid ratio of the volume of the quality and water of step (1) described intermediate product is 1.0g/L.
The titanium dioxide for the crystal face exposure that the present embodiment is prepared is that nanoscale is rodlike, specific surface area 28m2/ g, cruelly
The crystal face of dew is mainly { 010 } crystal face, which is 81.7%.
The active test method of photochemical catalytic oxidation ammonia and implementation of the titanium dioxide for the crystal face exposure that the present embodiment obtains
Example 1 is identical.
Ammonia conversion ratio is 18% after the optically catalytic TiO 2 reaction 2h for the crystal face exposure that the present embodiment is prepared,
The fitting reaction rate constant of catalysis oxidation ammonia is 0.0009.
Comparative example 1
Referring to embodiment 1, difference is the specific steps of this comparative example, and in step (1), the hydro-thermal reaction time is 48 small
When, the operation without step (2).
The product that this comparative example is prepared does not expose crystal face.
The active test method of photochemical catalytic oxidation ammonia and implementation of the titanium dioxide for the crystal face exposure that this comparative example obtains
Example 1 is identical.
Ammonia conversion ratio is 3% after the optically catalytic TiO 2 reaction 2h that the present embodiment is prepared, catalytic oxidation ammonia
The fitting reaction rate constant of gas is 0.0005.
Comparative example 2
Referring to embodiment 1, difference is the specific steps of this comparative example, anti-without the first time hydro-thermal in step (1)
It answers, fumed nano grade titanium dioxide P25 (average grain diameter 25nm) is mixed with water directly, hydro-thermal reaction is carried out at 170 DEG C,
Reaction time is 48h, and centrifuge separation is washed and dried to obtained solid, obtains product.
The product that this comparative example is prepared does not expose crystal face.
The active test method of photochemical catalytic oxidation ammonia and implementation of the titanium dioxide for the crystal face exposure that this comparative example obtains
Example 1 is identical.
Ammonia conversion ratio is 1% after the optically catalytic TiO 2 reaction 2h that the present embodiment is prepared, catalytic oxidation ammonia
The fitting reaction rate constant of gas is 0.0001.
Based on the above embodiments with comparative example it is found that the ammonia catalysis of the titanium dioxide of crystal face provided in this embodiment exposure
Good activity, preparation method can efficiently control based on which kind of crystal face of product exposure, and favorable repeatability, raw material is simple, price
It is cheap.Comparative example does not use the solution of the present invention, thus can not obtain effect of the invention.
The Applicant declares that the present invention is explained by the above embodiments detailed process equipment and process flow of the invention,
But the present invention is not limited to the above detailed process equipment and process flow, that is, it is above-mentioned detailed not mean that the present invention must rely on
Process equipment and process flow could be implemented.It should be clear to those skilled in the art, any improvement in the present invention,
Addition, selection of concrete mode of equivalence replacement and auxiliary element to each raw material of product of the present invention etc., all fall within of the invention
Within protection scope and the open scope.
Claims (10)
1. a kind of preparation method of the titanium dioxide of crystal face exposure, which is characterized in that the described method comprises the following steps:
(1) Nano titanium dioxide is mixed with alkaline solution, carries out first time hydro-thermal reaction, be separated by solid-liquid separation, obtained solid
For intermediate product；
(2) step (1) described intermediate product is mixed with water, carries out second of hydro-thermal reaction, be separated by solid-liquid separation, obtained solid is
The titanium dioxide of the crystal face exposure.
2. the method according to claim 1, wherein the Nano titanium dioxide is vapor phase method in step (1)
Nano titanium dioxide；
Preferably, the average grain diameter of the Nano titanium dioxide is 15nm-30nm, preferably 25nm.
3. method according to claim 1 or 2, which is characterized in that in step (1), the alkaline solution includes hydroxide
Sodium solution and/or potassium hydroxide, preferably sodium hydroxide solution；
Preferably, in step (1), in the alkaline solution, concentration hydroxy is 7mol/L-13mol/L, preferably 10mol/
L；
Preferably, in step (1), the solid-to-liquid ratio of the volume of the quality and alkaline solution of the Nano titanium dioxide is 14.2g/
L-28.4g/L。
4. method according to claim 1-3, which is characterized in that in step (1), the first time hydro-thermal reaction
Temperature be 140 DEG C -200 DEG C, preferably 190 DEG C；
Preferably, in step (1), the time of the first time hydro-thermal reaction is 12h-30h, preferably for 24 hours；
Preferably, described to be separated by solid-liquid separation as filtering and/or centrifugation in step (1)；
Preferably, in step (1), further includes: the solid obtained to separation of solid and liquid is washed and dried.
