CN106925258A - A kind of new Mo-Ti monocrystalline oxides nano material and its preparation and application - Google Patents
A kind of new Mo-Ti monocrystalline oxides nano material and its preparation and application Download PDFInfo
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- CN106925258A CN106925258A CN201511025505.4A CN201511025505A CN106925258A CN 106925258 A CN106925258 A CN 106925258A CN 201511025505 A CN201511025505 A CN 201511025505A CN 106925258 A CN106925258 A CN 106925258A
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- 239000002086 nanomaterial Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 69
- 150000002500 ions Chemical class 0.000 claims abstract description 25
- 239000002131 composite material Substances 0.000 claims abstract description 8
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 5
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 5
- 239000010936 titanium Substances 0.000 claims description 38
- 150000003839 salts Chemical class 0.000 claims description 30
- 239000007864 aqueous solution Substances 0.000 claims description 15
- 239000002738 chelating agent Substances 0.000 claims description 15
- 230000001699 photocatalysis Effects 0.000 claims description 13
- 239000011259 mixed solution Substances 0.000 claims description 12
- 238000007146 photocatalysis Methods 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 12
- 238000004146 energy storage Methods 0.000 claims description 8
- 230000002378 acidificating effect Effects 0.000 claims description 7
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 7
- 239000002243 precursor Substances 0.000 claims description 7
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 6
- 239000011609 ammonium molybdate Substances 0.000 claims description 6
- 229940010552 ammonium molybdate Drugs 0.000 claims description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 5
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 5
- 235000015393 sodium molybdate Nutrition 0.000 claims description 4
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 3
- OYMJNIHGVDEDFX-UHFFFAOYSA-J molybdenum tetrachloride Chemical class Cl[Mo](Cl)(Cl)Cl OYMJNIHGVDEDFX-UHFFFAOYSA-J 0.000 claims description 3
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 3
- 239000011684 sodium molybdate Substances 0.000 claims description 3
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 3
- 229910000348 titanium sulfate Inorganic materials 0.000 claims description 3
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 230000015556 catabolic process Effects 0.000 abstract description 14
- 238000006731 degradation reaction Methods 0.000 abstract description 14
- 238000010521 absorption reaction Methods 0.000 abstract description 8
- 238000003860 storage Methods 0.000 abstract description 5
- 239000000356 contaminant Substances 0.000 abstract description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 15
- 239000000463 material Substances 0.000 description 13
- 238000005286 illumination Methods 0.000 description 12
- 238000000034 method Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical class O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000002105 nanoparticle Substances 0.000 description 7
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 6
- 229940043267 rhodamine b Drugs 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000004847 absorption spectroscopy Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
- 239000005416 organic matter Substances 0.000 description 4
- 230000000505 pernicious effect Effects 0.000 description 4
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 4
- 230000004044 response Effects 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 238000000634 powder X-ray diffraction Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 230000001629 suppression Effects 0.000 description 3
- 150000003608 titanium Chemical class 0.000 description 3
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000005430 electron energy loss spectroscopy Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 150000002751 molybdenum Chemical class 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 229910052755 nonmetal Inorganic materials 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 230000000243 photosynthetic effect Effects 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000008707 rearrangement Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003911 water pollution Methods 0.000 description 2
- 241000208340 Araliaceae Species 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 206010044565 Tremor Diseases 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/28—Molybdenum
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- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
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Abstract
The present invention relates to a kind of new Mo-Ti monocrystalline oxides nano material and its preparation and application, in the nano material, Mo ionic compartmentations are doped into the lattice of TiO2, form the monocrystalline composite oxides structure without interface, and the mol ratio of Mo and Ti ions is 0.05~0.5.New Mo-Ti monocrystalline oxides nano material of the invention has near-infrared plasma resonance absorption characteristic, and with the characteristic of storage light induced electron, assigns the characteristic of its dark place degradation of contaminant.
Description
Technical field
The present invention relates to a kind of novel transition metal oxide of cation crystallographic doping, and in particular to a kind of new Mo-Ti
Monocrystalline oxide nano material and its preparation and application, belong to environmental catalysis material and technical field of nano material.
