CN107335420B - A kind of nano wire reticular structure calcium titanate visible light catalyst and its preparation method and application - Google Patents
A kind of nano wire reticular structure calcium titanate visible light catalyst and its preparation method and application Download PDFInfo
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- CN107335420B CN107335420B CN201710476163.0A CN201710476163A CN107335420B CN 107335420 B CN107335420 B CN 107335420B CN 201710476163 A CN201710476163 A CN 201710476163A CN 107335420 B CN107335420 B CN 107335420B
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- 239000002070 nanowire Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- 239000003054 catalyst Substances 0.000 title claims abstract description 33
- AOWKSNWVBZGMTJ-UHFFFAOYSA-N calcium titanate Chemical compound [Ca+2].[O-][Ti]([O-])=O AOWKSNWVBZGMTJ-UHFFFAOYSA-N 0.000 title claims abstract 13
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 75
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 51
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 51
- 239000000243 solution Substances 0.000 claims abstract description 50
- 238000006243 chemical reaction Methods 0.000 claims abstract description 46
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000010936 titanium Substances 0.000 claims abstract description 32
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 31
- 239000007864 aqueous solution Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000001257 hydrogen Substances 0.000 claims abstract description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 11
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 8
- 239000002351 wastewater Substances 0.000 claims abstract description 3
- 239000002002 slurry Substances 0.000 claims description 59
- 239000002243 precursor Substances 0.000 claims description 52
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 18
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 16
- 239000011591 potassium Substances 0.000 claims description 16
- 229910052700 potassium Inorganic materials 0.000 claims description 16
- 230000001376 precipitating effect Effects 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 15
- 239000011575 calcium Substances 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 12
- 229910052791 calcium Inorganic materials 0.000 claims description 12
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 10
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 10
- 229910021529 ammonia Inorganic materials 0.000 claims description 9
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000000428 dust Substances 0.000 claims description 9
- 238000005516 engineering process Methods 0.000 claims description 9
- 239000007795 chemical reaction product Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 239000002244 precipitate Substances 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 238000006136 alcoholysis reaction Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
- 239000010935 stainless steel Substances 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims 1
- 230000002349 favourable effect Effects 0.000 abstract description 10
- 230000001699 photocatalysis Effects 0.000 abstract description 7
- 239000002904 solvent Substances 0.000 abstract description 7
- 239000013078 crystal Substances 0.000 abstract description 4
- 238000007146 photocatalysis Methods 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 3
- 239000000843 powder Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000002425 crystallisation Methods 0.000 abstract 1
- 230000008025 crystallization Effects 0.000 abstract 1
- 238000002242 deionisation method Methods 0.000 abstract 1
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- WEUCVIBPSSMHJG-UHFFFAOYSA-N calcium titanate Chemical compound [O-2].[O-2].[O-2].[Ca+2].[Ti+4] WEUCVIBPSSMHJG-UHFFFAOYSA-N 0.000 description 46
- 206010001497 Agitation Diseases 0.000 description 36
- 238000013019 agitation Methods 0.000 description 36
- 239000008367 deionised water Substances 0.000 description 18
- 229910021641 deionized water Inorganic materials 0.000 description 18
- 238000004090 dissolution Methods 0.000 description 18
- 239000000463 material Substances 0.000 description 13
- 239000002253 acid Substances 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 230000015556 catabolic process Effects 0.000 description 7
- 238000006731 degradation reaction Methods 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 6
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 6
- 239000011941 photocatalyst Substances 0.000 description 6
- GHDSNRQFECQVII-UHFFFAOYSA-N [Ti].OOO Chemical compound [Ti].OOO GHDSNRQFECQVII-UHFFFAOYSA-N 0.000 description 5
- LUMVCLJFHCTMCV-UHFFFAOYSA-M potassium;hydroxide;hydrate Chemical compound O.[OH-].[K+] LUMVCLJFHCTMCV-UHFFFAOYSA-M 0.000 description 5
- 230000004044 response Effects 0.000 description 5
- 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 5
- 229940043267 rhodamine b Drugs 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 4
- NQTSTBMCCAVWOS-UHFFFAOYSA-N 1-dimethoxyphosphoryl-3-phenoxypropan-2-one Chemical compound COP(=O)(OC)CC(=O)COC1=CC=CC=C1 NQTSTBMCCAVWOS-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 238000002003 electron diffraction Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000000101 transmission high energy electron diffraction Methods 0.000 description 3
