CN109647483A - A kind of preparation method and applications for the titanium dioxide optical catalyst that boron is nitrogen co-doped - Google Patents
A kind of preparation method and applications for the titanium dioxide optical catalyst that boron is nitrogen co-doped Download PDFInfo
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- CN109647483A CN109647483A CN201910050887.8A CN201910050887A CN109647483A CN 109647483 A CN109647483 A CN 109647483A CN 201910050887 A CN201910050887 A CN 201910050887A CN 109647483 A CN109647483 A CN 109647483A
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 105
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 53
- 239000003054 catalyst Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 229910052796 boron Inorganic materials 0.000 title claims abstract description 28
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 19
- 230000003287 optical effect Effects 0.000 title claims abstract description 17
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000908 ammonium hydroxide Substances 0.000 claims abstract description 14
- 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 10
- 239000004065 semiconductor Substances 0.000 claims abstract description 10
- 229910000348 titanium sulfate Inorganic materials 0.000 claims abstract description 10
- 230000003115 biocidal effect Effects 0.000 claims abstract description 9
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000004327 boric acid Substances 0.000 claims abstract description 8
- 230000003197 catalytic effect Effects 0.000 claims abstract description 7
- 230000008030 elimination Effects 0.000 claims abstract description 5
- 238000003379 elimination reaction Methods 0.000 claims abstract description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 8
- 239000012498 ultrapure water Substances 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 6
- 239000002351 wastewater Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000003760 magnetic stirring Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000004570 mortar (masonry) Substances 0.000 claims description 4
- 229910052573 porcelain Inorganic materials 0.000 claims description 4
- 239000003306 quinoline derived antiinfective agent Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000002604 ultrasonography Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 238000011897 real-time detection Methods 0.000 claims description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims 1
- 230000000630 rising effect Effects 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 15
- 230000001699 photocatalysis Effects 0.000 abstract description 9
- 238000007146 photocatalysis Methods 0.000 abstract description 8
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
- 238000004062 sedimentation Methods 0.000 abstract description 4
- 239000007790 solid phase Substances 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 abstract description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 3
- -1 hydroxyl radical free radical Chemical class 0.000 abstract description 3
- 230000003993 interaction Effects 0.000 abstract description 3
- 230000001590 oxidative effect Effects 0.000 abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 abstract description 3
- 239000001301 oxygen Substances 0.000 abstract description 3
- 230000001376 precipitating effect Effects 0.000 abstract description 3
- 239000002699 waste material Substances 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000356 contaminant Substances 0.000 abstract description 2
- 238000000197 pyrolysis Methods 0.000 abstract description 2
- 239000010936 titanium Substances 0.000 abstract description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract 1
- 229910052719 titanium Inorganic materials 0.000 abstract 1
- DPSPPJIUMHPXMA-UHFFFAOYSA-N 9-fluoro-5-methyl-1-oxo-6,7-dihydro-1H,5H-pyrido[3,2,1-ij]quinoline-2-carboxylic acid Chemical compound C1CC(C)N2C=C(C(O)=O)C(=O)C3=C2C1=CC(F)=C3 DPSPPJIUMHPXMA-UHFFFAOYSA-N 0.000 description 9
- 229960000702 flumequine Drugs 0.000 description 9
- 150000002500 ions Chemical class 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 3
- 239000003504 photosensitizing agent Substances 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- TZHYBRCGYCPGBQ-UHFFFAOYSA-N [B].[N] Chemical compound [B].[N] TZHYBRCGYCPGBQ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 206010070834 Sensitisation Diseases 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000005662 electromechanics Effects 0.000 description 1
- 239000005447 environmental material Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229960001180 norfloxacin Drugs 0.000 description 1
- OGJPXUAPXNRGGI-UHFFFAOYSA-N norfloxacin Chemical compound C1=C2N(CC)C=C(C(O)=O)C(=O)C2=CC(F)=C1N1CCNCC1 OGJPXUAPXNRGGI-UHFFFAOYSA-N 0.000 description 1
- 229960001699 ofloxacin Drugs 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- HDUMBHAAKGUHAR-UHFFFAOYSA-J titanium(4+);disulfate Chemical class [Ti+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O HDUMBHAAKGUHAR-UHFFFAOYSA-J 0.000 description 1
- 229940126680 traditional chinese medicines Drugs 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000017105 transposition Effects 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- 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
- C02F2101/34—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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
-
- 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 titanium dioxide optical catalyst that boron is nitrogen co-doped, using titanium sulfate as titanium source, using ammonium hydroxide as precipitating reagent and nitrogen source and boric acid as boron source, the nitrogen co-doped titanium dioxide optical catalyst of boron is prepared for using simple sedimentation method combined solid-phase pyrolysis；It include: the preparation of the titanium dioxide predecessor of (1) nitrogen list doping；(2) preparation of the nitrogen co-doped titanium dioxide optical catalyst of boron.The method of the present invention is easy to operate, and the photochemical catalyst prepared has preferable pattern and higher photocatalysis performance.Simultaneously using nano semiconductor material as photochemical catalyst, by realizing special catalysis or conversion effet with the interfacial interaction of antibiotic contaminant molecule, the oxygen of catalyst surface and hydrone is set to be converted to the substance that superoxide radical, hydroxyl radical free radical etc. have strong oxidizing property, to achieve the purpose that antibiotic residue in catalytic elimination water environment, the formation that this method will not result in waste of resources with secondary pollution, and it is easy to operate.