Background technology
Currently, nano-TiO2Based photocatalyst as a kind of inexpensive, nontoxic, energy-conservation, efficient photocatalytic degradation air and
The material of organic pollutants, is paid attention to extensively by people.But due to its band gap wider can only by ultraviolet excitation, and
Only containing 3% or so ultraviolet in solar spectrum, its application in the depollution of environment in practice is greatly limited.To nano-TiO2
Effectively it is modified, is improved its light-use to visible region as current study hotspot.At present to TiO2It is modified
Method is concentrated mainly on three below aspect：Noble metal is combined, nonmetal doping and optical sensibilization, but noble metal
Composite cost is higher, the TiO of nonmetal doping2In visible region, absorption coefficient is relatively low, the photoactivated shakiness of organic dyestuff
The problems such as fixed, narrow-band semiconductor photosensitizer is susceptible to photoetch, therefore need a kind of stabilization of exploitation, low cost badly, can give birth in batches
The effective modified method for producing, to improve TiO2To the efficiency of light energy utilization of visible region.
The content of the invention
It is an object of the invention to provide a kind of preparation method of new Mo-Ti monocrystalline oxides nano material and its in energy storage
Application in terms of photocatalysis.
Here, the present invention provides a kind of new Mo-Ti monocrystalline oxides nano material, in the nano material, Mo ions
Substitute doping enters TiO2Lattice in, form the monocrystalline composite oxides structure without interface, the mol ratio of Mo and Ti ions is
0.05~0.5.
In the present invention, Mo uniform ions ground substitute doping enters TiO2Lattice in, form a kind of monocrystalline composite oxygen without interface
Compound semiconductor nanoparticle, i.e. Mo-TiO2Mo ionic lattices substitution TiO in nano particle2Part Ti ions, formed
A kind of monocrystalline composite oxides structure without interface, the nano-grain is uniform in size, well dispersed in aqueous, has
The absorption characteristic of total visible light spectrum, photocatalysis can be continued using light storage effect under non-illuminated conditions, realized round-the-clock
The light degradation of organic pollution and pernicious gas.New Mo-Ti monocrystalline oxides nano material of the invention has near-infrared etc.
Ion resonance absorption characteristic, and with the characteristic of storage light induced electron, assign the characteristic of its dark place degradation of contaminant.
It is preferred that in the nano material, the mol ratio of Mo and Ti ions is 0.05~0.1.
It is preferred that the particle size of the nano material is 5~200 nanometers.
The present invention also provides a kind of preparation method of the new Mo-Ti monocrystalline oxides nano material, it is characterised in that
Comprise the following steps：
1) Mo salt is made acidic aqueous solution, adds chelating agent, adds Ti salt and be sufficiently mixed and obtain mixed solution；
2) mixed solution is incubated 10~20 hours in 100~250 DEG C, cools down, is centrifuged, is dried to obtain precursor powder；
3) precursor powder is calcined 1~4 hour in 400~600 DEG C, the new Mo-Ti monocrystalline oxides nanometer material is obtained
Material.
The present invention utilizes a kind of new preparing process by ion exchange, Mo uniform ions ground substitute doping is entered TiO2Crystalline substance
In lattice, a kind of monocrystalline composite oxide semiconductor nano particle without interface is formed.Compared to pure TiO2, the inventive method system
Standby material is significantly improved to absorbing for visible region, is effectively increased the separative efficiency of photo-generate electron-hole, photocatalytic
5 times or so can be improved.Meanwhile, Mo can store TiO2The light induced electron produced in During Illumination, it is downward in non-illuminated conditions
Continuous photocatalysis, realizes the light degradation of round-the-clock organic pollution and pernicious gas, assigns TiO2New energy storage light is urged
Change characteristic.Preparation method simple and fast of the present invention, cost of material is low, indoors pollutant photocatalytic degradation, water pollution photocatalysis
Degraded and organic photosynthetic into etc. field have broad application prospects.