- 229910002971 CaTiO3 Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
-
- 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
- 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
- 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
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
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- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/003—Titanates
- C01G23/006—Alkaline earth titanates
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
- C01P2004/16—Nanowires or nanorods, i.e. solid nanofibres with two nearly equal dimensions between 1-100 nanometer
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- 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 invention discloses a kind of preparation methods of nano wire reticular structure calcium titanate visible light catalyst, oxyhydroxide including preparing titanium is precipitated with calcium nitrate aqueous solution as reaction raw materials, with deionization water as solvent, the potassium hydroxide that suitable concentration is added promotes crystallization, polyvinyl alcohol water solution is added and controls crystal growth, hydro-thermal reaction obtains the nano wire reticular structure calcium titanate visible light catalyst of favorable dispersibility at 180~230 DEG C.Present invention process is simple, easily controllable, at low cost, is easy to large-scale production.The microstructure of the powder of preparation is nano wire reticular structure, and has outstanding photocatalysis performance under visible light, and the product has broad prospects in terms of photocatalysis related application.The present invention also provides a kind of by the nano wire reticular structure calcium titanate visible light catalyst of above method preparation and its in the treatment of waste water and in the application decomposed in water hydrogen making.
Description
Technical field
The invention belongs to field of inorganic nonmetallic material, and in particular to a kind of nano wire reticular structure calcium titanate visible light is urged
Agent and its preparation method and application.
Background technique
Catalysis material can convert the water to the organic pollutant in Hydrogen Energy, and degradation environment, tool using solar energy
There is at low cost, high-efficiency cleaning, do not generate secondary pollution, has in the energy crisis for solving currently to face with environmental problem
Wide application prospect.But currently with TiO2Based on traditional catalysis material optical response range it is narrow, be only capable of using in sunlight
The middle ultraviolet region (λ < 400nm) less than 8%, can not visible light lower using energy and that the overwhelming majority is accounted in sunlight.
Therefore, find suitable visible light responsive photocatalyst, expand sunlight absorbable wave band improve the efficiency of solar energy utilization at
For the goal in research of numerous researchers.
Calcium titanate (CaTiO3) be a kind of typical perovskite structure composite oxides, most earlier than 1839 in mineral
It is found.CaTiO3It is widely used in electronic component, and is the main component for storing nuke rubbish synthesis rock.At room temperature,
CaTiO3It is orthohormbic structure, space group belongs to Pbnm.Since forbidden bandwidth is suitable for, band structure can easily be accommodated with microstructure,
And has many advantages, such as that cheap, raw material is simple, Environmental compatibility is strong, secondary pollution will not be caused to environment.
The forbidden bandwidth of calcium titanate is 3.4~3.5eV, and conduction band current potential is -0.56~-0.36eV (SHE), and valence band current potential is
2.94eV.Since the conduction band current potential of calcium titanate is defeated by hydrogen normal potential (0V), valence band current potential just in oxygen current potential (1.23eV),
Calcium titanate can be used for photochemical catalyzing hydrogen making and oxygen.But the forbidden bandwidth of calcium titanate is wider, optical response range is only
For ultraviolet band, currently generallys use doping and introduce impurity energy level to widen its optical response range to visible waveband, but adulterate
Ion is used as the migration of complex centre obstruction photo-generated carrier sometimes, to reduce photocatalytic activity.On the other hand, effectively
The generation and concentration for controlling the Lacking oxygen in semiconductor light-catalyst, can also effectively introduce intermediate level reduces forbidden bandwidth,
To widen optical response range to visible light, at the same Lacking oxygen can also promote as electron donor photo-generated carrier migration thus
Improve photocatalysis efficiency；Furthermore theoretical calculation proves that there is the calcium titanate of nanowire structure response can be generated to visible light, but
The report of pure calcium titanate photocatalyst there is no non-impurity-doped, without co-catalyst and with visible light activity at present.
Summary of the invention
The object of the present invention is to provide a kind of nano wire reticular structure calcium titanate visible light catalyst and preparation method thereof,
Using hydrothermal synthesis method.
