CN106693942B - A kind of preparation method of high mesoporous honeycomb titanium dioxide optical catalyst - Google Patents
A kind of preparation method of high mesoporous honeycomb titanium dioxide optical catalyst Download PDFInfo
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 185
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- 239000003054 catalyst Substances 0.000 title claims abstract description 29
- 230000003287 optical effect Effects 0.000 title claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 52
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000008367 deionised water Substances 0.000 claims abstract description 24
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 24
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims abstract description 22
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000001035 drying Methods 0.000 claims abstract description 20
- 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 abstract description 15
- 229910000348 titanium sulfate Inorganic materials 0.000 claims abstract description 15
- 238000001354 calcination Methods 0.000 claims abstract description 14
- 238000000227 grinding Methods 0.000 claims abstract description 6
- 239000013049 sediment Substances 0.000 claims description 52
- 238000002156 mixing Methods 0.000 claims description 26
- 238000005406 washing Methods 0.000 claims description 26
- 238000001816 cooling Methods 0.000 claims description 25
- 239000000243 solution Substances 0.000 claims description 22
- 239000007787 solid Substances 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 13
- 229910001868 water Inorganic materials 0.000 claims description 8
- 238000010790 dilution Methods 0.000 claims description 5
- 239000012895 dilution Substances 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 2
- 239000005864 Sulphur Substances 0.000 claims 2
- 239000007788 liquid Substances 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 12
- 238000007146 photocatalysis Methods 0.000 abstract description 11
- 230000005540 biological transmission Effects 0.000 abstract description 8
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 8
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 230000001376 precipitating effect Effects 0.000 abstract description 4
- 230000009257 reactivity Effects 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- 239000008187 granular material Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 description 17
- 230000015556 catabolic process Effects 0.000 description 15
- 238000006731 degradation reaction Methods 0.000 description 15
- 239000013078 crystal Substances 0.000 description 10
- 230000007547 defect Effects 0.000 description 7
- 238000010586 diagram Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000010936 titanium Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 6
- 229910052719 titanium Inorganic materials 0.000 description 6
- 229910010413 TiO 2 Inorganic materials 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 description 4
- 230000004913 activation Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 210000003850 cellular structure Anatomy 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- -1 has infusion process Chemical compound 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 2
- 229940012189 methyl orange Drugs 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- GIKNHHRFLCDOEU-UHFFFAOYSA-N 4-(2-aminopropyl)phenol Chemical compound CC(N)CC1=CC=C(O)C=C1 GIKNHHRFLCDOEU-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000001507 sample dispersion Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000516 sunscreening agent Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
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- 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—
-
- B01J35/40—
-
- B01J35/56—
-
- B01J35/61—
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
-
- 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
- C02F2305/10—Photocatalysts
Abstract
The invention discloses a kind of preparation methods of high mesoporous honeycomb titanium dioxide optical catalyst, titanium sulfate is added in deionized water first and carries out hydro-thermal reaction in a high pressure reaction kettle, autoclave is cooled down at room temperature after reaction, gained precipitating is washed with deionized repeatedly to neutrality, three-dimensional anatase titanium dioxide is obtained after drying and grinding, then anatase titanium dioxide is added in hydrazine hydrate solution and carries out hydro-thermal reaction in a high pressure reaction kettle, it cools down after reaction, gained precipitating is washed with the dilute sulfuric acid of 2mol/L repeatedly, it washs again through deionized water to neutrality drying, honeycomb titanium dioxide can be obtained through calcining again；The present invention has synthesized high mesoporous honeycomb titanium dioxide by two one-step hydrothermals, it can be seen that honeycomb structure intensive on titanium dioxide granule under transmission electron microscope, with big specific surface area, more reactivity sites can be generated when light-catalyzed reaction, photocatalysis efficiency is improved, so that stable in catalytic performance.
Description
Technical field
The invention belongs to photochemical catalyst preparation method field, it is related to a kind of high mesoporous honeycomb titanium dioxide optical catalyst
Preparation method
Background technique
In recent years, with global environmental pollution and ecological disruption, give people for free of contamination clean manufacturing
Greatly concern, a kind of attention of the photocatalysis technology as energy-efficient green environmental protection technique increasingly by various countries.It is benefit
Pollutant is decomposed into the lesser substance of nontoxic or toxicity with light radiation.In numerous photochemical catalysts, titanium dioxide due to
Safe and non-toxic, the advantages that performance is stable, without side-effects, long service life, thus applies in wastewater treatment, atmospheric cleaning, automatically cleaning
Layer, suncream preparation, degradation toxic organic compound etc. are widely used.Since Fujishima in 1972 and Honda discovery by
The TiO of light irradiation2The generation redox reaction that water can be made to continue on particle, titanium dioxide as photochemical catalyst research and answer
With more and more extensive.