It is preferred that the acidic aqueous solution PH is between 0~3, and under the acid condition, the hydrolysis speed of molybdenum salt and titanium salt
Degree is suitable, is conducive to both to grow into monocrystalline in the solution.The process that Mo salt, water, chelating agent, Ti salt mix is included：
Mo salt is added to the water the aqueous solution for obtaining Mo salt, PH is adjusted between 0~3, then adds chelating agent and Ti salt
Mixed solution is obtained in the aqueous solution of Mo salt.Wherein Mo salt is dissolved in the molar concentration preferably 0.1M~0.5M after water.Institute
Stating concentration can generate MoO more than 5M3Dephasign, it is too small that Mo can be unfavorable in TiO2In be uniformly distributed.
It is preferred that the Mo salt is at least one of ammonium molybdate, sodium molybdate, six molybdenum chlorides.
It is preferred that the Ti salt is at least one of butyl titanate, isopropyl titanate, titanium sulfate.
It is preferred that the chelating agent is hydrogen fluoride (HF), cetyl trimethylammonium bromide (CTAB), polyvinyl pyrrole
At least one of alkanone (PVP).Preferably, Mo salt, chelating agent, the concentration of Ti salt are respectively 0.05M~3M, 0.1
M~5M, 1M~6M.The addition of the chelating agent can be fully in suppression solution free Mo ions and Ti ions
Concentration is defined.
Invention further provides described new Mo-Ti monocrystalline oxides nano material answering in energy storage photocatalysis field
With.
Brief description of the drawings
Fig. 1 is Mo-TiO2Transmission electron microscope (TEM) photo and corresponding distribution diagram of element；It can be seen that Mo exists
TiO2It is uniformly distributed on matrix；
Fig. 2 is single Mo-TiO2The linear distribution figure of the electron energy loss spectroscopy (EELS) of middle different elements；It can be seen that Mo is in TiO2It is brilliant
Lattice inner homogeneous are distributed；
Fig. 3 is pure TiO2And Mo-TiO2X-ray powder diffraction figure；Due to the lattice substitute doping of Mo ion pair Ti ions,
Destroy TiO2Lattice symmetry and extinction conditions, original TiO is occurred in that in X-ray powder diffraction figure2Delustring crystal face such as
(100) (110) etc.；
Fig. 4 is pure TiO2And Mo-TiO2Ultraviolet-visible absorption spectroscopy figure；Mo-TiO2Absorption in visible region significantly increases
By force, and in 1000nm or so there is very strong plasma resonance absorption；
Fig. 5 is Mo-TiO2Ultraviolet-visible absorption spectroscopy figure before and after illumination；Mo-TiO after illumination2It is aobvious to absorbing for visible ray
Enhancing is write, and plasma resonance absorption is from 1000nm or so blue shifts to 800nm；
Fig. 6 is Mo-TiO2X-ray photoelectron energy spectrum diagram before and after illumination；Mo-TiO after illumination2Mo5+ ion concentrations in sample
Significantly improve, illustrate that it can store light induced electron；
Fig. 7 is pure TiO2And Mo-TiO2Rhodamine B light degradation lab diagram；Under the same terms, Mo-TiO in During Illumination2Sample
Degradation rate to rhodamine B is pure TiO25 times, after illumination 1h, be placed on dark place, Mo-TiO2The photoproduction electricity of storage
Son can continue rhodamine B degradation；
Fig. 8 is Mo-TiO2The circulation experiment figure of light degradation rhodamine B；Mo-TiO after being circulated by 5 times2Energy storage light degradation sieve
The activity of red bright B does not decline, and illustrates Mo-TiO2With good light energy storage stability.
Specific embodiment
The present invention is further illustrated below in conjunction with accompanying drawing and following implementation methods, it should be appreciated that accompanying drawing and following implementation methods are only
For illustrating the present invention, it is not intended to limit the present invention.
The Mo-Ti monocrystalline oxide nano materials that the present invention is provided, Mo uniform ions ground substitute doping enters TiO2Lattice
In, a kind of monocrystalline composite oxides structure without interface is formed, so as to obtain a kind of new Mo-Ti monocrystalline oxides nanometer material
Material.
