CN110420630A - A kind of black titanium dioxide photochemical catalyst and the preparation method and application thereof - Google Patents
A kind of black titanium dioxide photochemical catalyst and the preparation method and application thereof Download PDFInfo
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- CN110420630A CN110420630A CN201910822203.1A CN201910822203A CN110420630A CN 110420630 A CN110420630 A CN 110420630A CN 201910822203 A CN201910822203 A CN 201910822203A CN 110420630 A CN110420630 A CN 110420630A
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 194
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 78
- 239000003054 catalyst Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 238000001354 calcination Methods 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 241000195493 Cryptophyta Species 0.000 claims abstract description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229960000935 dehydrated alcohol Drugs 0.000 claims abstract description 26
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000010936 titanium Substances 0.000 claims abstract description 25
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 25
- 235000015110 jellies Nutrition 0.000 claims abstract description 24
- 239000008274 jelly Substances 0.000 claims abstract description 24
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 18
- 239000003112 inhibitor Substances 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 238000006460 hydrolysis reaction Methods 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 19
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 17
- 239000004202 carbamide Substances 0.000 claims description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 230000007062 hydrolysis Effects 0.000 claims description 12
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000011521 glass Substances 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 claims description 3
- 238000005660 chlorination reaction Methods 0.000 claims 1
- 238000004321 preservation Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 17
- 230000008569 process Effects 0.000 abstract description 8
- 238000005516 engineering process Methods 0.000 abstract description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 4
- 239000001301 oxygen Substances 0.000 abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 abstract description 4
- 235000010215 titanium dioxide Nutrition 0.000 description 77
- 230000000694 effects Effects 0.000 description 14
- 238000002156 mixing Methods 0.000 description 12
- 229930002875 chlorophyll Natural products 0.000 description 11
- 235000019804 chlorophyll Nutrition 0.000 description 11
- ATNHDLDRLWWWCB-AENOIHSZSA-M chlorophyll a Chemical compound C1([C@@H](C(=O)OC)C(=O)C2=C3C)=C2N2C3=CC(C(CC)=C3C)=[N+]4C3=CC3=C(C=C)C(C)=C5N3[Mg-2]42[N+]2=C1[C@@H](CCC(=O)OC\C=C(/C)CCC[C@H](C)CCC[C@H](C)CCCC(C)C)[C@H](C)C2=C5 ATNHDLDRLWWWCB-AENOIHSZSA-M 0.000 description 11
- 238000010586 diagram Methods 0.000 description 11
- 238000006555 catalytic reaction Methods 0.000 description 8
- 230000001699 photocatalysis Effects 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000007146 photocatalysis Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 5
- 238000013019 agitation Methods 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229910052724 xenon Inorganic materials 0.000 description 4
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 230000003301 hydrolyzing effect Effects 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 240000001414 Eucalyptus viminalis Species 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000012851 eutrophication Methods 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 238000007689 inspection Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 2
- 230000036961 partial effect Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- 241000251468 Actinopterygii Species 0.000 description 1
- 206010003497 Asphyxia Diseases 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 229910011208 Ti—N Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000011953 bioanalysis Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000034994 death Effects 0.000 description 1
- 231100000517 death Toxicity 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 230000002503 metabolic effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 238000001429 visible spectrum Methods 0.000 description 1
Classifications
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; Compounds thereof
-
- 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
-
- 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
-
- 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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/50—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
-
- 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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/007—Contaminated open waterways, rivers, lakes or ponds
-
- 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
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Agronomy & Crop Science (AREA)
- Inorganic Chemistry (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to water-treatment technology fields more particularly to a kind of black titanium dioxide photochemical catalyst and the preparation method and application thereof.Preparation method of the invention is hydrolyzed reaction, obtains jelly the following steps are included: will include that the first mixed liquor of titanium source and dehydrated alcohol is mixed with the second mixed liquor including inhibitor, water and dehydrated alcohol；The jelly is calcined under a nitrogen atmosphere, obtains black titanium dioxide photochemical catalyst.The present invention mixes the first mixed liquor with the second mixed liquor, and titanium source is met water and hydrolyzed, and obtains jelly；Jelly is calcined under a nitrogen atmosphere later, calcination process will form Lacking oxygen in titanium dioxide surface, while generate Ti3+, so that the band gap of titanium dioxide is narrowed, so as to which visible light is absorbed and utilized, effectively remove harmful algae in water body.