Since the physics and chemical characteristic and its crystal structure, crystal face, morphology and size of titanium dioxide are closely related, in recent years
Come, the controllable titanium dioxide of synthesis size and shape causes the extensive concern of domestic and international researcher.Nanoparticle size is smaller,
Specific surface area is bigger, and reactivity site is more, but the defect inside particle is also more；Intergranular interface is increased simultaneously,
As the capture trap of electrons and holes, photoelectric conversion efficiency is reduced.On the contrary, although big particle can be reduced inside particle
Defect and interface, but reduce specific surface area again, photoelectric conversion efficiency is also restrained.And in the photocatalytic process,
Grain surface is also an important factor for influencing photoelectric efficiency, so the cellular structure of material can not for the absorption of contaminant molecule
Ignore.Therefore, a kind of morphology controllable is developed, and synthetic method is simple, process cycle is short, and low-cost method has weight
The practical significance wanted.Currently, the method for synthesis of titanium dioxide mainly has infusion process, sol-gel method, hydrothermal synthesis method, alkoxide
Hydrolyze method, sluggish precipitation etc..The present invention uses two one-step hydrothermal synthesis of titanium dioxide, and product crystallinity obtained is high, dispersion
Property is good, and granular size is controllable, and photocatalysis performance is excellent.
However, electron-hole pair is easily compound due to titanium dioxide itself greater band gap, itself particle size, pattern hole
The factors such as the contradiction between road, crystallinity and photoelectric conversion efficiency, the photocatalytic degradation that these properties limit titanium dioxide have
The efficiency of machine pollutant.Such as: although photocatalysis effect is obvious under ultraviolet light for pure titinium dioxide at present, under visible light
Photocatalysis effect is unsatisfactory, and visible light application is more extensive in practice.Due to titania additive other elements
Photocatalysis efficiency and the hydrazine hydrate under the visible light of sample itself powerful reproducibility can be improved, therefore system is added
Hydrazine hydrate can not only introduce nitrogen atom doping, but also can destroy the tetravalence titanium ion on titanium dioxide surface to a certain extent,
Increase surface defect and increases mesoporous.The above are improve degradable organic pollutant under titanium dioxide natural light to have established solid base
Plinth.
Had the following problems: in the existing preparation process of titanium dioxide firstly, since at present industrial technology limitation, two
The technology of preparing of titanium oxide requires height, and morphology controllable is poor, easily forms large stretch of reunite；Secondly, made titanium dioxide is in visible light
Under photocatalysis efficiency it is integrally relatively low, therefore practicability is poor in practical degradation of contaminant；Finally, made pattern is difficult to
Form big specific surface.Such as the specific surface of P25 only about 50m2/g.So the defect based on existing preparation method, is badly in need of at present
A kind of preparation method improveing disadvantages described above.
In prior art basis, the present invention provides a kind of preparation sides of high mesoporous honeycomb optically catalytic TiO 2
Method.Using hydro-thermal reaction and heat treatment, change the appearance structure of titanium dioxide, preparation crystallinity is high, crystallite dimension is tiny, honeycomb
The titanium dioxide of shape structure has important application value to improve photocatalysis efficiency.
Summary of the invention
The present invention is in order to solve the above technical problems, provide a kind of preparation of high mesoporous honeycomb titanium dioxide optical catalyst
Method.
In order to solve the above technical problems, the present invention is achieved by the following technical scheme:
A kind of preparation method of high mesoporous honeycomb titanium dioxide optical catalyst, which is characterized in that specific preparation step is such as
Under:
One, the titanium sulfate solid for weighing 1.0g~1.5g, is dissolved in 30mL deionized water, is transferred to high pressure after evenly mixing
In reaction kettle, constant temperature is kept for 48 hours at 180 DEG C, is after reaction cooled down autoclave at room temperature, after cooling
It is 7 that the sediment of acquisition, which is washed with deionized to pH value, then will be ground after drying at the sediment after washing in an oven 60 DEG C
Mill, obtains three-dimensional anatase titanium dioxide；
Two, the three-dimensional anatase titanium dioxide that 0.5g~1.0g step 1 obtains is weighed, the hydrazine hydrate of 5~10mL is instilled
Solution, then above-mentioned mixed solution is settled to 30mL with deionized water, it is transferred in autoclave after evenly mixing, 120
DEG C~150 DEG C at kept for 48 hours, autoclave is cooled down at room temperature after reaction, the sediment that will be obtained after cooling
Being washed with the dilution heat of sulfuric acid of 2mol/L to pH value is 3, then being washed with deionized to pH value is 7, by the sediment after washing
It is ground after dry at 60 DEG C in an oven, finally calcining 2~4 hours at 400 DEG C~500 DEG C in Muffle furnace can be obtained Gao Jie
Hole honeycomb titanium dioxide.