A kind of preparation method of nano wire reticular structure calcium titanate visible light catalyst, comprising:
(1) butyl titanate is dissolved in ethylene glycol monomethyl ether, obtains solution of tetrabutyl titanate；
(2) under stirring, 20~40wt% ammonia spirit is added into the solution of tetrabutyl titanate of step (1) preparation,
It precipitates, be filtered, washed, obtain the oxyhydroxide precipitating of titanium；
(3) calcium nitrate is soluble in water, obtain calcium nitrate aqueous solution；
(4) potassium hydroxide is soluble in water, obtain potassium hydroxide aqueous solution；
(5) polyvinyl alcohol is soluble in water, obtain polyvinyl alcohol water solution；
(6) polyvinyl alcohol water solution prepared by step (5) is added in the potassium hydroxide aqueous solution of step (4) preparation,
Potassium hydroxide-polyvinyl alcohol water solution is obtained after mixing evenly；
(7) the oxyhydroxide precipitating of titanium is added in the calcium nitrate aqueous solution of step (3) preparation, stirs 1~5h；Again
Potassium hydroxide-polyvinyl alcohol water solution of step (6) preparation is added, is further continued for stirring at least 12h, obtains precursor slurry；Institute
It states in precursor slurry, the molar ratio of calcium and titanium is 1.0~2.0, the molar concentration of potassium hydroxide in the precursor slurry
For 0.4~1.5mol/L；
(8) precursor slurry is added in reaction kettle liner, the volume of added precursor slurry is reaction kettle liner volume
70~90%；
(9) the reaction kettle liner equipped with precursor slurry is placed in reaction kettle, seals, keeps the temperature 24 at 150~230 DEG C
~96 hours progress hydro-thermal process, then allow reaction kettle to naturally cool to room temperature, and after unloading kettle, with dust technology, washing reaction is produced repeatedly
Object filters, and drying obtains nano wire reticular structure calcium titanate visible light catalyst.
The present invention is prepared for visible light-responded and ties using non-impurity-doped technique for the first time at a lower temperature by hydro-thermal method
The calcium titanate powder of crystalline substance and favorable dispersibility.During hydrothermal synthesis, (001) that polyvinyl alcohol is adsorbed in calcium titanate is brilliant
Face, and inhibit its growth, cause calcium titanate along (001) that [110] crystal orientation is grown to nano wire reticular structure, while being suppressed
Face generates Lacking oxygen during the growth process, forms intermediate level, causes forbidden bandwidth to reduce, thus by the photoresponse model of calcium titanate
It encloses and widens from ultraviolet to visible light.
Ti in step (1), in the solution of tetrabutyl titanate4+Ion concentration is 0.25~1.0mol/L.
In step (2), the volume ratio of ammonia spirit and ethylene glycol monomethyl ether is 0.1~0.2.
In step (3), Ca in the calcium nitrate aqueous solution2+The concentration of ion is 1.5~4.0mol/L.
In step (4), the concentration of the potassium hydroxide aqueous solution is 2~10mol/L.
In step (5), the concentration of the polyvinyl alcohol water solution is 16~32g/L.
The total mol concentration of titanium is 0.1~0.3mol/L in the precursor slurry.
The quality volume fraction of polyvinyl alcohol is 4~13g/L in the precursor slurry.
(001) crystal face that polyvinyl alcohol is adsorbed in calcium titanate inhibits its growth, causes calcium titanate raw along (110) crystal plane direction
Lacking oxygen defect is generated when (001) that a length of nano wire reticular structure is suppressed simultaneously looks unfamiliar long, is adjusted in precursor pulp
The content of polyvinyl alcohol can control the production quantity of Lacking oxygen defect, reduce forbidden bandwidth thus by the photoresponse model of calcium titanate
It encloses and widens from ultraviolet to visible light.
In preparation process of the present invention, the reaction kettle used is polytetrafluoroethylliner liner, the closed reaction kettle of stainless steel external member.
Preferably, in step (7), with dust technology, washing reaction product is obtained with removing the by-product in product repeatedly
The calcium titanate of pure phase.
In preparation process of the present invention, the calcium nitrate, potassium hydroxide, butyl titanate, ethylene glycol monomethyl ether, polyvinyl alcohol
Purity be not less than chemistry it is pure.
Wherein, the polyvinyl alcohol is PVA-124, and alcoholysis degree is 98~99 (m01) %, and average degree of polymerization (n) is 2400
~2500.