Description
Technical field
The present invention relates to water-treatment technology fields more particularly to a kind of black titanium dioxide photochemical catalyst and preparation method thereof
With application.
Background technique
Currently, water body in lake eutrophication is got worse, and cyanobacterial bloom outburst is the important of water eutrophication
One of characterization and China or even the whole world water environmental problems the most serious.The freshwater lake and reservoir in China 66% are long-term
By the infringement of cyanobacterial bloom.The generation of wawter bloom can cause the generation of the deaths by suffocation such as fish and aquatic animal, toxic gas
With the forfeiture of water ecosystem function etc., human health is directly endangered.The Control Technology of harmful algae mainly include physical method,
Chemical method and bioanalysis, but in place of these traditional algae removal technologies all Shortcomings, cause the prevention and control process of wawter bloom algae especially
It is difficult, it shoulders heavy responsibilities.
Nano material photocatalysis technology provides new thinking for the improvement of water environment pollution, a large number of studies show that, it utilizes
Nano material photocatalytic process can successfully inhibit the growth of bloom blue algae, or even gradually degrade frustule and detrimental metabolic production
Object, wherein TiO2Because having the unique performance such as low in cost, nonhazardous, high-efficient to obtain extensive research.But TiO2Band gap
Wider, light abstraction width is confined to the ultraviolet region that wavelength is less than 387nm, to limit TiO2The efficiency of light energy utilization, especially
It is that cannot make full use of visible light abundant in nature.Currently, TiO2Study on the modification focus on widening its visible spectrum
Response range is to increase the efficiency of light energy utilization, but in terms of current research achievement, it is seen that the utilization rate of solar energy is not high, needs
The modification method for preparing of innovation improves the utilization rate of visible light, is answered with accelerating popularization of the photocatalysis technology in terms of controlling algae algal control
With.
The appearance of black titanium dioxide overcomes the above problem, and there is excellent visible absorption performance and surface reaction to live
Property, therefore there is stronger photocatalysis characteristic.The representative preparation method of black titanium dioxide has hydrogen reduction method, aluminothermic reduction
Method, solution-evaporation, but there are the drawbacks such as security risk and the high requirements on the equipment for the above method.How to utilize mild simple
Energy band is narrow for method preparation, the black titanium dioxide more than defect is the key that promote photocatalysis technology except algae field is applied.
Summary of the invention
The purpose of the present invention is to provide a kind of black titanium dioxide photochemical catalyst and the preparation method and application thereof, the present invention
The black titanium dioxide photochemical catalyst band gap of preparation is relatively narrow, can fully absorb visible light, can effectively remove the nocuousness in water body
Algae, and preparation method is simple, mild.
In order to achieve the above-mentioned object of the invention, the present invention the following technical schemes are provided:
The present invention provides a kind of preparation methods of black titanium dioxide photochemical catalyst, comprising the following steps:
By the first mixed liquor for including titanium source and dehydrated alcohol and the second mixed liquor including inhibitor, water and dehydrated alcohol
Mixing, is hydrolyzed reaction, obtains jelly；
The jelly is calcined under a nitrogen atmosphere, obtains black titanium dioxide photochemical catalyst.
Preferably, the titanium source includes butyl titanate or titanium tetrachloride；The inhibitor includes concentrated hydrochloric acid or concentrated nitric acid.
Preferably, in the mixed system of the hydrolysis, titanium source, inhibitor, water and dehydrated alcohol molar ratio be
(3.0~4.0): 1:(23.0~24.0): (42.0~43.0).
It preferably, further include urea in first mixed liquor；When further including urea in the first mixed liquor, the hydrolysis
In the mixed system of reaction, titanium source, urea, inhibitor, water and dehydrated alcohol molar ratio be (3.0~4.0): (0.28~
1.11): 1:(23.0~24.0): (42.0~43.0).