Compared with prior art the beneficial effects of the present invention are:
1. the mesoporous honeycomb titanium dioxide of height prepared by the present invention is easy to operate compared with other techniques, error is smaller,
Safety and stability is reliable；And the temperature range prepared is smaller to technique sample effects produced, strong operability.
2. the mesoporous honeycomb titanium dioxide of height prepared by the present invention is under transmission electron microscope it can be seen that having similar honeycomb
The high meso-hole structure of the Large ratio surface of shape, and made sample dispersion is preferable, size tiny (about 10nm), crystallinity are high.
3. the photocatalysis effect of the mesoporous honeycomb titanium dioxide of height prepared by present invention relationship commodity P25 under visible light
It is more significant, therefore it is more suitable practical application.
4, the present invention can not only be mixed during preparing high mesoporous honeycomb titanium dioxide by using hydrazine hydrate
The nitrogen sensitive to visible light, and the titanic ion activation on surface can be changed to trivalent titanium ion, thus in table
Face forms point defect, and then improves the activation energy of system.
5, the mesoporous honeycomb titanium dioxide of height prepared by the present invention makes titanium dioxide from business perspective relative inexpensiveness
A possibility that certain and actuality, have been established in the large-scale production of photochemical catalyst.
Detailed description of the invention
The present invention will be further described below with reference to the drawings:
Fig. 1 is prepared using a kind of preparation method of high mesoporous honeycomb titanium dioxide optical catalyst of the present invention
The mesoporous honeycomb titanium dioxide of height process flow chart；
Fig. 2 is prepared using a kind of preparation method of high mesoporous honeycomb titanium dioxide optical catalyst of the present invention
The mesoporous honeycomb titanium dioxide of height X ray diffracting spectrum；
Fig. 3 is prepared using a kind of preparation method of high mesoporous honeycomb titanium dioxide optical catalyst of the present invention
Transmission electron microscope figure of the mesoporous honeycomb optically catalytic TiO 2 of height under 50nm ratio；
Fig. 4 is prepared using a kind of preparation method of high mesoporous honeycomb titanium dioxide optical catalyst of the present invention
Transmission electron microscope figure of the mesoporous honeycomb optically catalytic TiO 2 of height under 25nm ratio；
Fig. 5 is prepared using a kind of preparation method of high mesoporous honeycomb titanium dioxide optical catalyst of the present invention
Transmission electron microscope figure of the mesoporous honeycomb optically catalytic TiO 2 of height under 10nm ratio；
Fig. 6 is prepared using a kind of preparation method of high mesoporous honeycomb titanium dioxide optical catalyst of the present invention
The degradation rate of the mesoporous honeycomb optically catalytic TiO 2 of height and the effect picture that compares of the degradation rate of common P25；
Fig. 7 is that a kind of high mesoporous honeycomb titanium dioxide of the present invention is used in each embodiment of specific embodiment
The degradation rate for each sample that the preparation method of photochemical catalyst is prepared compares histogram；
Fig. 8 is high mesoporous bee in a kind of preparation method of high mesoporous honeycomb titanium dioxide optical catalyst of the present invention
The formation mechenism figure of nest shape titanium dioxide；
Fig. 9 is three-dimensional anatase laminated structure schematic diagram；
Figure 10 is that mesoporous titanium dioxide structure forms rear crystal grain distribution schematic diagram；
Figure 11 is step 1 in a kind of preparation method of high mesoporous honeycomb titanium dioxide optical catalyst of the present invention
The three-dimensional Detitanium-ore-type plate-like titanium dioxide crystalline mi dot matrix schematic diagram prepared；
Figure 12 is step 2 in a kind of preparation method of high mesoporous honeycomb titanium dioxide optical catalyst of the present invention
In mix the mesoporous honeycomb titanium dioxide crystal dot matrix schematic diagram of height formed after hydrazine hydrate.