The present invention also provides a kind of nano wire reticular structure calcium titanate visible light catalytics prepared by the above method
Agent, the nano wire reticular structure calcium titanate visible light catalyst crystallinity and favorable dispersibility and have the netted knot of nano wire
Structure.
It is a further object of the present invention to provide a kind of nano wire reticular structure calcium titanates prepared by the above method can
The application of light-exposed catalyst in the treatment of waste water and the application in decomposition water hydrogen making.
The beneficial effects of the present invention are:
The present invention, which is prepared for crystallinity and favorable dispersibility using simple hydro-thermal method, has the titanium of nano wire reticular structure
Sour calcium visible-light photocatalyst.Nano wire reticular structure calcium titanate visible-light photocatalyst prepared by the present invention can with outstanding
Light-exposed catalytic activity can more fully utilize solar energy, have broad application prospects in fields such as photocatalytic applications.
Hydro-thermal method device therefor of the invention is simple, easy control of process conditions, and composite mixed without carrying out, and the cost of preparation also compares
It is lower, it is easy to industrialized production.
Detailed description of the invention
Fig. 1 is the X-ray diffraction of nano wire reticular structure calcium titanate visible light catalyst particle prepared by embodiment 1
(XRD) map；
Fig. 2 is the scanning electron microscope of nano wire reticular structure calcium titanate visible light catalyst prepared by embodiment 1
(SEM) photo；
Fig. 3 is the transmission electron microscope of nano wire reticular structure calcium titanate visible light catalyst prepared by embodiment 1
(TEM) photo and selective electron diffraction (SAED) photo (a), high resolution transmission electron microscopy (HRTEM) photo (b)；
Fig. 4 is nano wire reticular structure calcium titanate visible light catalyst (a) and commercial titanium dioxide prepared by embodiment 1
P25 (b), commercial calcium titanate (c) rhodamine B degradation (RhB) degradation efficiency curve control figure under visible light；
Fig. 5 is nano wire reticular structure calcium titanate visible light catalyst (a) prepared by embodiment 1 and commercial calcium titanate (b)
Water is decomposed under visible light prepares hydrogen efficiency curve control figure.
Specific embodiment
The present invention is further illustrated below in conjunction with drawings and examples.
Embodiment 1
(1) 1.71g butyl titanate is weighed, is added in 10ml ethylene glycol monomethyl ether, magnetic agitation obtains metatitanic acid to dissolving
Four butyl acetate solutions；
(2) under stirring, the mass concentration 30% of 1.5ml is added into the solution of tetrabutyl titanate of step (1) preparation
Ammonia spirit, precipitate, filter, washing, obtain titanium oxyhydroxide precipitating；
(3) 1.26g calcium nitrate is weighed, is added in 10ml deionized water, magnetic agitation to dissolution；
(4) 2.0g potassium hydroxide is weighed, is added in 10ml deionized water, magnetic agitation to dissolution；
(5) 8.0g polyvinyl alcohol is weighed, is added in 250ml deionized water, heats 90 DEG C of magnetic agitations to dissolution；
(6) 9ml is taken to be added to potassium hydroxide water prepared by step (4) from polyvinyl alcohol water solution prepared by step (5)
It is sufficiently stirred to obtain potassium hydroxide-polyvinyl alcohol water solution in solution；
(7) the oxyhydroxide precipitating of titanium is added in the calcium nitrate aqueous solution of step (3) preparation, magnetic agitation is at least
1h；Potassium hydroxide-the polyvinyl alcohol water solution prepared in step (6) is added, magnetic agitation at least 12h is further continued for, before obtaining
Body slurry；The total mol concentration of titanium is 0.13mol/L in precursor slurry, and the molar ratio of calcium and titanium is in precursor slurry
1.06, the molar concentration of potassium hydroxide is 0.89mol/L in precursor slurry, the quality volume of polyvinyl alcohol in precursor slurry
Score is 7.2g/L.
(8) precursor slurry is added in reaction kettle liner, the volume of added slurry is the 80% of reaction kettle liner volume；
(9) the reaction kettle liner equipped with precursor slurry is placed in reaction kettle, seals, keeps the temperature 48 hours at 200 DEG C
Solvent heat treatment is carried out, then reaction kettle is allowed to naturally cool to room temperature, after unloading kettle, with dust technology washing reaction product repeatedly, mistake
Filter, drying, obtains the nano wire reticular structure calcium titanate visible light catalyst of favorable dispersibility.