Preferably, it is stirred in the hydrolysis reaction using glass bar, the time of hydrolysis is 1~3min.
Preferably, the temperature of the calcining is 400~600 DEG C, and soaking time is 2~4h.
It preferably, further include being dried to jelly before the calcining, the temperature of the drying is 60~80 DEG C, the time
For 10~12h.
Preferably, the mode first mixed liquor mixed with second mixed liquor are as follows: the second mixed liquor is added dropwise
It is mixed into the first mixed liquor.
The present invention provides the black titanium dioxide photochemical catalysts that preparation method described in above scheme is prepared.
The present invention provides black titanium dioxide photochemical catalysts described in above scheme in visible light catalytic removal algae
Using.
The present invention provides a kind of preparation methods of black titanium dioxide photochemical catalyst, comprising the following steps: will include titanium
First mixed liquor of source and dehydrated alcohol is mixed with the second mixed liquor for including inhibitor, water and dehydrated alcohol, is hydrolyzed anti-
It answers, obtains jelly；The jelly is calcined under a nitrogen atmosphere, obtains black titanium dioxide photochemical catalyst.This hair
Bright to mix the first mixed liquor with the second mixed liquor, titanium source is met water and is hydrolyzed, and obtains jelly；Later by jelly in nitrogen
Under the conditions of calcined, calcination process will form Lacking oxygen in titanium dioxide surface, while generate Ti3+, make the band of titanium dioxide
Gap narrows, and so as to which visible light is absorbed and utilized, effectively removes the harmful algae in water body.Embodiment the result shows that, this hair
The minimum band-gap energy of bright black titanium dioxide obtained is 1.47eV, under visible light, to microcystic aeruginosa chlorophyll after 10h
Degradation rate up to 72.5%.
In addition, black titanium dioxide photochemical catalyst prepared by the present invention also have under visible light illumination it is reusable,
The advantages that stability is good.
Detailed description of the invention
Fig. 1 is 0.6N/b-TiO made from embodiment 12The SEM and TEM of photochemical catalyst scheme；
Fig. 2 is the XRD diagram of difference N doping black titanium dioxide photochemical catalyst made from embodiment 1；
Fig. 3 is the energy band gap diagram according to drawn by the UV-vis data of different N doping black titanium dioxides in embodiment 1；
Fig. 4 is removal of the black titanium dioxide of difference N doping amount made from embodiment 1 to microcystic aeruginosa chlorophyll
Effect；
Fig. 5 is 0.6N-N obtained in embodiment 22XRD diagram of the photochemical catalyst under different calcination temperatures；
Fig. 6 is the XRD diagram of the titanium dioxide obtained by calcining at 500 DEG C under different calcination atmospheres；
Fig. 7 is energy band gap diagram drawn by the UV-vis data of the white titania according to obtained by comparative example；
Fig. 8 be prepared under different calcination temperatures according to embodiment 2 obtained by 0.6N-N2The UV-vis number of black titanium dioxide
According to drawn energy band gap diagram；
Fig. 9 is removal effect of the titanium dioxide made from embodiment 2 and comparative example to microcystic aeruginosa chlorophyll；
Figure 10 is 0.6N/b-TiO2Recycling three times remove algae effect.
Specific embodiment
The present invention provides a kind of preparation methods of black titanium dioxide photochemical catalyst, comprising the following steps:
By the first mixed liquor for including titanium source and dehydrated alcohol and the second mixed liquor including inhibitor, water and dehydrated alcohol
Mixing, is hydrolyzed reaction, obtains jelly；
The jelly is calcined under a nitrogen atmosphere, obtains black titanium dioxide photochemical catalyst.
The present invention will include the first mixed liquor of titanium source and dehydrated alcohol and include the second of inhibitor, water and dehydrated alcohol
Mixed liquor mixing, is hydrolyzed reaction, obtains jelly.In the present invention, the titanium source preferably includes butyl titanate or four
Titanium chloride, more preferably butyl titanate；The inhibitor preferably includes concentrated hydrochloric acid or concentrated nitric acid, more preferably concentrated hydrochloric acid.In
In the present invention, the concentration of the concentrated hydrochloric acid is preferably 12mol/L；The concentration of the concentrated nitric acid is preferably 16mol/L.The present invention adds
Inhibiting can inhibit the hydrolysis rate of titanium source, avoid hydrolyzing the too fast performance to photochemical catalyst and have an adverse effect.