Specific embodiment
The present invention is explained in detail with reference to the accompanying drawing:
The invention discloses a kind of preparation methods of high mesoporous honeycomb titanium dioxide optical catalyst, first add titanium sulfate
Enter and carry out hydro-thermal reaction in deionized water in a high pressure reaction kettle, after reaction cools down autoclave at room temperature, it will
Gained precipitating is washed with deionized repeatedly to neutrality, obtains three-dimensional anatase titanium dioxide after drying and grinding, then will be sharp
Titanium ore type titanium dioxide is added in hydrazine hydrate solution carries out hydro-thermal reaction in a high pressure reaction kettle, cools down after reaction, will
Gained precipitating is washed with the dilute sulfuric acid of 2mol/L repeatedly.Then after being washed to neutral drying, then through calcining bee can be obtained
Nest shape titanium dioxide.The present invention has synthesized high mesoporous honeycomb titanium dioxide, the process flow of this method by two one-step hydrothermals
Figure is as shown in Figure 1, specific preparation process is as follows:
One, the titanium sulfate solid for weighing 1.0g~1.5g, is dissolved in 30mL deionized water, is transferred to high pressure after evenly mixing
In reaction kettle, constant temperature is kept for 48 hours at 180 DEG C, is after reaction cooled down autoclave at room temperature, after cooling
It is 7 that the sediment of acquisition, which is washed with deionized to pH value, then will be ground after drying at the sediment after washing in an oven 60 DEG C
Mill, obtains three-dimensional anatase titanium dioxide；
Two, the three-dimensional anatase titanium dioxide that 0.5g~1.0g step 1 obtains is weighed, the hydrazine hydrate of 5~10mL is instilled
Solution, then above-mentioned mixed solution is settled to 30mL with deionized water, it is transferred in autoclave after evenly mixing, 120
DEG C~150 DEG C at kept for 48 hours, autoclave is cooled down at room temperature after reaction, the sediment that will be obtained after cooling
Being washed with the dilution heat of sulfuric acid of 2mol/L to pH value is 3, then being washed with deionized to pH value is 7, by the sediment after washing
It is ground after dry at 60 DEG C in an oven, finally calcining 2~4 hours at 400 DEG C~500 DEG C in Muffle furnace can be obtained Gao Jie
Hole honeycomb titanium dioxide.
A kind of preparation method of high mesoporous honeycomb titanium dioxide optical catalyst of the present invention, reaction mechanism process is such as
Under:
Its formation mechenism forms the [Ti (H that ligancy is 6 as shown in figure 8, titanium ion is dissolved in water2O)6]4+, [Ti (H2O)6]4+
Continuous dehydrogenation is dehydrated to form oxygen bridge structure, with the continuous progress of reaction, forms one-dimensional metatitanic acid structure.One-dimensional metatitanic acid structure is continuous
Dehydration forms oxygen bridge structure, highly crystalline three-dimensional Detitanium-ore-type plate-like titanium dioxide is finally formed in the case where orienting adhewsive action, such as
Shown in Fig. 9.Fig. 9 describes three-dimensional anatase laminated structure, and each bulk portion illustrates the anatase crystal grain of a crystallization, ellipse
Circular portion is crystal grain enlarged drawing, that is, microcosmic schematic diagram of titanium dioxide lattice, as shown in figure 11.
The sheet anatase as shown in Figure 9 of acquisition is added in hydrazine hydrate, hydrazine hydrate N2H4The OH ionized out-And H2O into
Enter into anatase, it in crystal grain titanium atom and oxygen atom react, generate HTiO3-(titanium hydroxyl).Then, HTiO3-It wears
Grain surface is crossed to spread to outside.At the same time, these location proximates being pierced generate the vacancy flow of opposite direction, with titanium hydroxyl
Flowing mutually balance.OH-A large amount of presence can promote HTiO3-Quickly generate, finally, HTiO3-It is resulted in Void diffusing
Cellular structure is formed inside anatase.Final as shown in Figure 10, some original anatase crystal grain positions form mesoporous i.e. figure
Middle black portions.Its microcosmic lattice structure is as shown in figure 11, as can be seen from the figure this piece synthesized by one step hydro thermal method
The anatase structured crystallinity with height of shape.During hydration hydrazine reaction is added, the nitrogen in hydrazine hydrate can part substitution
Oxygen in titanium dioxide forms point defect, and hydrazine ion can change the oriented trivalent titanium ion of the titanic ion activation on surface
Trend, thus surface formed point defect, and then improve system activation energy, ultimately form doping point as shown in figure 12
Battle array structure, to improve photocatalysis efficiency.