5. method according to claim 1-4, which is characterized in that in step (2), step (1) the intermediate production
The solid-to-liquid ratio of the volume of the quality and water of object is 0.7g/L-1.4g/L；
Preferably, in step (2), the temperature of second of hydro-thermal reaction is 150 DEG C -220 DEG C, preferably 170 DEG C -200 DEG C,
Further preferably 170 DEG C or 200 DEG C；
Preferably, in step (2), the time of second of hydro-thermal reaction is 18h-30h, preferably for 24 hours；
Preferably, described to be separated by solid-liquid separation as filtering and/or centrifugation in step (2)；
Preferably, in step (2), further includes: the solid obtained to separation of solid and liquid is washed and dried.
6. method according to claim 1-5, which is characterized in that step (1) the first time hydro-thermal reaction and
Step (2) second of hydro-thermal reaction carries out in hydrothermal reactor；
Preferably, the hydrothermal reactor contains polytetrafluoroethylliner liner.
7. method according to claim 1-6, which is characterized in that the described method comprises the following steps:
(1) the fumed nano grade titanium dioxide that average grain diameter is 25nm is mixed with 10mol/L sodium hydroxide solution, is placed in and contains
Have in the hydrothermal reactor of polytetrafluoroethylliner liner, first time hydro-thermal reaction is carried out at 190 DEG C, the reaction time is solid-liquid for 24 hours
Separation, is washed and is dried to obtained solid, obtain intermediate product；
Wherein, the solid-to-liquid ratio of the volume of the quality and sodium hydroxide solution of the fumed nano grade titanium dioxide is 14.2g/L-
28.4g/L；
(2) step (1) described intermediate product is mixed with water, is placed in the hydrothermal reactor containing polytetrafluoroethylliner liner,
Second of hydro-thermal reaction is carried out at 170 DEG C or 200 DEG C, the reaction time is for 24 hours, to be separated by solid-liquid separation, wash to obtained solid
And drying, obtain the titanium dioxide of crystal face exposure；
Wherein, the solid-to-liquid ratio of the volume of the quality and water of step (1) described intermediate product is 0.7g/L-1.4g/L.
8. the titanium dioxide of the crystal face exposure of method preparation according to claim 1-7, which is characterized in that described
The crystal face of the titanium dioxide exposure of crystal face exposure includes { 101 } crystal face and/or { 010 } crystal face.
9. the titanium dioxide of crystal face exposure according to claim 8, which is characterized in that the titanium dioxide of the crystal face exposure
Pattern be it is octahedronlike and/or rodlike；
Preferably, the specific surface area of the titanium dioxide of the crystal face exposure is 20m2/g-40m2/g。
10. the purposes of the titanium dioxide of crystal face exposure according to claim 8 or claim 9, which is characterized in that the crystal face exposure
Titanium dioxide be used for photochemical catalytic oxidation ammonia.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110227433A (en) * | 2019-06-26 | 2019-09-13 | 浙江大学 | A kind of Detitanium-ore-type TiO2The preparation method of crystal face hetero-junctions |
| CN111850653A (en) * | 2020-06-23 | 2020-10-30 | 清华大学 | Method and system for preparing titanium dioxide with exposed high-activity surface by using femtosecond laser |
-
2018
- 2018-08-01 CN CN201810862501.9A patent/CN108946800A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110227433A (en) * | 2019-06-26 | 2019-09-13 | 浙江大学 | A kind of Detitanium-ore-type TiO2The preparation method of crystal face hetero-junctions |
| CN110227433B (en) * | 2019-06-26 | 2020-10-23 | 浙江大学 | Anatase type TiO2Preparation method of crystal face heterojunction |
| CN111850653A (en) * | 2020-06-23 | 2020-10-30 | 清华大学 | Method and system for preparing titanium dioxide with exposed high-activity surface by using femtosecond laser |
| WO2021258523A1 (en) * | 2020-06-23 | 2021-12-30 | 清华大学 | Method and system for preparing titanium dioxide having exposed high-activity surface by using femtosecond laser |
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