CN107986380A - A kind of N doping coateds TiO2The technique of photocatalyst for degrading waste water - Google Patents
A kind of N doping coateds TiO2The technique of photocatalyst for degrading waste water Download PDFInfo
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- CN107986380A CN107986380A CN201711253833.9A CN201711253833A CN107986380A CN 107986380 A CN107986380 A CN 107986380A CN 201711253833 A CN201711253833 A CN 201711253833A CN 107986380 A CN107986380 A CN 107986380A
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- 238000000034 method Methods 0.000 title claims abstract description 25
- 239000002351 wastewater Substances 0.000 title claims abstract description 16
- 230000000593 degrading effect Effects 0.000 title description 7
- 239000011941 photocatalyst Substances 0.000 title description 4
- 239000003054 catalyst Substances 0.000 claims abstract description 24
- 239000000975 dye Substances 0.000 claims abstract description 22
- 230000008569 process Effects 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 230000001699 photocatalysis Effects 0.000 claims abstract description 9
- 239000011258 core-shell material Substances 0.000 claims abstract description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 41
- 239000000843 powder Substances 0.000 claims description 34
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 26
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 12
- 239000012298 atmosphere Substances 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 239000012279 sodium borohydride Substances 0.000 claims description 12
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- 229910052724 xenon Inorganic materials 0.000 claims description 9
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 9
- 230000003197 catalytic effect Effects 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 239000004202 carbamide Substances 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims description 5
- 229940043267 rhodamine b Drugs 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 claims description 2
- 238000005286 illumination Methods 0.000 claims 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 claims description 2
- 229940012189 methyl orange Drugs 0.000 claims description 2
- 229960000907 methylthioninium chloride Drugs 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 230000015556 catabolic process Effects 0.000 abstract description 5
- 238000006731 degradation reaction Methods 0.000 abstract description 5
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 4
- 239000010919 dye waste Substances 0.000 abstract description 3
- 230000000694 effects Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 238000011160 research Methods 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000000356 contaminant Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000006303 photolysis reaction Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000004506 ultrasonic cleaning Methods 0.000 description 2
- 235000003255 Carthamus tinctorius Nutrition 0.000 description 1
- 244000020518 Carthamus tinctorius Species 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 150000001454 anthracenes Chemical class 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 231100000299 mutagenicity Toxicity 0.000 description 1
- 230000007886 mutagenicity Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
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- 238000006467 substitution reaction Methods 0.000 description 1
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- 238000010998 test method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Classifications
-
- 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
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/39—
-
- 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
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- 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
- C02F2101/34—Organic compounds containing oxygen
-
- 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
- C02F2101/36—Organic compounds containing halogen
-
- 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 for the treatment of process of photocatalytic degradation of dye waste water, unordered nano-encapsulated type TiO that its visible light catalyst used adulterates for N2Photochemical catalyst.The unordered nano-encapsulated type TiO with thin multi-layer core-shell structure is made in the catalyst first2, then N is mixed in original position in its lattice, and the doping of the specificity and N element of structure improves TiO jointly2To the Photocatalytic activity of organic dyestuff.The present invention solves the problems, such as that dye wastewater degradation efficiency is low in the prior art, the organic dyestuff suitable for pollution degradation water body.
Description
Technical field
The present invention relates to a kind for the treatment of process of photocatalytic degradation of dye waste water, the unordered nano-encapsulated type adulterated using N
TiO2Photochemical catalyst, the special structure of the photochemical catalyst and N element are in TiO2Doping between lattice has been obviously improved TiO2Photocatalysis
The visible light catalysis activity of agent, the treatment process have the advantages that easy to operate, of low cost, degradation efficiency is high.
Background technology
In textile printing and dyeing process, largely use pollution environment and harmful auxiliary agent, these auxiliary agents big
Discharged more in the form of liquid, inevitably into water body environment, cause water pollution.If rhdamine B is with carcinogenic
And mutagenicity, the chroma in waste water containing rhodamine B is deep, organic pollution content is high, biological degradability is poor, with conventional method
Such as physisorphtion, Fenton process are difficult to administer, and cause to pollute water quality long-term degradation, seriously endanger the strong of water body environment and the mankind
Health, therefore seem particularly significant and urgent to the degradation treatment of this kind of waste water.