In the present invention, the monocrystalline composite oxides structure without interface of the nano material, by Mo ion pair Ti ions
Lattice substitute doping so that the material is significantly improved to absorbing for visible region, is effectively increased photo-generate electron-hole
Separative efficiency, photocatalysis performance improves 5 times or so.Meanwhile, Mo can store TiO2The photoproduction electricity produced in During Illumination
Son, photocatalysis is continued under non-illuminated conditions, realizes the light degradation of round-the-clock organic pollution and pernicious gas, is assigned
Give TiO2New energy storage photocatalysis characteristic.
Mo-TiO of the invention2Nano material by ion-exchange prepare, including mixed solution prepare, in uniform temperature
Lower hydro-thermal insulation a period of time will prepare precursor powder and then will remove surface organic matter in high-temperature calcination, make crystal lattice rearrangement, be obtained
Mo-TiO2Nano particle.Specifically, as an example, the preparation on mixed solution, Ke Yiwei：Mo salt is first dissolved in water
And add acid to be modulated into acidic aqueous solution, and then add chelating agent to be sufficiently mixed it in the acidic aqueous solution, finally add again
Enter after Ti salt is sufficiently mixed and obtain mixed solution.Wherein acidic aqueous solution PH is conveniently between 0~3.PH value is more than 3
When, the titanium salt hydrolysis speed of growth is too fast, and Mo ions are difficult to be doped into the lattice of TiO2.Hydro-thermal is incubated preference temperature
100~250 DEG C, soaking time is generally at 10~20 hours.Question response is cooled down after terminating, is centrifuged, is dried to obtain precursor
End.Precursor powder is calcined 1~4 hour in 400~600 DEG C, you can the new Mo-Ti monocrystalline oxides are obtained and receive
Rice material.Wherein, the Mo salt can be at least one of ammonium molybdate, sodium molybdate, six molybdenum chlorides.The Ti salt can be with
It is at least one of butyl titanate, isopropyl titanate, titanium sulfate.The chelating agent can be hydrogen fluoride, cetyl trimethyl
At least one of ammonium bromide, polyvinylpyrrolidone.And Mo salt, chelating agent, the concentration of Ti salt are respectively 0.05M~3
M, 0.1M~5M, 1M~6M.The addition of the chelating agent can be fully in suppression solution free Mo ions and Ti
The concentration of ion is defined.Wherein Mo salt is dissolved in the molar concentration preferably 0.1M~0.5M after water.The concentration is more than 5M
MoO can be generated3Dephasign, it is too small to be unfavorable for Mo being uniformly distributed in TiO2.
Mo-TiO of the invention2The preparation of nano material, more specifically, as an example, such as can include following
Step：
First, mixed solution is configured：A certain amount of Mo salt (such as ammonium molybdate) is slowly added in the aqueous solution, being stirred at room temperature makes
It is sufficiently mixed, and the PH of solution is adjusted between 0~3；Appropriate chelating agent (such as hydrogen fluorine is added in reaction system
Acid), stir；) be slowly added in the aqueous solution of Mo salt, room temperature a certain amount of Ti salt (such as butyl titanate)
Stirring is sufficiently mixed it.
Then, the nano material is obtained after hydro-thermal insulation and calcining：By mixed solution add water heating kettle in, certain
Temperature hydro-thermal held for some time.Question response is cooled down after terminating, is centrifuged, dried, and obtains powder sample；Powder sample is existed
400 DEG C of calcining 1h, remove surface organic matter, make crystal lattice rearrangement, and Mo-TiO is obtained2Nano particle.
In the present invention, it is the hydrolysis rate phase for molybdenum salt with titanium salt that the solution ph of Mo salt is adjusted between 0~3
When.Chelating agent played a part of to be the concentration of free Mo ions in abundant suppression solution with Ti ions, if exceed with
Upper scope, the then Mo-TiO of unfavorable synthetic single crystal2Nano material.The ion-exchange that the present invention is used, compare other preparations
Method, with simplicity, the characteristics of grow controllable, uniform.