Description
Technical field
The present invention relates to technical field of environmental material preparation, specially a kind of titanium dioxide optical catalyst that boron is nitrogen co-doped
Preparation method and applications.
Background technique
TiO2Photochemical catalyst because have many advantages, such as cheap, chemical stability is high, green high-efficient by people concern, but
It is, since its wide forbidden band makes traditional TiO2The ultraviolet radioactive in sunlight less than 5% can only be utilized；And TiO2Electricity generates
Light induced electron and hole-recombination probability it is high, cause photocatalysis efficiency lower.Therefore, in order to solve the problems, such as two above, scientific research
Worker is to TiO2Carried out a series of linguistic term, mainly have noble metal loading, ion doping, semiconductor material it is compound,
Surface sensitization and surface acid are base-modified etc. to improve TiO2The photocatalytic activity of photochemical catalyst promotes TiO2Photocatalysis technology
Application.Since the cost is relatively high for noble metal, the application of noble metal loading method in practice, and noble metal loading are limited
It may reunite when excessively high, easily become the compound center of electrons and holes, reduce its photocatalytic activity.And surface is photosensitive
Changing photosensitizer used must satisfy: be readily adsorbed in TiO2Surface, and it intensifies state energy level and TiO2Conduction level phase
Matching.But currently used most of photosensitizers can only absorb part sunlight, it is low to the utilization rate of sunlight and photosensitive
Agent and equally it is adsorbed on TiO2There are absorption competitions between the pollutant on surface, and in addition itself drop can also occur under light illumination for photosensitizer
Solution, therefore the practical application of this method is more difficult.
To TiO2Lattice in be doped ion, generating defect even can change crystal form, can promote light induced electron
TiO is efficiently separated or expanded with hole2Optical response range, to change the photocatalytic activity of photochemical catalyst.Ion doping
It mainly include the methods of the doping of metal ion list, the doping of nonmetallic ion list and codope.Ion co-doped TiO2Avoid list
The drawbacks of one doping is brought, preferably to improve TiO2Photocatalytic activity, existing research shows the TiO after codope2Photocatalysis
Agent absorption band red shift improves the Photocatalytic Degradation Property of pollutant under Uv and visible light photograph.
Therefore, TiO is improved by doping2The Photocatalytic Degradation Property of catalyst is a good problem to study.
Summary of the invention
In order to meet the needs of above-mentioned technology development, the present invention provides one kind to be pyrolyzed with simple sedimentation method combined solid phase
Method prepares the nitrogen co-doped TiO of boron2The preparation method and application of nano-photocatalyst.