But how to use clean energy resource high efficiency, low cost, it is still one and huge challenge and there is far-reaching meaning
Justice.So there is an urgent need to develop new energy such as solar energy, wind energy, tide energy, biological energy source, the hydrogen using environmentally friendly and high energy storage by people
Energy, ocean energy etc., can cost-effectively substitute fossil and mineral resources, real on the premise of environmental protection and human health
Effectively converting and not influencing people for the existing energy is normally lived.A large amount of Novel environment-friendlymaterial materials are come into being in recent years.Nanometer
TiO2Material be exactly it is this can environment purification and efficiently utilize solar energy green functional material.It not only has oxidability
By force, excellent chemical stability, energy expenditure, without follow-up secondary pollution the advantages that, but also there is cheap, nontoxic nothing
Evil, can long-time service the features such as, therefore enjoy the favor and concern of photocatalysis researcher in recent years, and it extensively should
For the quick magnificent solar cell of new energy field such as dyestuff, photodissociation aquatic products hydrogen, microwave absorption, light absorption, biological medicine processing, light
Lie prostrate battery, photocatalysis, lithium ion battery etc..
But semiconductor TiO2Material there is also some it is serious the defects of, such as pure TiO2The photo-generate electron-hole of photochemical catalyst
To short life, light abstraction width is narrow low with light conversion efficiency, limits the application of solid powder th-1 catalyst.So need to receiving
The pattern of rice titanium dioxide is modified and study on the modification, and it is extremely urgent to sun efficiency of light absorption to improve it.Therefore, close
Reason ground prepares Hydrogen Energy with solar energy and conductor oxidate and effectively Environment control will be subject to people more and more to pay attention to.
From solar-energy photo-voltaic cell under the conditions of Japanese Scientists Fujishima and Honda discovery ultraviolet light in 1972
TiO2During electrode there occurs the interesting fact of photocatalytic water since, since nearly half a century, researchers are put into largely
Energy research TiO2Modification, illustrate analyze its catalytic mechanism, with deepening continuously for research, light-catalyzed reaction mechanism is further
It is clear, on TiO2The fast rapid-result focus of research, and also achieve different degrees of progress in all fields, but from
The theoretical research stage in laboratory is still on the whole, also has very big distance apart from industrial applications, in order to effectively improve
TiO2The catalytic activity of catalyst, currently used method include that narrow gap semiconductor is compound therewith, metal and nonmetal ion
Doping, noble metal loading, surface photosensitizer the methods of come change catalytic inner crystalline structure and outside surface group
Into and property reduce catalyst band gap distance, improve catalyst to the absorbability of visible ray reach enhancing TiO2Photocatalytic
The purpose of energy.
In recent years, Mao etc. employs a kind of breakthrough method for hydrogenation and is prepared for a unordered nano-TiO2, thus method
The TiO being prepared into2Energy gap there was only 1.54eV, possess very outstanding visible absorption performance and photolysis water hydrogen
Performance, but modification is doped to it, and use it for the organic pollution in photocatalyst for degrading water body and relevant degraded
Then there has been no systematic research for technique.
The content of the invention
The shortcomings that in order to overcome the above-mentioned prior art, it is an object of the invention to provide a kind of photocatalytic degradation of dye waste water
Treatment process, it uses light-catalysed mode to degrade dyestuff therein, and used photochemical catalyst is the unordered nanometer of N doping
Coated TiO2。
Realize technical scheme：Waste water from dyestuff is handled by the way of a kind of Visible Light Induced Photocatalytic, and is prepared for one
The unordered nano-encapsulated type TiO that N of the kind with excellent Photocatalytic activity is adulterated2Photochemical catalyst.
The treatment process of the Visible Light Induced Photocatalytic waste water from dyestuff, includes the following steps：
The unordered nano-encapsulated type TiO that N is adulterated2Photochemical catalyst is added to concentration as in 8mg/L~25mg/L waste water from dyestuff,
Room temperature, stirring visible light catalytic 0.5~3h of reaction are carried out under the xenon lamp of 400W~600W, the photochemical catalyst and waste water from dyestuff
Ratio is 35~45g：100L, the liquid level distance of xenon lamp and the waste water from dyestuff is 18cm~22cm, when one section of illumination reaction
Between after, close xenon lamp, complete the degraded to dyestuff.The dyestuff is at least one in methyl orange, methylene blue, rhodamine B
Kind.