In the present invention, first mixed liquor is preferably mixed to get by titanium source and dehydrated alcohol.In the present invention, described
Mixing preferably carries out under agitation, and the rate of the stirring is preferably 300~500rpm, and the time of stirring is preferably 1~
3h。
In the present invention, it is also preferable to include urea for first mixed liquor.When first mixed liquor further includes urea,
The preparation of first mixed liquor preferably includes following steps: urea being added in dehydrated alcohol, after stirring, continuously adds titanium
Source simultaneously continues to stir, and obtains the first mixed liquor.In the present invention, the rate of the stirring is preferably 300~500rpm.In this hair
In bright, total mixing time is preferably controlled in 1~3h.
In the present invention, second mixed liquor is preferably mixed to get by inhibitor, water and dehydrated alcohol.In the present invention
In, the mixing preferably carries out under agitation, and the rate of the stirring is preferably 300~500rpm, and the time of stirring is excellent
It is selected as 1~3h.
After obtaining the first mixed liquor and the second mixed liquor, the present invention mixes first mixed liquor and second mixed liquor
It closes, obtains hydrolysis reaction system.In the present invention, in the hydrolysis reaction system, titanium source, inhibitor, water and dehydrated alcohol
Molar ratio is preferably (3.0~4.0): 1:(23.0~24.0): (42.0~43.0), more preferably 3.43:1:23.13:
42.93.When further including urea in first mixed liquor, titanium source in the hydrolysis reaction system, urea, inhibitor, water and
The molar ratio of dehydrated alcohol is preferably (3.0~4.0): (0.28~1.11): 1:(23.0~24.0): (42.0~43.0), more
Preferably 3.43:(0.28~1.11): 1:23.13:42.93.In the present invention, the dehydrated alcohol is in the first mixed liquor and
Capacity distribution in two mixed liquors is preferably 2:1.
In the present invention, the mode that first mixed liquor is mixed with second mixed liquor is preferred are as follows: by the second mixing
Drop is added in the first mixed liquor and is mixed.In the present invention, the rate of the dropwise addition is preferably (3~4) mL/min.This hair
It is bright to be conducive to react more uniform by the way of being added dropwise, and reaction speed is controlled, guarantee complete hydrolysis.Mixing of the present invention
It does not use any stirring condition in the process, if mixing under agitation, will lead to the second mixed liquor and be not added that finish will
Form white solid.
After obtaining hydrolysis reaction system, reaction is hydrolyzed in the hydrolysis reaction system by the present invention, obtains jelly.In
In the present invention, preferably it is stirred using glass bar in the hydrolysis reaction, the time of hydrolysis is preferably 1~
3min.Timing the time of hydrolysis of the present invention refers to after the first mixed liquor is mixed with the second mixed liquor, is arrived
Form the time of jelly.The present invention is stirred using glass bar compared to for mechanical stirring, and stirring rate is more slow, no
It will form and continuously stir, be conducive to titanium source and gradually hydrolyze, react more abundant.The present invention is not special to the rate of the stirring
It is required that, it can be ensured that hydrolysis sufficiently carries out, and 1~3min of stirring can form jelly.In specific reality of the invention
It applies in example, stirring rate 30rpm.In hydrolytic process of the present invention, titanium source is hydrolyzed, and generates the forerunner of titanium dioxide
Body.When in raw material further including urea, in the hydrolytic process, titanium source is hydrolyzed, and generates the presoma of titanium dioxide, and is urinated
It is plain then be dissolved in water, generate NH4+It is dispersed in jelly.
After obtaining jelly, the present invention calcines the jelly under a nitrogen atmosphere, obtains black titanium dioxide
Photochemical catalyst.
Before calcining, it is also preferable to include jelly is successively dried and ground by the present invention.In the present invention, the drying
Temperature be preferably 60~80 DEG C, the time is preferably 10~12h.The present invention does not have particular/special requirement to the partial size after the grinding,
Those skilled in the art rule of thumb control the degree of grinding.