Below by several embodiments to a kind of system of high mesoporous honeycomb titanium dioxide optical catalyst of the present invention
Preparation Method makes further instructions:
Embodiment 1
One, the titanium sulfate solid that quality is 1.0g is weighed, is dissolved in 30mL deionized water, is transferred to high pressure after evenly mixing
In reaction kettle, constant temperature is kept for 48 hours at 180 DEG C, is after reaction cooled down autoclave at room temperature, after cooling
It is 7 that the sediment of acquisition, which is washed with deionized to pH value, then will be ground after drying at the sediment after washing in an oven 60 DEG C
Mill, obtains three-dimensional anatase titanium dioxide；
Two, the three-dimensional anatase titanium dioxide that 1.0g step 1 obtains is weighed, instills the hydrazine hydrate solution of 10mL, then use
Above-mentioned mixed solution is settled to 30mL by deionized water, is transferred in autoclave after evenly mixing, and constant temperature is protected at 150 DEG C
It holds 48 hours, after reaction cools down autoclave at room temperature, the sediment obtained after cooling is dilute with 2mol/L
It is 3 that sulfuric acid solution, which is washed to pH value, then being washed with deionized to pH value is 7, by 60 DEG C in an oven of the sediment after washing
It is ground after drying, high mesoporous honeycomb titanium dioxide can be obtained within finally calcining at constant temperature 4 hours at 500 DEG C in Muffle furnace.
Test results are shown in figure 2 through X-ray diffraction for 1 sample of gained example, and abscissa A is 2 θ of angle of diffraction in the figure,
Ordinate B is diffracted intensity, is anatase titanium dioxide with (X-ray diffraction standard card) comparative analysis of standard PDF card,
Diffracting spectrum peak shape sharply illustrates that crystallinity height, crystal grain are tiny.As shown in figure 3, the transmission electron microscope under 50nm ratio
It is in figure it can be seen that many such as cellular cavity.As shown in figure 4, can be in the transmission electron microscope figure under 25nm ratio
See the dispersibility of sample preferably.As shown in figure 5, it can be seen that rule row in the transmission electron microscope figure under 10nm ratio
The lattice fringe of column, (001) crystal face of counter sample are consistent with the result of XRD test.Sample is degraded methyl orange under visible light
Solution, the degradation rate after 120 minutes are 97.1%, and the degradation rate comparison diagram with common P25 is as shown in fig. 6, abscissa A is drop
The time is solved, unit is minute, and ordinate B is degradation rate, with remaining methyl orange concentration C and initial orange concentration C0Ratio come
It indicates, as can be seen from the figure 1 sample degradation of example is more efficient.
Embodiment 2
One, the titanium sulfate solid that quality is 1.5g is weighed, is dissolved in 30mL deionized water, is transferred to high pressure after evenly mixing
In reaction kettle, constant temperature is kept for 48 hours at 180 DEG C, is after reaction cooled down autoclave at room temperature, after cooling
It is 7 that the sediment of acquisition, which is washed with deionized to pH value, then will be ground after drying at the sediment after washing in an oven 60 DEG C
Mill, obtains three-dimensional anatase titanium dioxide；
Two, the three-dimensional anatase titanium dioxide that 0.5g step 1 obtains is weighed, instills the hydrazine hydrate solution of 10mL, then use
Above-mentioned mixed solution is settled to 30mL by deionized water, is transferred in autoclave after evenly mixing, and constant temperature is protected at 150 DEG C
It holds 48 hours, after reaction cools down autoclave at room temperature, the sediment obtained after cooling is dilute with 2mol/L
It is 3 that sulfuric acid solution, which is washed to pH value, then being washed with deionized to pH value is 7, by 60 DEG C in an oven of the sediment after washing
It is ground after lower drying, high mesoporous honeycomb titanium dioxide can be obtained within finally calcining at constant temperature 3 hours at 500 DEG C in Muffle furnace.
Obtained 2 sample of example is degraded methyl orange solution under visible light, and the degradation rate after 120 minutes is 95.4%.