The unordered nano-encapsulated type TiO of N doping2Preparation method, be specifically realized by the following steps：
First, unordered nano-encapsulated type TiO2Preparation：
A, by TiO2And NaBH4Mixing, grinds 0.5~1h, obtains mixture, the TiO2With NaBH4Mass ratio be 1：（0.6
~0.7）；
B, the mixture for obtaining step a is moved into alumina crucible, then is placed in tube furnace, with 10 DEG C/min under nitrogen atmosphere
The speed of~20 DEG C/min maintains 0.5~1h, then furnace cooling under this condition from room temperature to 300 DEG C~400 DEG C
To room temperature, the powder after being reacted；
C, the powder obtained step b is moved into alumina crucible, then is placed in tube furnace, under argon gas atmosphere with 10 DEG C/min~
The speed of 20 DEG C/min maintains 0.5~1h under this condition from room temperature to 300 DEG C~400 DEG C, then cools to the furnace
Room temperature, and with repeatedly washing and the drying of second alcohol and water, the powder after being reacted；
D, the powder for obtaining step c again with NaBH4Mixing, grinds 1~2h, obtains mixture, the powder that the step c is obtained
End and NaBH4Mass ratio be 1：(0.8~0.9)；
E, the mixture for obtaining step d is moved into alumina crucible, then is placed in tube furnace, with 2 DEG C/min under argon gas atmosphere
The speed of~5 DEG C/min maintains 0.5~1h under this condition from room temperature to 300 DEG C~400 DEG C, then furnace cooling,
Powder after being reacted；
F, the powder after reaction is washed 2~5 times respectively successively with ethanol and deionized water, is finally carried out in air dry oven
It is dry, obtain TiO2Powder；
G, the TiO for obtaining step f2Powder is moved into alumina crucible, then is placed in tube furnace, in air atmosphere with 2 DEG C/
The speed of min~5 DEG C/min handles 0.5~2h under this condition from room temperature to 300 DEG C~500 DEG C, then with furnace cooling
But to room temperature, unordered nano-encapsulated type TiO is obtained2。
The unordered nano-encapsulated type TiO2With multi-layer core-shell structure, TiO is followed successively by from inside to outside2Crystal nuclear, reduction amorphous
Layer, oxidation crystal layer, reduction amorphous layer, oxidation crystal layer, thickness is gradually thinning and is in close contact, the thin multi-layer core-shell structure
Enhance the quick conduction of light induced electron and its separation with hole.
2nd, the unordered nano-encapsulated type TiO of N doping2Preparation：
By unordered nano-encapsulated type TiO made from a certain amount of step 12It is uniformly mixed, is placed in full of inert atmosphere with urea
In tube furnace, with the speed of 2 DEG C/min~5 DEG C/min from room temperature to 400 DEG C~500 DEG C, and 2h is maintained, then with furnace cooling
But to room temperature, the unordered nano-encapsulated type TiO of N doping is obtained2, wherein unordered nano-encapsulated type TiO2Mass ratio with urea is
1：(0.3~0.5).
Rhodamine B（Rhodamine B, RhB）Safflower powder generally is called, a length of 553.2nmn of its maximum absorption wave.Luo Dan
Bright B dyestuffs are initially used to the organic dyestuff as oxa anthracenes, this dyestuff has certain causing toxicity, its suction in aqueous
Luminosity is stronger, and smaller, test process simple and convenient is influenced by external condition, therefore selects RhB as target contaminant to simulate
Assess the catalytic efficiency of catalysis material.
Specific test method is as follows：The RhB solution 100mL of 10mg/L is prepared as reaction contaminant, adds suitable N
The unordered nano-encapsulated type TiO of doping2, it is placed on the progress ultrasonic disperse regular hour in ultrasonic cleaning machine.Then by the solution
It is put into camera bellows, under the irradiation such as xenon lamp of filtering ultraviolet light, investigates the degrading activity of different time catalyst.