X-ray diffraction (XRD) map of gained nano wire reticular structure calcium titanate visible light catalyst is shown in Fig. 1, scanning electricity
Sub- microscope photograph (SEM) sees Fig. 2, transmission electron microscope and selective electron diffraction, high resolution transmission electron microscopy (TEM,
SAED, HRTEM) photo is shown in Fig. 3, wherein Fig. 3 (a) is transmission electron microscope (TEM) photo and selective electron diffraction (SAED)
Photo；Fig. 3 (b) is high resolution transmission electron microscopy mirror (HRTEM) photo.
Fig. 4 is nano wire reticular structure calcium titanate visible light catalyst (a) prepared by the embodiment of the present invention 1 and commercial dioxy
Change the degradation efficiency curve control figure of titanium P25 (b), commercial calcium titanate (c) rhodamine B degradation (RhB) under visible light.It can by figure
See commercial calcium titanate and commercial titanium dioxide P25 does not have the ability of visible light responsible photocatalytic rhodamine B degradation, and this hair
The nano wire reticular structure calcium titanate visible light catalyst of bright preparation then can photocatalytic degradation rhodamine B under visible light,
When degradation proceeds to 160 minutes, the rhodamine B more than 80% has been degraded.It is rung as it can be seen that visible light has successfully been obtained in the present invention
The calcium titanate photocatalyst answered.
Fig. 5 is nano wire reticular structure calcium titanate visible light catalyst (a) prepared by the embodiment of the present invention 1 and commercial metatitanic acid
Calcium (b) decomposes water under visible light and prepares hydrogen efficiency curve control figure.As seen from the figure, when the reaction time reaches 6h, commercial titanium
Hydrogen generation efficiency is 5 μm of ol/g to sour calcium under visible light, nano wire reticular structure calcium titanate visible light catalyst prepared by example 1
Hydrogen generation efficiency is then 30 μm of ol/g, is 5 times of commercial calcium titanate, it is seen that the present invention, which is successfully prepared, can be used for visible photocatalysis water
The calcium titanate photocatalyst of hydrogen making.
Embodiment 2
(1) 1.65g butyl titanate is weighed, is added in 10ml ethylene glycol monomethyl ether, magnetic agitation obtains metatitanic acid to dissolving
Four butyl acetate solutions；
(2) under stirring, the mass concentration 30% of 1.5ml is added into the solution of tetrabutyl titanate of step (1) preparation
Ammonia spirit, precipitate, filter, washing, obtain titanium oxyhydroxide precipitating；
(3) 1.26g calcium nitrate is weighed, is added in 10mL deionized water, magnetic agitation to dissolution；
(4) 1.68g potassium hydroxide is weighed, is added in 10ml deionized water, magnetic agitation to dissolution；
(5) 8.0g polyvinyl alcohol is weighed.It is added in 250ml deionized water, heats 90 DEG C of magnetic agitations to dissolution；
(6) 7ml is taken to be added to potassium hydroxide water prepared by step (4) from polyvinyl alcohol water solution prepared by step (5)
It is sufficiently stirred to obtain potassium hydroxide-polyvinyl alcohol water solution in solution；
(7) the oxyhydroxide precipitating of titanium is added in calcium nitrate aqueous solution, magnetic agitation at least 1h；Add step
(6) potassium hydroxide-polyvinyl alcohol water solution prepared in, is further continued for magnetic agitation at least 12h, obtains precursor slurry；Preceding body
The total mol concentration of titanium is 0.12mol/L in somaplasm material, and the molar ratio of calcium and titanium is 1.10 in precursor slurry, precursor slurry
The molar concentration of potassium hydroxide is 0.75mol/L in material, and the quality volume fraction of polyvinyl alcohol is 5.6g/L in precursor slurry.
(8) precursor slurry is added in reaction kettle liner, the volume of added slurry is the 80% of reaction kettle liner volume；
(9) the reaction kettle liner equipped with precursor slurry is placed in reaction kettle, seals, keeps the temperature 24 hours at 200 DEG C
Solvent heat treatment is carried out, then reaction kettle is allowed to naturally cool to room temperature, after unloading kettle, with dust technology washing reaction product repeatedly, mistake
Filter, drying, obtains the nano wire reticular structure calcium titanate visible light catalyst of favorable dispersibility.