Embodiment 3
One, the titanium sulfate solid that quality is 1.25g is weighed, is dissolved in 30mL deionized water, is transferred to height after evenly mixing
It presses in reaction kettle, constant temperature is kept for 48 hours at 180 DEG C, is after reaction cooled down autoclave at room temperature, will be cooled down
It is 7 that the sediment obtained afterwards, which is washed with deionized to pH value, then will be at the sediment after washing in an oven 60 DEG C after drying
Grinding, obtains three-dimensional anatase titanium dioxide；
Two, the three-dimensional anatase titanium dioxide that 1.0g step 1 obtains is weighed, instills the hydrazine hydrate solution of 5mL, then use
Above-mentioned mixed solution is settled to 30mL by deionized water, is transferred in autoclave after evenly mixing, and constant temperature is protected at 150 DEG C
It holds 48 hours.Autoclave is cooled down at room temperature after reaction, the sediment obtained after cooling is dilute with 2mol/L
It is 3 that sulfuric acid solution, which is washed to pH value, then being washed with deionized to pH value is 7, by 60 DEG C in an oven of the sediment after washing
It is ground after lower drying, high mesoporous honeycomb titanium dioxide can be obtained within finally calcining at constant temperature 4 hours at 450 DEG C in Muffle furnace.
Obtained 3 sample of example is degraded methyl orange solution under visible light, and degradation rate is 91.3% after 120 minutes.
Embodiment 4
One, the titanium sulfate solid that quality is 1.0g is weighed, is dissolved in 30mL deionized water, is transferred to high pressure after evenly mixing
In reaction kettle, constant temperature is kept for 48 hours at 180 DEG C, is after reaction cooled down autoclave at room temperature, after cooling
It is 7 that the sediment of acquisition, which is washed with deionized to pH value, then will be ground after drying at the sediment after washing in an oven 60 DEG C
Mill, obtains three-dimensional anatase titanium dioxide；
Two, the three-dimensional anatase titanium dioxide that 1.0g step 1 obtains is weighed, the hydrazine hydrate solution of 7.5mL is instilled, then
Above-mentioned mixed solution is settled to 30mL with deionized water, is transferred in autoclave after evenly mixing, the constant temperature at 120 DEG C
It is kept for 48 hours, is after reaction cooled down autoclave at room temperature, by the sediment obtained after cooling with 2mol/L's
It is 3 that dilution heat of sulfuric acid, which is washed to pH value, then being washed with deionized to pH value is 7, by the sediment after washing in an oven 60
It is ground after drying at DEG C, high mesoporous honeycomb titanium dioxide can be obtained within finally calcining at constant temperature 4 hours at 400 DEG C in Muffle furnace
Titanium.
Obtained 4 sample of example is degraded methyl orange solution under visible light, and degradation rate is 89.6% after 120 minutes.
Embodiment 5
One, the titanium sulfate solid that quality is 1.0g is weighed, is dissolved in 30mL deionized water, is transferred to high pressure after evenly mixing
In reaction kettle, constant temperature is kept for 48 hours at 180 DEG C, is after reaction cooled down autoclave at room temperature, after cooling
It is 7 that the sediment of acquisition, which is washed with deionized to pH value, then will be ground after drying at the sediment after washing in an oven 60 DEG C
Mill, obtains three-dimensional anatase titanium dioxide；
Two, the three-dimensional anatase titanium dioxide that 0.75g step 1 obtains is weighed, the hydrazine hydrate solution of 10mL is instilled, then
Above-mentioned mixed solution is settled to 30mL with deionized water, is transferred in autoclave after evenly mixing, the constant temperature at 130 DEG C
It is kept for 48 hours, is after reaction cooled down autoclave at room temperature, by the sediment obtained after cooling with 2mol/L's
It is 3 that dilution heat of sulfuric acid, which is washed to pH value, then being washed with deionized to pH value is 7, by the sediment after washing in an oven 60
It is ground after drying at DEG C, high mesoporous honeycomb titanium dioxide can be obtained within finally calcining at constant temperature 2 hours at 500 DEG C in Muffle furnace
Titanium.
Obtained 5 sample of example is degraded methyl orange solution under visible light, and degradation rate is 90.7% after 120 minutes.
The degradation rate comparison diagram for the sample that each embodiment is prepared is as shown in Figure 7, it is seen that 1 sample of example is photocatalysis effect
Best, it is that degradation rate is highest in all samples.