Compared with prior art, the present invention has the following advantages：
1st, compared with prior art, processing method of the invention is easy to operate, easy control of reaction conditions, of low cost, has
Potential industrial applications prospect；
2nd, photochemical catalyst of the present invention to prepare reaction condition gentle, it is easy to operate, it is dangerous small.Prepared with simple annealing steps
Possesses the TiO of multi-layer core-shell structure2, the TiO of this special multi-layer core-shell structure2Photochemical catalyst more effectively inhibits photoproduction
Electronics and hole it is compound, extend the service life in electronics and hole, increase electron concentration, make it as photochemical catalyst for degrading
Activity during dyestuff is significantly improved；
3rd, the doping of N enables N element to enter TiO2Lattice in, cause distortion of lattice, N element improves TiO2Catalyst
Ratio surface, it can improve light absorpting ability of the catalyst to visible ray, so as to improve the visible light catalytic efficiency of material.
Embodiment
With reference to specific embodiment the present invention is further elaborated the solution of the present invention.
Embodiment 1
First, unordered nano-encapsulated type TiO2Preparation：
A, by TiO2And NaBH4Mixing, grinds 0.5h, obtains mixture, the TiO2With NaBH4Mass ratio be 1：0.65；
B, the mixture for obtaining step a is moved into alumina crucible, then is placed in tube furnace, with 10 DEG C/min under nitrogen atmosphere
Speed from room temperature to 350 DEG C, and maintain 0.5h under this condition, room temperature then cooled to the furnace, after being reacted
Powder；
C, the powder for obtaining step b is moved into alumina crucible, then is placed in tube furnace, with 10 DEG C/min's under argon gas atmosphere
Speed maintains 0.5h under this condition from room temperature to 400 DEG C, then cools to room temperature with the furnace, and more with second alcohol and water
Secondary washing and drying, the powders A after being reacted；
D, the powders A for obtaining step c again with NaBH4Mixing, grinds 1.5h, obtains mixture, the powder that the step c is obtained
Last A and NaBH4Mass ratio be 1：0.85；
E, the mixture for obtaining step d is moved into alumina crucible, then is placed in tube furnace, with 2 DEG C/min under argon gas atmosphere
Speed from room temperature to 400 DEG C, and maintain 0.5h under this condition, then furnace cooling, the powder after being reacted；
F, the powder after reaction is washed 2~5 times respectively successively with ethanol and deionized water, is finally carried out in air dry oven
It is dry, obtain TiO2Powder；
G, the TiO for obtaining step f2Powder is moved into alumina crucible, then is placed in tube furnace, in air atmosphere with 2 DEG C/
The speed of min~5 DEG C/min handles 0.5~2h under this condition from room temperature to 300 DEG C~500 DEG C, then with furnace cooling
But to room temperature, unordered nano-encapsulated type TiO is obtained2Powder B.
2nd, the unordered nano-encapsulated type TiO of N doping2Preparation：
By obtained unordered nano-encapsulated type TiO in a certain amount of step 12Powder B is uniformly mixed with urea, is placed in full of lazy
In the tube furnace of property atmosphere, with the speed of 2 DEG C/min from room temperature to 400 DEG C, and 2h is maintained, then cool to room with the furnace
Temperature, obtains the unordered nano-encapsulated type TiO of N doping2, wherein powders A or unordered nano-encapsulated type TiO2Mass ratio with urea is
1：(0.3~0.5).
The treatment process of RhB waste water is as follows：The RhB solution 100mL of three parts of 10mg/L is prepared as reaction contaminant, difference
Add obtained undoped powders A in equivalent embodiment 1, the unordered nano-encapsulated type of undoped powder B and N doping
TiO2, it is placed in ultrasonic cleaning machine and carries out ultrasonic disperse 0.5h.Then the solution is put into 30min in camera bellows, keep xenon lamp with
The liquid level distance of waste water from dyestuff is 20cm, then under the xenon lamp irradiation of filtering ultraviolet light, every in 30min sampling analysis sample liquids
The concentration of RhB, so as to investigate the degrading activity of different time catalyst, specific data are referring to table 1 below：
The photocatalytic activity test of the different samples of table 1.
From the data analysis in table 1, once reduced, for the powders A of oxidation processes compared to only passing through, by going back twice
Former, the unordered nano-encapsulated type TiO of oxidation processes2Photocatalytic degradation RhB activity it is clearly more powerful, this is because locating twice
Introduced after reason gradually thin multi-layer core-shell structure enhances the quick conduction of light induced electron and its separation with hole from inside to outside, from
And enhance TiO2Photocatalytic activity.In addition, again it can be seen that the doping of N element equally can be carried significantly from upper table
Rise unordered nano-encapsulated type TiO2Photocatalytic activity.It can be seen from the above that the unordered nanometer bag that N made from the solution of the present invention is adulterated
Wrap up in type TiO2With excellent photocatalyst for degrading effect.