In the present invention, the temperature of the calcining is preferably 400~600 DEG C, and more preferably 500 DEG C；Soaking time is preferred
For 2~4h.The present invention preferably is selected from the temperature that room temperature rises to calcining, and heating rate is preferably 4~6 DEG C/min.When heating rate mistake
When fast, the possible uneven heating of sample generates distortion of lattice, lattice is caused to can increase, reduces sample crystallization；If heating rate mistake
Low, the retention time is too long under low temperature procedure, and it is not high to may cause activity.The present invention calcines under a nitrogen atmosphere, dioxy
Change titanium precursors hydrolysis to generate titanium dioxide and form Lacking oxygen in titanium dioxide surface, while generating Ti3+, make titanium dioxide
Band gap narrows, so as to which visible light is absorbed and utilized.
When raw material also contains urea, the N in calcination process from urea can enter TiO2In lattice, formed Ti-N or
Person's N-O key, further promotes the band gap of titanium dioxide to narrow.It, can be in catalyst surface due to being calcined in nitrogen atmosphere
Form Ti3+The defects of/Lacking oxygen, so obtained catalyst is in black.
The present invention provides the black titanium dioxide photochemical catalysts that preparation method described in above scheme is prepared.In this hair
In bright, the doping of the nitrogen is determined by above-mentioned preparation method；When for N doping, nitrogen-atoms is preferably incorporated in TiO2Lattice
In.In the present invention, the partial size of the black titanium dioxide photochemical catalyst is preferably 10~20nm.
The present invention provides black titanium dioxide photochemical catalysts described in above scheme in visible light catalytic removal algae
Using.
In the present invention, the application preferably includes following steps: by black titanium dioxide photochemical catalyst and containing algae
Water mixing carries out light-catalyzed reaction under visible light conditions.In the present invention, the black titanium dioxide photochemical catalyst is in water
Concentration in body is preferably 0.1~0.3g/L；The algae is preferably microcystic aeruginosa；The OD of the algae680Value is preferably
0.1~0.3, number of cells is preferably (1.0~4.0) × 106Cell/mL, chlorophyll concentration are preferably 0.2~0.9mg/L.
In the present invention, the temperature of the light-catalyzed reaction is preferably 25~30 DEG C；The time of the light-catalyzed reaction is excellent
It is selected as 8~10h.Light-catalyzed reaction of the present invention preferably carries out under agitation, and the rate of the stirring is preferably 300~
500rpm。
The present invention does not have particular/special requirement, the visible light in any source to the source of the visible light.Of the invention
In specific embodiment, preferably using xenon lamp as light source, and the visible light that wavelength is greater than 420nm is obtained using edge filter.
Below with reference to embodiment to black titanium dioxide photochemical catalyst provided by the invention and the preparation method and application thereof into
Row detailed description, but they cannot be interpreted as limiting the scope of the present invention.
Embodiment 1
(1) 400rpm in different quality urea (0,0.2,0.4,0.6,0.8g) addition 20mL dehydrated alcohol is weighed respectively to stir
1h is mixed, 14mL butyl titanate is then added, continues 400rpm and stirs 1h, form the first mixed liquor；
(2) concentrated hydrochloric acid 1mL, deionized water 5mL and 10mL dehydrated alcohol are stirred at 400rpm 1h, forms the second mixing
Liquid；
(3) the second mixed liquor is added in the first mixed liquor dropwise (3mL/min), is stirred to form white size with glass bar
Shape substance；
(4) white gum substance is placed in 80 DEG C of baking ovens dry 12h, grinding forms powdery white substance；
(5) whiteness of different N doping amounts is placed in the tube furnace in nitrogen atmosphere, 4 DEG C/min is warming up to 500
DEG C, 2h is kept the temperature, black titanium dioxide photochemical catalyst is formed, is denoted as 0N/b-TiO respectively2、0.2N/b-TiO2、0.4N/b-TiO2、
0.6N/b-TiO2、0.8N/b-TiO2。
In the present embodiment, (0N/b-TiO in the black titanium dioxide of different N doping amounts used2、0.2N/b-TiO2、
0.4N/b-TiO2、0.6N/b-TiO2、0.8N/b-TiO2), the molar ratio of urea and butyl titanate is respectively 0,0.0033:
0.04、0.0067:0.04、0.0100:0.04、0.0133:0.04。
Fig. 1 is 0.6N/b-TiO made from the embodiment of the present invention 12The SEM and TEM of photochemical catalyst scheme, and wherein a is SEM figure,
B is TEM figure.As shown in Figure 1, black titanium dioxide photochemical catalyst is in uniform spherical structure, and particle diameter distribution is in 12nm or so.