Claims (6)
1. a kind of preparation method of high mesoporous honeycomb titanium dioxide optical catalyst, which is characterized in that specific preparation process is as follows:
One, the titanium sulfate solid for weighing 1.0g~1.5g, is dissolved in 30mL deionized water, is transferred to reaction under high pressure after evenly mixing
In kettle, constant temperature is kept for 48 hours at 180 DEG C, is after reaction cooled down autoclave at room temperature, will be obtained after cooling
Sediment to be washed with deionized to pH value be 7, then will it is dry at the sediment after washing in an oven 60 DEG C after grind, obtain
To three-dimensional anatase titanium dioxide；
Two, the three-dimensional anatase titanium dioxide that 0.5g~1.0g step 1 obtains is weighed, the hydrazine hydrate for instilling 5~10mL is molten
Liquid, then above-mentioned mixed solution is settled to 30mL with deionized water, it is transferred in autoclave after evenly mixing, at 120 DEG C
It is kept for 48 hours at~150 DEG C, after reaction cools down autoclave at room temperature, the sediment obtained after cooling is used
It is 3 that the dilution heat of sulfuric acid of 2mol/L, which is washed to pH value, then being washed with deionized to pH value is 7, and the sediment after washing is existed
In baking oven it is dry at 60 DEG C after grind, finally calcine that height can be obtained within 2~4 hours is mesoporous at 400 DEG C~500 DEG C in Muffle furnace
Honeycomb titanium dioxide.
2. a kind of preparation method of high mesoporous honeycomb titanium dioxide optical catalyst according to claim 1, feature exist
In: specific preparation process is as follows:
One, the titanium sulfate solid that quality is 1.0g is weighed, is dissolved in 30mL deionized water, is transferred to reaction under high pressure after evenly mixing
In kettle, constant temperature is kept for 48 hours at 180 DEG C, is after reaction cooled down autoclave at room temperature, will be obtained after cooling
Sediment to be washed with deionized to pH value be 7, then will it is dry at the sediment after washing in an oven 60 DEG C after grind, obtain
To three-dimensional anatase titanium dioxide；
Two, weigh the three-dimensional anatase titanium dioxide that 1.0g step 1 obtains, instill the hydrazine hydrate solution of 10mL, then spend from
Above-mentioned mixed solution is settled to 30mL by sub- water, is transferred in autoclave after evenly mixing, and constant temperature keeps 48 at 150 DEG C
Hour, autoclave is cooled down at room temperature after reaction, by the dilute sulfuric acid of the sediment 2mol/L obtained after cooling
It is 3 that solution, which is washed to pH value, then being washed with deionized to pH value is 7, will be done at the sediment after washing in an oven 60 DEG C
High mesoporous honeycomb titanium dioxide can be obtained for finally calcining at constant temperature 4 hours at 500 DEG C in Muffle furnace in grinding after dry.
3. a kind of preparation method of high mesoporous honeycomb titanium dioxide optical catalyst according to claim 1, feature exist
In specific preparation process is as follows:
One, the titanium sulfate solid that quality is 1.5g is weighed, is dissolved in 30mL deionized water, is transferred to reaction under high pressure after evenly mixing
In kettle, is kept for 48 hours, after reaction cooled down autoclave at room temperature, by what is obtained after cooling in 180 DEG C of constant temperature
It is 7 that sediment, which is washed with deionized to pH value, then will be ground after drying at the sediment after washing in an oven 60 DEG C, is obtained
Three-dimensional anatase titanium dioxide；
Two, weigh the three-dimensional anatase titanium dioxide that 0.5g step 1 obtains, instill the hydrazine hydrate solution of 10mL, then spend from
Above-mentioned mixed solution is settled to 30mL by sub- water, is transferred in autoclave after evenly mixing, and constant temperature keeps 48 at 150 DEG C
Hour, autoclave is cooled down at room temperature after reaction, by the dilute sulfuric acid of the sediment 2mol/L obtained after cooling
It is 3 that solution, which is washed to pH value, then being washed with deionized to pH value is 7, will be done at the sediment after washing in an oven 60 DEG C
High mesoporous honeycomb titanium dioxide can be obtained for finally calcining at constant temperature 3 hours at 500 DEG C in Muffle furnace in grinding after dry.
4. a kind of preparation method of high mesoporous honeycomb titanium dioxide optical catalyst according to claim 1, feature exist
In: specific preparation process is as follows:
One, the titanium sulfate solid that quality is 1.25g is weighed, is dissolved in 30mL deionized water, it is anti-to be transferred to high pressure after evenly mixing
It answers in kettle, constant temperature is kept for 48 hours at 180 DEG C, is after reaction cooled down autoclave at room temperature, will be obtained after cooling
It is 7 that the sediment obtained, which is washed with deionized to pH value, then will be ground after drying at the sediment after washing in an oven 60 DEG C,
Obtain three-dimensional anatase titanium dioxide；
Two, weigh the three-dimensional anatase titanium dioxide that 1.0g step 1 obtains, instill the hydrazine hydrate solution of 5mL, then spend from
Above-mentioned mixed solution is settled to 30mL by sub- water, is transferred in autoclave after evenly mixing, and constant temperature keeps 48 at 150 DEG C
Hour, autoclave is cooled down at room temperature after reaction, by the dilute sulfuric acid of the sediment 2mol/L obtained after cooling
It is 3 that solution, which is washed to pH value, then being washed with deionized to pH value is 7, will be done at the sediment after washing in an oven 60 DEG C
High mesoporous honeycomb titanium dioxide can be obtained for finally calcining at constant temperature 4 hours at 450 DEG C in Muffle furnace in grinding after dry.