The foregoing is only a preferred embodiment of the present invention, but protection scope of the present invention be not limited thereto,
Any one skilled in the art the invention discloses technical scope in, technique according to the invention scheme and its
Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Claims (5)
1. a kind for the treatment of process of Visible Light Induced Photocatalytic waste water from dyestuff, includes the following steps：
The unordered nano-encapsulated type TiO that N is adulterated2Photochemical catalyst is added to concentration as in 8mg/L~25mg/L waste water from dyestuff,
Room temperature, stirring visible light catalytic 0.5~3h of reaction are carried out under the xenon lamp of 400W~600W, the photochemical catalyst and waste water from dyestuff
Ratio is 35~45g：100L, the liquid level distance of xenon lamp and the waste water from dyestuff is 18cm~22cm, when one section of illumination reaction
Between after, close xenon lamp, complete the degraded to dyestuff.
2. treatment process as claimed in claim 1, the dyestuff is at least one in methyl orange, methylene blue, rhodamine B
Kind.
3. treatment process as claimed in claim 1, it is characterised in that the unordered nano-encapsulated type TiO of the N doping2It can be seen that
The preparation method of photochemical catalyst is first to prepare the unordered nano-encapsulated type TiO with thin multi-layer core-shell structure2, then in TiO2It is brilliant
N element is adulterated in lattice to be made.
4. treatment process according to claim 3, it is characterised in that the unordered nano-encapsulated of the thin multi-layer core-shell structure
Type TiO2Preparation method it is as follows：
A, by TiO2And NaBH4Mixing, grinds 0.5~1h, obtains mixture, the TiO2With NaBH4Mass ratio be 1：（0.6
~0.7）；
B, the mixture for obtaining step a is moved into alumina crucible, then is placed in tube furnace, with 10 DEG C/min under nitrogen atmosphere
The speed of~20 DEG C/min maintains 0.5~1h, then furnace cooling under this condition from room temperature to 300 DEG C~400 DEG C
To room temperature, the powder after being reacted；
C, the powder obtained step b is moved into alumina crucible, then is placed in tube furnace, under argon gas atmosphere with 10 DEG C/min~
The speed of 20 DEG C/min maintains 0.5~1h under this condition from room temperature to 300 DEG C~400 DEG C, then cools to the furnace
Room temperature, and with repeatedly washing and the drying of second alcohol and water, the powder after being reacted；
D, the powder for obtaining step c again with NaBH4Mixing, grinds 1~2h, obtains mixture, the powder that the step c is obtained
End and NaBH4Mass ratio be 1：(0.8~0.9)；
E, the mixture for obtaining step d is moved into alumina crucible, then is placed in tube furnace, with 2 DEG C/min under argon gas atmosphere
The speed of~5 DEG C/min maintains 0.5~1h under this condition from room temperature to 300 DEG C~400 DEG C, then furnace cooling,
Powder after being reacted；
F, the powder after reaction is washed 2~5 times respectively successively with ethanol and deionized water, is finally carried out in air dry oven
It is dry, obtain TiO2Powder；
G, the TiO for obtaining step f2Powder is moved into alumina crucible, then is placed in tube furnace, in air atmosphere with 2 DEG C/
The speed of min~5 DEG C/min handles 0.5~2h under this condition from room temperature to 300 DEG C~500 DEG C, then with furnace cooling
But to room temperature, unordered nano-encapsulated type TiO is obtained2。
5. according to 3 or 4 any one of them treatment process of claim, it is characterised in that described in TiO2N members are adulterated in lattice
The method of element is as follows：By unordered nano-encapsulated type TiO made from a certain amount of step 12It is uniformly mixed with urea, is placed in being full of
In the tube furnace of inert atmosphere, with the speed of 2 DEG C/min~5 DEG C/min from room temperature to 400 DEG C~500 DEG C, and 2h is maintained,
Then cool to room temperature with the furnace, obtain the unordered nano-encapsulated type TiO of N doping2, wherein unordered nano-encapsulated type TiO2With urea
Mass ratio be 1：(0.3~0.5).
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