The purpose of the present invention is realized as follows:
A kind of preparation method for the titanium dioxide optical catalyst that boron is nitrogen co-doped, comprising the following steps: step 1: nitrogen list doping
TiO2The preparation of presoma；Step 2: the nitrogen co-doped TiO of boron2Preparation；
Nitrogen list adulterates TiO in the step one2Presoma the preparation method comprises the following steps: first weighing the titanium sulfate of set amount in beaker
In, the ultrapure water of set amount is added into beaker, ultrasound dissolves titanium sulfate sufficiently, then places the beaker on magnetic stirring apparatus
It is sufficiently stirred, ammonium hydroxide is added dropwise into beaker using separatory funnel；With the pH value of pH meter real-time detection solution, until pH
Until value rises to 11, stops that ammonium hydroxide is added, stand 10 minutes after continuing stirring 30 minutes, obtained lurid colloidal sol is turned
Vacuum filter is carried out to Buchner funnel, and uses ultrapure water and ethanol washing colloidal sol 2 ~ 3 times respectively, is deposited in drying box for what is obtained
In dried 8 hours at 80 DEG C, be made nitrogen list adulterate TiO2Presoma；
The nitrogen co-doped TiO of boron in the step two2The preparation method comprises the following steps: weighing the boric acid of set amount and one system the step of 1 gram
The nitrogen list obtained adulterates TiO2Presoma is fully ground and is allowed to be sufficiently mixed uniformly in porcelain mortar, then will mixing
Uniform mixture transfer places it in Muffle furnace in crucible, is made up to the programmed rate of setting set
Fixed temperature is kept for two hours at a set temperature, takes out after natural cooling, be fully ground again, and boron nitrogen is made and is co-doped with
Miscellaneous TiO2Nano semiconductor photochemical catalyst；
It is about 1 drop/sec that the rate in titanium sulfate solution, which is added dropwise, in ammonium hydroxide in the step one, and the pH of harsh control solution
Value, to guarantee that nitrogen content is basicly stable；
Boric acid used in the step two and nitrogen list adulterate TiO2The mass ratio of presoma is 0.05:1~0.5:1, preferably
Than for 0.3:1；
Programmed rate used in the step two is 4 ~ 10 DEG C/minute, preferably than being 4 DEG C/minute；
Temperature set by temperature programming used in the step two is 350 DEG C, 400 DEG C, 450 DEG C or 500 DEG C, preferably warm
Degree is 450 DEG C；
The nitrogen co-doped TiO of the boron that preparation method as described above obtains2The application of Nano semiconductor photochemical catalyst: it is applied to
The catalytic elimination fluoroquinolone antibiotic in antibiotic waste water；
(Ti (the SO of titanium sulfate used in the present invention4)2, 96%), boric acid, ammonium hydroxide and ethyl alcohol be to analyze pure, be purchased from the examination of traditional Chinese medicines chemistry
Agent Co., Ltd；Ultrapure waterIt is prepared by Milli-Q Plus system；
The antibiotic such as flumequine, lavo-ofloxacin and Norfloxacin are purchased from lark prestige chemical reagent Co., Ltd.
Positive beneficial effect: the present invention realizes sedimentation method combined solid-phase pyrolysis and prepares the nitrogen co-doped titanium dioxide of boron
Photochemical catalyst and its purpose for the waste water containing fluoroquinolone antibiotic of degrading.The method of the present invention is easy to operate, the light prepared
Catalyst has preferable pattern and higher photocatalysis performance.Simultaneously using nano semiconductor material as photochemical catalyst, pass through
Realize special catalysis or conversion effet with the interfacial interaction of antibiotic contaminant molecule, make catalyst surface oxygen and
Hydrone is converted to the substance that superoxide radical, hydroxyl radical free radical etc. have strong oxidizing property, to reach catalytic elimination water environment
The purpose of middle antibiotic residue, the formation that this method will not result in waste of resources with secondary pollution, and it is easy to operate, it is a kind of green
The high-efficient treatment method that colour circle is protected.
Detailed description of the invention
Fig. 1 is with flumequine (FLU) for pollutant, the boron of the different content optically catalytic TiO 2 nitrogen co-doped to boron
The influence of energy.
Fig. 2 is scanning electron microscope (SEM) figure of the photochemical catalyst of preparation；
Fig. 3 is X-ray diffraction (XRD) figure of the photochemical catalyst of preparation；
Fig. 4 is degradation efficiency table of the nitrogen co-doped titanium dioxide optical catalyst of boron to three kinds of fluoquinolones.
Specific embodiment
Below with reference to specific implementation example, the present invention will be further described.
A kind of preparation method for the titanium dioxide optical catalyst that boron is nitrogen co-doped, comprising the following steps: step 1: nitrogen list is mixed
Miscellaneous TiO2The preparation of presoma；Step 2: the nitrogen co-doped TiO of boron2Preparation.