5. a kind of preparation method of high mesoporous honeycomb titanium dioxide optical catalyst according to claim 1, feature exist
In specific preparation process is as follows:
One, the titanium sulfate solid that quality is 1.0g is weighed, is dissolved in 30mL deionized water, is transferred to reaction under high pressure after evenly mixing
In kettle, constant temperature is kept for 48 hours at 180 DEG C, is after reaction cooled down autoclave at room temperature, will be obtained after cooling
Sediment to be washed with deionized to pH value be 7, then will it is dry at the sediment after washing in an oven 60 DEG C after grind, obtain
To three-dimensional anatase titanium dioxide；
Two, the three-dimensional anatase titanium dioxide that 1.0g step 1 obtains is weighed, instills the hydrazine hydrate solution of 7.5mL, then spend
Above-mentioned mixed solution is settled to 30mL by ionized water, is transferred in autoclave after evenly mixing, and constant temperature is kept at 120 DEG C
48 hours, autoclave is cooled down at room temperature after reaction, by the sediment obtained after cooling dilute sulphur of 2mol/L
Acid solution wash to pH value is 3, then being washed with deionized to pH value is 7, will be at the sediment after washing in an oven 60 DEG C
It is ground after drying, high mesoporous honeycomb titanium dioxide can be obtained within finally calcining at constant temperature 4 hours at 400 DEG C in Muffle furnace.
6. a kind of preparation method of high mesoporous honeycomb titanium dioxide optical catalyst according to claim 1, feature exist
In specific preparation process is as follows:
One, the titanium sulfate solid that quality is 1.0g is weighed, is dissolved in 30mL deionized water, is transferred to reaction under high pressure after evenly mixing
In kettle, constant temperature is kept for 48 hours at 180 DEG C, is after reaction cooled down autoclave at room temperature, will be obtained after cooling
Sediment to be washed with deionized to pH value be 7, then will it is dry at the sediment after washing in an oven 60 DEG C after grind, obtain
To three-dimensional anatase titanium dioxide；
Two, the three-dimensional anatase titanium dioxide that 0.75g step 1 obtains is weighed, instills the hydrazine hydrate solution of 10mL, then spend
Above-mentioned mixed solution is settled to 30mL by ionized water, is transferred in autoclave after evenly mixing, and constant temperature is kept at 130 DEG C
48 hours, autoclave is cooled down at room temperature after reaction, by the sediment obtained after cooling dilute sulphur of 2mol/L
Acid solution wash to pH value is 3, then being washed with deionized to pH value is 7, will be at the sediment after washing in an oven 60 DEG C
It is ground after drying, high mesoporous honeycomb titanium dioxide can be obtained within finally calcining at constant temperature 2 hours at 500 DEG C in Muffle furnace.
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| CN101422725A (en) * | 2007-11-02 | 2009-05-06 | 中国科学院过程工程研究所 | Preparation method and use of visible light responsive nitrogen-doped titanium dioxide nano-tube |
| CN102327779A (en) * | 2011-07-04 | 2012-01-25 | 山东轻工业学院 | Preparation method and application of nitrogen-doped titanium dioxide heterojunction structure |
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| CN101422725A (en) * | 2007-11-02 | 2009-05-06 | 中国科学院过程工程研究所 | Preparation method and use of visible light responsive nitrogen-doped titanium dioxide nano-tube |
| CN102327779A (en) * | 2011-07-04 | 2012-01-25 | 山东轻工业学院 | Preparation method and application of nitrogen-doped titanium dioxide heterojunction structure |
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| One-step construction of N/Ti3+ codoped TiO2 nanotubes photoelectrode with high photoelectrochemical and photoelectrocatalytic performance;Xiuwen Cheng et al.;《Electrochimica Acta》;20151104;第442-448页 |
| One-Step Template-Free Route for Synthesis of Mesoporous N-Doped Titania Spheres;Bo Chi et al.;《J. Phys. Chem. C》;20071204;第6189-6193页 |
| 微波掺氮改性纳米二氧化钛的研究;邓仕英等;《化学与生物工程》;20120331;第13-17页 |
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