Embodiment 3
(1) 1.68g butyl titanate is weighed, is added in 10ml ethylene glycol monomethyl ether, magnetic agitation obtains metatitanic acid to dissolving
Four butyl acetate solutions；
(2) under stirring, the mass concentration 30% of 1.5ml is added into the solution of tetrabutyl titanate of step (1) preparation
Ammonia spirit, precipitate, filter, washing, obtain titanium oxyhydroxide precipitating；
(3) 1.45g calcium nitrate is weighed, is added in 10mL deionized water, magnetic agitation to dissolution；
(4) 1.68g potassium hydroxide is weighed, is added in 10ml deionized water, magnetic agitation to dissolution；
(5) 8.0g polyvinyl alcohol is weighed, is added in 250ml deionized water, heats 90 DEG C of magnetic agitations to dissolution；
(6) potassium hydroxide for taking 7ml that step (4) preparation is added from polyvinyl alcohol water solution prepared by step (5) is water-soluble
It is sufficiently stirred to obtain potassium hydroxide-polyvinyl alcohol water solution in liquid；
(7) the oxyhydroxide precipitating of titanium is added in calcium nitrate aqueous solution, magnetic agitation at least 1h；Add step
(6) potassium hydroxide-polyvinyl alcohol water solution prepared in, is further continued for magnetic agitation at least 12h, obtains precursor slurry；Preceding body
The total mol concentration of titanium is 0.12mol/L in somaplasm material, and the molar ratio of calcium and titanium is 1.24 in precursor slurry, precursor slurry
The molar concentration of potassium hydroxide is 0.75mol/L in material, and the quality volume fraction of polyvinyl alcohol is 5.6g/L in precursor slurry.
(8) precursor slurry is added in reaction kettle liner, the volume of added slurry is the 80% of reaction kettle liner volume；
(9) the reaction kettle liner equipped with precursor slurry is placed in reaction kettle, seals, keeps the temperature 24 hours at 200 DEG C
Solvent heat treatment is carried out, then reaction kettle is allowed to naturally cool to room temperature, after unloading kettle, with dust technology washing reaction product repeatedly, mistake
Filter, drying, obtains the nano wire reticular structure calcium titanate visible light catalyst of favorable dispersibility.
Embodiment 4
(1) 1.65g butyl titanate is weighed, is added in 10ml ethylene glycol monomethyl ether, magnetic agitation obtains metatitanic acid to dissolving
Four butyl acetate solutions；
(2) under stirring, the mass concentration 25% of 2ml is added into the solution of tetrabutyl titanate of step (1) preparation
Ammonia spirit precipitates, and filters, washing, obtains the oxyhydroxide precipitating of titanium；
(3) 1.52g calcium nitrate is weighed, is added in 10mL deionized water, magnetic agitation to dissolution；
(4) 1.92g potassium hydroxide is weighed, is added in 10ml deionized water, magnetic agitation to dissolution；
(5) 8.0g polyvinyl alcohol is weighed, is added in 250ml deionized water, heats 90 DEG C of magnetic agitations to dissolution；
(6) 8ml is taken to be added to potassium hydroxide water prepared by step (4) from polyvinyl alcohol water solution prepared by step (5)
It is sufficiently stirred to obtain potassium hydroxide-polyvinyl alcohol water solution in solution；
(7) the oxyhydroxide precipitating of titanium is added in calcium nitrate aqueous solution, magnetic agitation at least 1h；Add step
(6) potassium hydroxide-polyvinyl alcohol water solution prepared in, is further continued for magnetic agitation at least 12h, obtains precursor slurry；Preceding body
The total mol concentration of titanium is 0.12mol/L in somaplasm material, and the molar ratio of calcium and titanium is 1.31 in precursor slurry, precursor slurry
The molar concentration of potassium hydroxide is 0.86mol/L in material, and the quality volume fraction of polyvinyl alcohol is 6.4g/L in precursor slurry.
(8) precursor slurry is added in reaction kettle liner, the volume of added slurry is the 80% of reaction kettle liner volume；
(9) the reaction kettle liner equipped with precursor slurry is placed in reaction kettle, seals, keeps the temperature 36 hours at 200 DEG C
Solvent heat treatment is carried out, then reaction kettle is allowed to naturally cool to room temperature, after unloading kettle, with dust technology washing reaction product repeatedly, mistake
Filter, drying, obtains the nano wire reticular structure calcium titanate visible light catalyst of favorable dispersibility.