Nitrogen list adulterates TiO in the step one2Presoma the preparation method comprises the following steps: first weighing the titanium sulfate of set amount in burning
In cup, the ultrapure water of set amount is added into beaker, ultrasound dissolves titanium sulfate sufficiently, then places the beaker magnetic stirring apparatus
On be sufficiently stirred, ammonium hydroxide is added dropwise into beaker using separatory funnel, ammonium hydroxide had not only done precipitating reagent but also had been nitrogen source；Use pH meter
The pH value of real-time detection solution until pH value rises to 11 stops that ammonium hydroxide is added, and stands 10 points after continuing stirring 30 minutes
Obtained lurid colloidal sol is turned to Buchner funnel and carries out vacuum filter, and uses ultrapure water and ethanol washing colloidal sol 2 respectively by clock
~ 3 times, being deposited in drying box of obtaining is dried 8 hours at 80 DEG C, nitrogen list is made and adulterates TiO2Presoma.
The nitrogen co-doped TiO of boron in the step two2The preparation method comprises the following steps: weighing the boric acid of set amount and the step of 1 gram
Nitrogen list made from one adulterates TiO2Presoma is fully ground in porcelain mortar and is allowed to be sufficiently mixed uniformly, then will
Uniformly mixed mixture shifts in crucible, and places it in Muffle furnace, is made up to the programmed rate of setting
Set temperature is kept for two hours at a set temperature, takes out after natural cooling, be fully ground again, and boron nitrogen is made
Codope TiO2Nano semiconductor photochemical catalyst.
The photocatalysis performance evaluation of prepared photochemical catalyst in the present invention: in XPA-7 type photochemical reactor (purchased from south
Capital Xu Jiang electromechanics factory) in carry out, with 500W xenon lamp irradiate, will 50 mL flumequine (FLU) simulated wastewaters be added crystal reaction tube in
And its initial value is measured, photochemical catalyst obtained is then added, carries out magnetic agitation and maintains the catalyst in suspension or showy shape
State first carries out dark place absorption-desorption and balances 30 min, light source is then turned on, prior before the light-catalyzed reaction that turn on light
1.5 mL of point in time sampling of setting filters out solid-phase catalyst using 0.22 μm of micro-filter, and the solution after separation is high
Effect liquid phase chromatogram (HPLC) method is in λmax The concentration of FLU is measured at=238 nm, and passes through formula:Degradation rate is calculated, whereinC 0The concentration of flumequine solution when to reach adsorption equilibrium,C tIt is anti-
It is between seasonabletWhen the concentration of flumequine solution that is measured by sampling.
Embodiment 1
Step 1, nitrogen list adulterate TiO2The preparation of presoma:
Weighing 5 g titanium sulfates and being dissolved in joined in the beaker of 300 mL ultrapure waters in advance, and ultrasound is allowed to be completely dissolved, and then will
Beaker is placed on magnetic stirring apparatus, and pH meter intercalation reaction liquid is surveyed reacting liquid pH value, and constantly carry out magnetic agitation, by matter
Amount until the pH value of reaction solution is increased to 11 just stops that ammonium hydroxide is added dropwise than being added dropwise in above-mentioned solution for the ammonium hydroxide of 25 wt%,
Ammonium hydroxide had not only done precipitating reagent but also had been nitrogen source.10 minutes are stood after continuing stirring 30 minutes, the lurid colloidal sol transposition cloth that will be obtained
Family name's funnel carries out vacuum filter, and uses ultrapure water and ethanol washing colloidal sol 2 ~ 3 times respectively, is deposited in what is obtained in drying box
It is dried 8 hours at 80 DEG C, nitrogen list is made and adulterates TiO2Presoma.
Step 2, the nitrogen co-doped TiO of boron2Preparation:
Weigh the boric acid and 1 gram of nitrogen list doping TiO of 300 and 500 mg2Presoma is fully ground simultaneously in porcelain mortar
It is allowed to be sufficiently mixed uniformly, then shift uniformly mixed mixture in crucible, and place it in Muffle furnace, with 4
DEG C/minute programmed rate point make up to 450 DEG C, kept for two hours at 450 DEG C, then taken out after natural cooling, then
It is secondary to be fully ground, the nitrogen co-doped TiO of boron is made2Nano semiconductor photochemical catalyst.
Photocatalysis performance evaluation: taking gained sample in step 2 to carry out photocatalytic degradation test in photochemical reactor,
It measures in the photochemical catalyst 4 hours and 98.3% is reached to the catalytic degradation efficiency of FLU.
