CN106391136A - Preparation method of molecular imprinting Co-doped TiO2 having high catalytic degradation activity and selectivity under visible light - Google Patents
Preparation method of molecular imprinting Co-doped TiO2 having high catalytic degradation activity and selectivity under visible light Download PDFInfo
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 189
- 230000015556 catabolic process Effects 0.000 title claims abstract description 84
- 238000006731 degradation reaction Methods 0.000 title claims abstract description 84
- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 32
- 230000000694 effects Effects 0.000 title claims abstract description 31
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 19
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims abstract description 13
- 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 abstract description 11
- 229940043267 rhodamine b Drugs 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract 2
- 239000000243 solution Substances 0.000 claims description 137
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 51
- 239000008367 deionised water Substances 0.000 claims description 41
- 229910021641 deionized water Inorganic materials 0.000 claims description 41
- 238000003756 stirring Methods 0.000 claims description 41
- 238000006243 chemical reaction Methods 0.000 claims description 33
- 239000007787 solid Substances 0.000 claims description 31
- 238000005406 washing Methods 0.000 claims description 31
- 239000003054 catalyst Substances 0.000 claims description 27
- 239000000203 mixture Substances 0.000 claims description 19
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 16
- 239000004005 microsphere Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- 238000002474 experimental method Methods 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 11
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 11
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 claims description 8
- -1 after dissolving Substances 0.000 claims description 7
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 7
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical group OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Chemical group OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 3
- 229960004889 salicylic acid Drugs 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 2
- IQUPABOKLQSFBK-UHFFFAOYSA-N 2-nitrophenol Chemical group OC1=CC=CC=C1[N+]([O-])=O IQUPABOKLQSFBK-UHFFFAOYSA-N 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 claims 1
- 238000002242 deionisation method Methods 0.000 claims 1
- 238000000527 sonication Methods 0.000 claims 1
- 239000011941 photocatalyst Substances 0.000 abstract description 23
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 abstract description 11
- 229910001981 cobalt nitrate Inorganic materials 0.000 abstract description 11
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 3
- 239000000178 monomer Substances 0.000 abstract description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 abstract 1
- 229910052799 carbon Inorganic materials 0.000 abstract 1
- 239000003999 initiator Substances 0.000 abstract 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 40
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 40
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 30
- 238000005119 centrifugation Methods 0.000 description 30
- 229960000583 acetic acid Drugs 0.000 description 20
- 238000013019 agitation Methods 0.000 description 20
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 20
- 238000001514 detection method Methods 0.000 description 20
- 239000012362 glacial acetic acid Substances 0.000 description 20
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 20
- 239000000843 powder Substances 0.000 description 20
- 239000000047 product Substances 0.000 description 20
- 239000007788 liquid Substances 0.000 description 14
- 239000007864 aqueous solution Substances 0.000 description 10
- 230000000593 degrading effect Effects 0.000 description 10
- 229910052736 halogen Inorganic materials 0.000 description 10
- 150000002367 halogens Chemical class 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 10
- 230000007935 neutral effect Effects 0.000 description 10
- 239000011780 sodium chloride Substances 0.000 description 10
- 239000006228 supernatant Substances 0.000 description 10
- OEHNVKBOQOXOJN-UHFFFAOYSA-N 2-(4-nitrophenyl)phenol Chemical compound OC1=CC=CC=C1C1=CC=C([N+]([O-])=O)C=C1 OEHNVKBOQOXOJN-UHFFFAOYSA-N 0.000 description 3
- 239000000356 contaminant Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 229920000344 molecularly imprinted polymer Polymers 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000002186 photoactivation Effects 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000003643 water by type Substances 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/069—Hybrid organic-inorganic polymers, e.g. silica derivatized with organic groups
-
- B01J35/39—
Abstract
The invention discloses a preparation method of a molecular imprinting Co-doped TiO2 having high catalytic degradation activity and selectivity under visible light, and belongs to the technical field of preparation of photocatalysts. According to the method, tetrabutyl titanate is taken as a carbon source, cobalt nitrate is an element source, rhodamine B (RhB) serves as a target molecule, p-phenylenediamine is a functional monomer, ammonium persulfate is an initiator, and a solvent method is used to synthesize the molecular imprinting Co-doped TiO2. The synthesized molecular imprinting Co-doped TiO2 has a stronger capability of absorbing an organic pollutant, and has a higher catalytic degradation activity for the organic pollutant under the visible light. The catalytic degradation capability of the molecular imprinting Co-doped TiO2 is 3.37 times that of Co-doped TiO2, and has a higher practical application value.