Embodiment 5
(1) 1.65g butyl titanate is weighed, is added in 10ml ethylene glycol monomethyl ether, magnetic agitation obtains metatitanic acid to dissolving
Four butyl acetate solutions；
(2) under stirring, the mass concentration 30% of 1.5ml is added into the solution of tetrabutyl titanate of step (1) preparation
Ammonia spirit, precipitate, filter, washing, obtain titanium oxyhydroxide precipitating；
(3) 1.60g calcium nitrate is weighed, is added in 10mL deionized water, magnetic agitation to dissolution；
(4) 1.68g potassium hydroxide is weighed, is added in 10ml deionized water, magnetic agitation to dissolution；
(5) 8.0g polyvinyl alcohol is weighed, is added in 250ml deionized water, heats 90 DEG C of magnetic agitations to dissolution；
(6) 13ml is taken to be added to potassium hydroxide water prepared by step (4) from polyvinyl alcohol water solution prepared by step (5)
It is sufficiently stirred to obtain potassium hydroxide-polyvinyl alcohol water solution in solution；
(7) the oxyhydroxide precipitating of titanium is added in calcium nitrate aqueous solution, magnetic agitation at least 1h；Add step
(6) potassium hydroxide-polyvinyl alcohol water solution prepared in, is further continued for magnetic agitation at least 12h, obtains precursor slurry；Preceding body
The total mol concentration of titanium is 0.12mol/L in somaplasm material, and the molar ratio of calcium and titanium is 1.39 in precursor slurry, precursor slurry
The molar concentration of potassium hydroxide is 0.75mol/L in material, and the quality volume fraction of polyvinyl alcohol is 10.4g/ in precursor slurry
L。
(8) precursor slurry is added in reaction kettle liner, the volume of added slurry is the 80% of reaction kettle liner volume；
(9) the reaction kettle liner equipped with precursor slurry is placed in reaction kettle, seals, keeps the temperature 24 hours at 200 DEG C
Solvent heat treatment is carried out, then reaction kettle is allowed to naturally cool to room temperature, after unloading kettle, with dust technology washing reaction product repeatedly, mistake
Filter, drying, obtains the nano wire reticular structure calcium titanate visible light catalyst of favorable dispersibility.
Embodiment 6
(1) 1.65g butyl titanate is weighed, is added in 10ml ethylene glycol monomethyl ether, magnetic agitation obtains metatitanic acid to dissolving
Four butyl acetate solutions；
(2) under stirring, the mass concentration 30% of 1.5ml is added into the solution of tetrabutyl titanate of step (1) preparation
Ammonia spirit, precipitate, filter, washing, obtain titanium oxyhydroxide precipitating；
(3) 1.73g calcium nitrate is weighed, is added in 10mL deionized water, magnetic agitation to dissolution；
(4) 2.0g potassium hydroxide is weighed, is added in 10ml deionized water, magnetic agitation to dissolution；
(5) 8.0g polyvinyl alcohol is weighed, is added in 250ml deionized water, heats 90 DEG C of magnetic agitations to dissolution；
(6) 7ml is taken to be added to potassium hydroxide water prepared by step (4) from polyvinyl alcohol water solution prepared by step (5)
It is sufficiently stirred to obtain potassium hydroxide-polyvinyl alcohol water solution in solution；
(7) the oxyhydroxide precipitating of titanium is added in calcium nitrate aqueous solution, magnetic agitation at least 1h；Add step
(6) potassium hydroxide-polyvinyl alcohol water solution prepared in, is further continued for magnetic agitation at least 12h, obtains precursor slurry；Preceding body
The total mol concentration of titanium is 0.12mol/L in somaplasm material, and the molar ratio of calcium and titanium is 1.51 in precursor slurry, precursor slurry
The molar concentration of potassium hydroxide is 0.89mol/L in material, and the quality volume fraction of polyvinyl alcohol is 5.6g/L in precursor slurry.