The present invention realize sedimentation method combined solid-phase thermal point-score prepare the nitrogen co-doped titanium dioxide optical catalyst of boron and its
Purpose for the waste water containing fluoroquinolone antibiotic of degrading.The method of the present invention is easy to operate, the photochemical catalyst prepared have compared with
Good pattern and higher photocatalysis performance.Simultaneously using nano semiconductor material as photochemical catalyst, by being polluted with antibiotic
The interfacial interaction of object molecule realizes special catalysis or conversion effet, is converted to the oxygen of catalyst surface and hydrone
Superoxide radical, hydroxyl radical free radical etc. have the substance of strong oxidizing property, to reach antibiotic residue in catalytic elimination water environment
Purpose, the formation that this method will not result in waste of resources with secondary pollution, and easy to operate is a kind of environmentally protective efficient
Processing method.
It should finally be noted the above description is only a preferred embodiment of the present invention, it is served only for technical solution of the present invention
It is described in more detail.Conceive according to the present invention for those skilled in the art the nonessential improvement of make several and
Adjustment, all belongs to the scope of protection of the present invention.
Claims (8)
1. a kind of preparation method for the titanium dioxide optical catalyst that boron is nitrogen co-doped, which comprises the following steps: step
One: nitrogen list adulterates TiO2The preparation of presoma；Step 2: the nitrogen co-doped TiO of boron2Preparation.
2. a kind of preparation method of the nitrogen co-doped titanium dioxide optical catalyst of boron according to claim 1, feature exist
In nitrogen list adulterates TiO in the step one2Presoma the preparation method comprises the following steps: first weigh the titanium sulfate of set amount in beaker,
The ultrapure water of set amount is added into beaker, ultrasound dissolves titanium sulfate sufficiently, it is enterprising then to place the beaker magnetic stirring apparatus
Row is sufficiently stirred, and ammonium hydroxide is added dropwise into beaker using separatory funnel；With the pH value of pH meter real-time detection solution, until pH value
Until rising to 11, stops that ammonium hydroxide is added, stand 10 minutes after continuing stirring 30 minutes, obtained lurid colloidal sol is turned to
Buchner funnel carries out vacuum filter, and uses ultrapure water and ethanol washing colloidal sol 2 ~ 3 times respectively, is deposited in what is obtained in drying box
It is dried 8 hours at 80 DEG C, nitrogen list is made and adulterates TiO2Presoma.
3. a kind of preparation method of the nitrogen co-doped titanium dioxide optical catalyst of boron according to claim 1, feature exist
In the nitrogen co-doped TiO of boron in the step two2The preparation method comprises the following steps: weighing the boric acid of set amount and one being made the step of 1 gram
Nitrogen list adulterate TiO2Presoma is fully ground and is allowed to be sufficiently mixed uniformly, then will be mixed equal in porcelain mortar
Even mixture shifts in crucible, and places it in Muffle furnace, is made up to the programmed rate of setting set
Temperature, at a set temperature keep two hours, take out after natural cooling, be fully ground again, be made boron it is nitrogen co-doped
TiO2Nano semiconductor photochemical catalyst.
4. a kind of preparation method of the nitrogen co-doped titanium dioxide optical catalyst of boron according to claim 1 or 2, feature
Be: the rate that ammonium hydroxide is added dropwise in titanium sulfate solution in the step one is about 1 drop/sec, and harsh control solution
PH value.
5. a kind of preparation method of the nitrogen co-doped titanium dioxide optical catalyst of boron according to claim 1 or 3, feature
It is: boric acid used in the step two and nitrogen list doping TiO2The mass ratio of presoma is 0.05:1~0.5:1.
6. a kind of preparation method of the nitrogen co-doped titanium dioxide optical catalyst of boron according to claim 1 or 3, feature
Be: programmed rate used in the step two is 4 ~ 10 DEG C/minute.
7. a kind of preparation method of the nitrogen co-doped titanium dioxide optical catalyst of boron according to claim 1 or 3, feature
Be: temperature set by temperature programming used in the step two is 350 DEG C, 400 DEG C, 450 DEG C or 500 DEG C.
8. the nitrogen co-doped TiO of the boron that preparation method according to claim 1 or 2 obtains2Nano semiconductor photochemical catalyst is answered
With, it is characterised in that: it is applied to the catalytic elimination fluoroquinolone antibiotic in antibiotic waste water.
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