Fig. 2 is the XRD diagram of difference N doping black titanium dioxide photochemical catalyst made from the embodiment of the present invention 1.It can by Fig. 2
Know occur the titanium dioxide of rutile and anatase in black titanium dioxide photochemical catalyst, and can be due to N doping amount
Difference and the object Phase Proportion of the rutile that generates and anatase is different, so as to cause different photocatalysis performances.
Fig. 3 is the energy band according to drawn by the UV-vis data of different N doping black titanium dioxides in the embodiment of the present invention 1
Gap figure.From the figure 3, it may be seen that N doping influences the band-gap energy of black titanium dioxide, wherein 0.6N doping is best, the band of resulting materials
Gap can be minimum, is 1.47eV, and 0.4N adulterates the band-gap energy highest of resulting black titanium dioxide, is 1.59eV.Band-gap energy is got over
Small this material of explanation is easier by excited by visible light, helps to improve photocatalysis performance.With the band-gap energy of ordinary titanium dioxide
3.2eV is compared, and band-gap energy is substantially reduced.
Application examples 1
Black titanium dioxide (0~0.8N/b-TiO of the different N doping amounts of Example 12), 20mg is respectively taken, is added respectively
To 100mL, OD680Value for 0.2 algae solution in, be uniformly mixed, be placed under xenon lamp (λ > 420nm, optical power 50W), in 25 DEG C,
Light-catalyzed reaction 10h is carried out under conditions of 400rpm, completes the removal to harmful algae, is to investigate with frustule Determination of Chlorophyll content
Index.
The algae solution under radiation of visible light not add any catalyst is as blank group.
Fig. 4 is that the black titanium dioxide of the different N doping amounts prepared in the embodiment of the present invention 1 is green to microcystic aeruginosa leaf
The removal effect of element.As shown in Figure 4, in the case where no catalysis material, it is seen that light is unobvious to microcystic aeruginosa removal effect.
With the addition of black titanium dioxide photochemical catalyst, the degradation efficiency of frustule Determination of Chlorophyll is improved, wherein 0.6N/b-TiO2's
Except algae effect is best, 72.5% has been reached to the degradation rate of microcystic aeruginosa chlorophyll after the 10h that degrades.
By the result in above-mentioned Fig. 1~4 it is found that the method system that the present invention is calcined by simple collosol and gel and nitrogen atmosphere
The standby black titanium dioxide photochemical catalyst formed has the characteristics that uniform particle sizes, rutile/anatase mix, and 0.6N is adulterated
The band-gap energy that has of black titanium dioxide is minimum, photocatalytic degradation effect is optimal.
Embodiment 2
Black titanium dioxide is prepared under different calcination temperatures, comprising the following steps:
(1) it weighs different quality urea (0,0.6g) respectively to be added in 20mL dehydrated alcohol, 400rpm stirs 1h, then adds
Enter 14mL butyl titanate, continues 400rpm and stir 1h, form the first mixed liquor；
(2) concentrated hydrochloric acid 1mL, deionized water 5mL and 10mL dehydrated alcohol are stirred at 400rpm 1h, forms the second mixing
Liquid；
(3) second mixed liquor is added in the first mixed liquor dropwise (4mL/min), stirred with glass bar to be formed it is white
Color colloid substance；
(4) white gum substance is placed in 80 DEG C of baking ovens dry 12h, grinding forms powdery white substance；
(5) whiteness of different N doping amounts is placed in the tube furnace in nitrogen atmosphere, 4 DEG C/min is warming up to 400,
500,600 DEG C, 2h is kept the temperature, is formed under nitrogen atmosphere and calcines resulting black titanium dioxide, be denoted as 0.6N-N respectively2(400℃)、
0.6N-N2(500℃)、0.6N-N2(600℃)、0N-N2(500℃)。
Comparative example
Calcining prepares titanium dioxide in air atmosphere:
The whiteness for the different N doping amounts that step (4) in embodiment 2 obtains is placed in Muffle furnace, 4 DEG C/min liter
Temperature keeps the temperature 2h to 500 DEG C, and gained white titania is denoted as 0N-AIR (500 DEG C), 0.6N-AIR (500 DEG C).