(8) precursor slurry is added in reaction kettle liner, the volume of added slurry is the 80% of reaction kettle liner volume；
(9) the reaction kettle liner equipped with precursor slurry is placed in reaction kettle, seals, keeps the temperature 30 hours at 200 DEG C
Solvent heat treatment is carried out, then reaction kettle is allowed to naturally cool to room temperature, after unloading kettle, with dust technology washing reaction product repeatedly, mistake
Filter, drying, obtains the nano wire reticular structure calcium titanate visible light catalyst of favorable dispersibility.
Claims (8)
1. a kind of preparation method of nano wire reticular structure calcium titanate visible light catalyst characterized by comprising
(1) butyl titanate is dissolved in ethylene glycol monomethyl ether, obtains solution of tetrabutyl titanate；
(2) under stirring, 20~40wt% ammonia spirit is added into the solution of tetrabutyl titanate of step (1) preparation, precipitate,
It is filtered, washed, obtains the oxyhydroxide precipitating of titanium；
(3) calcium nitrate is soluble in water, obtain calcium nitrate aqueous solution；
(4) potassium hydroxide is soluble in water, obtain potassium hydroxide aqueous solution；
(5) polyvinyl alcohol is soluble in water, obtain polyvinyl alcohol water solution；
(6) polyvinyl alcohol water solution prepared by step (5) is added in the potassium hydroxide aqueous solution of step (4) preparation, stirring
Potassium hydroxide-polyvinyl alcohol water solution is obtained after uniformly；
(7) the oxyhydroxide precipitating of titanium is added in the calcium nitrate aqueous solution of step (3) preparation, stirs 1~5h；It adds
Potassium hydroxide-polyvinyl alcohol water solution of step (6) preparation is further continued for stirring at least 12h, obtains precursor slurry；Before described
In body slurry, the molar ratio of calcium and titanium is 1.0~2.0, and the molar concentration of potassium hydroxide is 0.4 in the precursor slurry
~1.5mol/L, the quality volume fraction of polyvinyl alcohol is 4~13g/L in the precursor slurry；
(8) precursor slurry is added in reaction kettle liner, the volume of added precursor slurry is the 70 of reaction kettle liner volume
~90%；
(9) the reaction kettle liner equipped with precursor slurry is placed in reaction kettle, is sealed, 24~96 are kept the temperature at 150~230 DEG C
Hour hydro-thermal process is carried out, then reaction kettle is allowed to naturally cool to room temperature, after unloading kettle, with dust technology washing reaction product repeatedly,
Filtering, drying, obtains nano wire reticular structure calcium titanate visible light catalyst.
2. the preparation method of nano wire reticular structure calcium titanate visible light catalyst according to claim 1, feature exist
In in step (4), the concentration of the potassium hydroxide aqueous solution is 2~10mol/L；In step (5), the polyvinyl alcohol is water-soluble
The concentration of liquid is 16~32g/L.
3. the preparation method of nano wire reticular structure calcium titanate visible light catalyst according to claim 1, feature exist
In the total mol concentration of titanium is 0.1~0.3mol/L in the precursor slurry.
4. the preparation method of nano wire reticular structure calcium titanate visible light catalyst according to claim 1, feature exist
In the reaction kettle is polytetrafluoroethylliner liner, the closed reaction kettle of stainless steel external member.
5. the preparation method of nano wire reticular structure calcium titanate visible light catalyst according to claim 1, feature exist
In the polyvinyl alcohol is PVA-124, and alcoholysis degree is 98~99 (m01) %, and average degree of polymerization is 2400~2500.
6. a kind of nano wire reticular structure calcium titanate visible light of method preparations described in any item according to claim 1~5 is urged
Agent.
7. a kind of nano wire reticular structure calcium titanate visible light of method preparations described in any item according to claim 1~5 is urged
The application of agent in the treatment of waste water.
8. a kind of nano wire reticular structure calcium titanate visible light of method preparations described in any item according to claim 1~5 is urged
Agent is decomposing the application in water hydrogen making.
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| CN106040214A (en) * | 2016-05-31 | 2016-10-26 | 浙江大学 | Method for preparing high-activity calcium titanate/calcium hydroxide mixed photocatalyst |
| CN106517319A (en) * | 2016-10-27 | 2017-03-22 | 浙江大学 | Preparation method for calcium titanate micron particles |
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| CN106040214A (en) * | 2016-05-31 | 2016-10-26 | 浙江大学 | Method for preparing high-activity calcium titanate/calcium hydroxide mixed photocatalyst |
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