It is characteristic of the invention that：New Mo-Ti monocrystalline oxides nano material of the invention, compared to pure TiO2, the material
Material is significantly improved to absorbing for visible region, is effectively increased the separative efficiency of photo-generate electron-hole, and photocatalysis performance is improved
5 times or so.Meanwhile, Mo can store TiO2The light induced electron produced in During Illumination, continuity light is urged under non-illuminated conditions
Change is acted on, and realizes the light degradation of round-the-clock organic pollution and pernicious gas, assigns TiO2New energy storage photocatalysis is special
Property.Preparation method simple and fast of the present invention, cost of material is low, indoors pollutant photocatalytic degradation, water pollution photocatalytic degradation
With organic photosynthetic into etc. field have broad application prospects.
Embodiment is enumerated further below to describe the present invention in detail.It will similarly be understood that following examples are served only for this hair
Bright to be further described, it is impossible to be interpreted as limiting the scope of the invention, those skilled in the art is of the invention
Some nonessential modifications and adaptations that the above is made belong to protection scope of the present invention.Following specific technique ginsengs of example
Number etc. is also only an example in OK range, i.e. those skilled in the art can be done in suitable scope by the explanation of this paper
Selection, and do not really want to be defined in the concrete numerical value of hereafter example.
Embodiment 1
0.3g ammonium molybdates are slowly added in the aqueous solution of 1ml, being stirred at room temperature is sufficiently mixed it, and add a small amount of watery hydrochloric acid to incite somebody to action
The PH of solution is adjusted to 2.The hydrofluoric acid of 1.5ml is added in reaction system, is stirred.By the butyl titanate of 5ml
It is slowly added in the aqueous solution of ammonium molybdate, being stirred at room temperature is sufficiently mixed it.By in mixed solution addition water heating kettle, it is being heated to
150 DEG C of insulation 10h.Question response is cooled down after terminating, is centrifuged, dried, and obtains powder sample.By powder sample at 400 DEG C
Calcining 1h, removes surface organic matter, and Mo-TiO is obtained2Nano particle.
Fig. 1 is Mo-TiO2Transmission electron microscope (TEM) photo and corresponding Elemental redistribution, by photo it can be seen that：Mo
In TiO2It is evenly distributed on matrix, and Mo-TiO2It is monocrystalline.
Fig. 2 is single Mo-TiO2The linear distribution of the electron energy loss spectroscopy (EELS) of middle different elements, by photo it can be seen that：
It is doped into TiO Mo uniform ions2Lattice in.
Fig. 3 is pure TiO2And Mo-TiO2X-ray powder diffraction, it can be seen that the crystallization of sample is all fine.While by
In Mo in TiO2Ionic compartmentation in lattice, destroys the periodicity of its lattice so that original Anatase TiO2In should
(100) and (110) crystal face diffraction of delustring is strengthened.
Fig. 4 is pure TiO2And Mo-TiO2Ultraviolet-visible absorption spectroscopy, it can be seen that Mo-TiO2In the suction of visible region
Receipts increase significantly, while also there is the plasma resonance absorption of obvious near infrared region.
Fig. 5 is Mo-TiO2Ultraviolet-visible absorption spectroscopy before and after illumination, it can be seen that Mo-TiO2Absorbed after irradiation
Significantly increase, the color of sample is also substantially deepened.
Fig. 6 is Mo-TiO2X-ray photoelectron power spectrum before and after illumination, it can be seen that Mo-TiO2The Mo after illumination5+
The content of ion is significantly increased, and illustrates that it has photoelectronic storge quality, is placed on Mo after the 24h of dark place5+The content of ion
It has been declined that, illustrated that the photoelectron of storage reacts with other chemical substances.
Fig. 7 is pure TiO2And Mo-TiO2Rhodamine B degradation experiment, it can be seen that same light shine under the conditions of, Mo-
TiO2The efficiency of light degradation rhodamine B is pure TiO25 times or so, while Mo-TiO in the dark2Can also continue to sieve of degrading
Red bright B, realizes round-the-clock degradable organic pollutant.