Fig. 5 is 0.6N-N obtained in the embodiment of the present invention 22XRD diagram of the photochemical catalyst under different calcination temperatures.By scheming
5 it is found that under a nitrogen atmosphere, with the raising of calcination temperature, the anatase titania ratio of generation increases.
Fig. 6 is the XRD diagram of the titanium dioxide obtained by calcining at 500 DEG C under different calcination atmospheres, and titanium dioxide sample is specific
Are as follows: the 0.6N-N of embodiment 22(500℃)、0N-N20N-AIR (500 DEG C), the 0.6N-AIR (500 of (500 DEG C) and comparative example
℃).It will be appreciated from fig. 6 that black titanium dioxide made under nitrogen atmosphere and the white titania prepared under air atmosphere
In there is the titanium dioxide of rutile and anatase, and in the white titania calcined in air of anatase crystal
Proportion is greater than in nitrogen atmosphere proportion in black titanium dioxide obtained by calcining.
Fig. 7 is energy band gap diagram drawn by the UV-vis data of the white titania according to obtained by comparative example；
Fig. 8 be prepared under different calcination temperatures according to embodiment 2 obtained by 0.6N-N2Black titanium dioxide UV-vis data
Drawn energy band gap diagram.As shown in Figure 8, calcination temperature influences band-gap energy size, 0.6N-N2(400℃)、0.6N-N2(500℃)、
0.6N-N2The band-gap energy of (600 DEG C) is respectively 2.58eV, 1.47eV and 1.53eV.Calcination temperature is 500 DEG C, and resulting light is urged
The band-gap energy of agent is minimum.As shown in Figure 7, under 500 DEG C of calcination temperatures, 0N-AIR (500 DEG C), 0.6N-AIR (500 DEG C) band
Gap can be respectively 2.51eV and 2.50eV, hence it is evident that be greater than calcining gained photochemical catalyst in a nitrogen atmosphere.Illustrate that calcination temperature is
500 DEG C, calcination atmosphere is that the band-gap energy of black titanium dioxide obtained by nitrogen is minimum.
Application examples 2
Take titanium dioxide (0N-AIR (500 DEG C), 0.6N-AIR (500 DEG C), 0.6N- prepared in comparative example and embodiment 2
N2(400℃)、0.6N-N2(500℃)、0.6N-N2(600℃)、0N-N2(500 DEG C)), 20mg is respectively taken, is respectively added to
100mL、OD680Value for 0.2 algae solution in, be uniformly mixed, be placed under xenon lamp (λ > 420nm, optical power 50W), in 25 DEG C,
Light-catalyzed reaction 10h is carried out under conditions of 400rpm, completes the removal to harmful algae, is to investigate with frustule Determination of Chlorophyll content
Index.
Fig. 9 is removal effect of the titanium dioxide made from the embodiment of the present invention 2 and comparative example to microcystic aeruginosa chlorophyll.
As shown in Figure 9, it calcines in air atmosphere and in (400 DEG C) of the low temperature resulting titanium dioxide of calcining except algae effect is unobvious, and
In a nitrogen atmosphere calcine and calcination temperature at 500 and 600 DEG C obtained by titanium dioxide significantly improve except algae effect, optimal material
Material is 0.6N-N2(500℃)。
By the result in above-mentioned Fig. 5~9 it is found that calcination atmosphere and calcination temperature influence the object Phase Proportion and band of photochemical catalyst
Gap energy size, to finally influence to remove algae effect.It is 0.6N-N that gained, which removes the highest photochemical catalyst of algae efficiency, in embodiment 22
Result obtained in (500 DEG C) and embodiment 1, embodiment 2 is identical, illustrates 0.6N-N2(500 DEG C) can be used as most optimum materials into
One step is investigated.
Application examples 3
Investigate optimal photochemical catalyst 0.6N/b-TiO2Except the stability during algae, comprising the following steps: take 20mg optimal
Photochemical catalyst 0.6N/b-TiO2, it is added to 100mL, OD680Value for 0.2 algae solution in, be uniformly mixed, be placed in xenon lamp (λ >
420nm, optical power 50W) under, light-catalyzed reaction 10h is carried out under conditions of 25 DEG C, 400rpm, harmful algae is gone in completion
It removes, using the chlorophyll content extracted in frustule as inspection target.And after the completion of reaction, 5000rpm is centrifugated photocatalysis
Clear water and washes of absolute alcohol 3 times are used in agent respectively, after 80 DEG C of oven dryings, repeat next time except algae is tested, repeat altogether
3 times.After per treatment, alga-killing rate is calculated as inspection target using the chlorophyll extracted in frustule, the results are shown in Figure 10.
Figure 10 is most optimum materials 0.6N/b-TiO of the present invention2Recycling three times remove algae effect.As shown in Figure 10, pass through
After 3 cyclic tests, 0.6N/b-TiO of the present invention2Alga-killing rate after photochemical catalyst reaction 10h is under the 78.5% of first time
66.8% is dropped to, only has dropped 11.7%.This illustrates that black titanium dioxide photochemical catalyst of the invention has excellent stability,
It is reusable.
As seen from the above embodiment, the present invention provides a kind of black titanium dioxide photochemical catalyst and preparation method thereof with answer
With, it is not only mild using the method for the present invention, simple, and the band gap for the black titanium dioxide being prepared narrows, and can be absorbed
Using visible light, the harmful algae in water body is effectively removed.In addition, black titanium dioxide photochemical catalyst prepared by the present invention also has
Have the advantages that reusable, stability is good under visible light illumination.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of preparation method of black titanium dioxide photochemical catalyst, which comprises the following steps:
The first mixed liquor including titanium source and dehydrated alcohol is mixed with the second mixed liquor for including inhibitor, water and dehydrated alcohol
It closes, reaction is hydrolyzed, obtains jelly；
The jelly is calcined under a nitrogen atmosphere, obtains black titanium dioxide photochemical catalyst.
2. preparation method according to claim 1, which is characterized in that the titanium source includes butyl titanate or four chlorinations
Titanium；The inhibitor includes concentrated hydrochloric acid or concentrated nitric acid.
3. preparation method according to claim 1 or 2, which is characterized in that in the mixed system of the hydrolysis, titanium
Source, inhibitor, water and dehydrated alcohol molar ratio be (3.0~4.0): 1:(23.0~24.0): (42.0~43.0).
4. preparation method according to claim 1, which is characterized in that further include urea in first mixed liquor；When
When further including urea in one mixed liquor, in the mixed system of the hydrolysis, titanium source, urea, inhibitor, water and dehydrated alcohol
Molar ratio be (3.0~4.0): (0.28~1.11): 1:(23.0~24.0): (42.0~43.0).
5. preparation method according to claim 1, which is characterized in that carried out in the hydrolysis reaction using glass bar
Stirring, the time of hydrolysis are 1~3min.
6. preparation method according to claim 1, which is characterized in that the temperature of the calcining is 400~600 DEG C, heat preservation
Time is 2~4h.
7. preparation method according to claim 1 or 6, which is characterized in that further include being carried out to jelly before the calcining
Drying, the temperature of the drying are 60~80 DEG C, and the time is 10~12h.
8. preparation method according to claim 1, which is characterized in that by first mixed liquor and second mixed liquor
Mixed mode are as follows: the second mixed liquor is added drop-wise in the first mixed liquor and is mixed.
9. the black titanium dioxide photochemical catalyst that any one of claim 1~8 preparation method is prepared.
10. application of the black titanium dioxide photochemical catalyst described in claim 9 in visible light catalytic removal algae.
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