Fig. 8 is Mo-TiO2The circulation experiment of rhodamine B degradation, after being circulated by 5 times, Mo-TiO2Round-the-clock drop
The efficiency for solving rhodamine B is not reduced, it can be seen that Mo-TiO2With good photocatalysis stability.
Embodiment 2
0.63g sodium molybdates are slowly added in the aqueous solution of 3ml, being stirred at room temperature is sufficiently mixed it, and add a small amount of watery hydrochloric acid to incite somebody to action
The PH of solution is adjusted to 0.The polyvinylpyrrolidone of 500mg is added in reaction system, is stirred.By 10ml's
Isopropyl titanate is slowly added in the aqueous solution of ammonium molybdate, and being stirred at room temperature is sufficiently mixed it.By mixed solution add water heating kettle in,
It is being heated to 200 DEG C of insulation 10h.Question response is cooled down after terminating, is centrifuged, dried, and obtains powder sample.By powder sample
1.5h is calcined at 500 DEG C, surface organic matter is removed, Mo-TiO is obtained2Nano particle.
Claims (10)
1. a kind of new Mo-Ti monocrystalline oxides nano material, it is characterised in that in the nano material, Mo ionic compartmentations are doped into TiO2Lattice in, form the monocrystalline composite oxides structure without interface, the mol ratio of Mo and Ti ions is 0.05~0.5.
2. nano material according to claim 1, it is characterised in that in the nano material, the mol ratio of Mo and Ti ions is 0.05~0.1.
3. nano material according to claim 1 and 2, it is characterised in that the particle size of the nano material is 5~200 nanometers.
4. the preparation method of the new Mo-Ti monocrystalline oxides nano material any one of a kind of claims 1 to 3, it is characterised in that comprise the following steps：
1）Mo salt is made acidic aqueous solution, chelating agent is added, is added Ti salt and be sufficiently mixed and obtain mixed solution；
2）The mixed solution is incubated 10~20 hours in 100~250 DEG C, is cooled down, be centrifuged, be dried to obtain precursor powder；
3）Precursor powder is calcined 1~4 hour in 400~600 DEG C, the new Mo-Ti monocrystalline oxides nano material is obtained.
5. preparation method according to claim 4, it is characterised in that the acidic aqueous solution PH is between 0~3.
6. the preparation method according to claim 4 or 5, it is characterised in that the Mo salt is at least one of ammonium molybdate, sodium molybdate, six molybdenum chlorides.
7. the preparation method according to any one of claim 4 to 6, it is characterised in that the Ti salt is at least one of butyl titanate, isopropyl titanate, titanium sulfate.
8. the preparation method according to any one of claim 4 to 7, it is characterised in that the chelating agent is at least one of hydrogen fluoride, cetyl trimethylammonium bromide, polyvinylpyrrolidone.
9. the preparation method according to any one of claim 4 to 8, it is characterised in that Mo salt, chelating agent, the concentration of Ti salt are respectively 0.05 M~3 M, 0.1 M~5 M, 1 M~6 M.
10. application of the new Mo-Ti monocrystalline oxides nano material any one of a kind of claims 1 to 3 in energy storage photocatalysis field.
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| CN109569574A (en) * | 2017-09-28 | 2019-04-05 | 中国科学院金属研究所 | A kind of body phase codope visible-light photocatalysis material and its preparation method and application |
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| CN109482173A (en) * | 2017-09-11 | 2019-03-19 | 中国科学院金属研究所 | A kind of bulk phase-doped nano-photocatalyst material and its preparation method and application |
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| CN111036191B (en) * | 2019-12-13 | 2023-04-14 | 吉林师范大学 | Preparation method of metal molybdenum-doped modified titanium dioxide visible-light-driven photocatalyst |
| CN114573150A (en) * | 2022-04-02 | 2022-06-03 | 淄博新华纸业有限公司 | Papermaking sewage treatment process |
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