Description
Technical field
The present invention relates to one kind has high catalytic degradation activity and selective molecular engram Co doping under visible light
TiO2Preparation method, belong to photocatalyst preparation technical field.
Background technology
Due to having cheap, low toxicity, high stability and high catalytic activity, TiO2Become a kind of extensively concerned light to urge
Agent, using TiO2Photocatalytic oxidation processes the aspects such as organic pollutants and has broad application prospects.But TiO2Partly lead
There are some defects in actual applications such as in body photocatalyst：Greater band gap (E.=3.2eV), only it is less than in wavelength
Under the ultraviolet excitation of 387.5nm, valence-band electrons just can transit to formation light induced electron on conduction band and separate with hole, and ultraviolet light
3%～5% is only accounted in natural light, therefore not high to the utilization rate of natural light.In order to improve Ti02Photocatalysis performance, research
Worker is with regard to Ti02Preparation method, doping, catalyst carrier, the aspect such as heat treatment done many researchs, wherein doping because
It is easily realized, effect substantially, have wide range of applications, and become study hotspot.These polluted-waters are administered, preferably
Method be the organic pollution that first photoactivation processes low concentration high poison, then use the process of biodegradable method.But TiO2
It is difficult to optionally remove the latter, because TiO2There is no selectivity.Therefore, how to make TiO2Having selectivity is in practical application
The major issue facing.
In order that TiO2There is selectivity it has been proposed that many methods.One of them is molecular imprinting and TiO2
In conjunction with using poisonous organic pollution as template molecule, TiO being improved with this2Absorption to this pollutant, thus strengthen
TiO2Degraded to it.Molecular imprinting is a kind of polymer technology, it using target molecule as template, using monomer and friendship
There is polyreaction under certain condition in connection agent, then by target molecule eluting, ultimately form to have and have phase with target molecule
As space structure, and can specific bond target molecule molecularly imprinted polymer.Because molecularly imprinted polymer has very
Good specific recognition and extensive practicality, and the advantages of high chemical stability, low price, thus receive the general of people
All over concern.
But molecular engram TiO2It is typically all degradation of contaminant under the conditions of ultraviolet.This is primarily due to TiO2It is wide the taboo
Band quasiconductor, only has response in ultraviolet region, and wavelength only account for the 5% of sunshine gross energy in the ultraviolet light of below 400nm,
The energy of sunlight is concentrated mainly on the visible-range of 400-700nm, accounts for the 43% of gross energy.In order that molecular engram
TiO2Can degradation of contaminant under visible light, with the TiO of doping2Replace TiO2, molecular engram TiO is increased with this2Utilization
It is worth.
Content of the invention
The purpose of the present invention：By TiO2Doping techniques are combined with molecular imprinting, on the one hand using the TiO of doping2Strengthen
Catalyst, for the absorbability of visible ray, improves its photocatalysis effect in visible region, on the other hand utilizes molecule to print
Mark technology improves catalyst to the selective absorption of pollutant and degradation capability, prepares and has high catalytic degradation under visible light
The molecular engram doping TiO of activity and selectivity2Catalyst.
Technical scheme：One kind has high catalytic degradation activity and selective molecular engram Co under visible light
Doping TiO2Preparation method, follow the steps below：
(1)TiO2Preparation：
7mL butyl titanate is mixed with 40mL glacial acetic acid as solution A, will be molten as B for 40mL saturated nacl aqueous solution
B solution is added dropwise over solution A by liquid under agitation, after completion of dropping, continue stirring 30 minutes, after then reacting its
Add ptfe autoclave, put into baking oven, 200 DEG C are reacted 24 hours, and reaction finishes, products therefrom centrifugation will be reacted, use
Deionized water and washing with alcohol for several times, gained solid are dried at 80 DEG C, are pulverized last, finally, powder is put into tubular type
Stove, calcines 2～4 hours for 500 DEG C, obtains Co doping TiO2.
(2) Co doping TiO2Preparation：
7mL butyl titanate is mixed as solution A with 40mL glacial acetic acid, 0.09g cobalt nitrate is dissolved in 40mL saturation
B solution, as B solution, is added dropwise over solution A by sodium chloride solution under agitation, after completion of dropping, continues 30 points of stirring
Clock, after then reacting, it adds ptfe autoclave, puts into baking oven, and 200 DEG C are reacted 24 hours, and reaction finishes, will be anti-
Products therefrom is answered to be centrifuged, deionized water and washing with alcohol for several times, gained solid are dried at 80 DEG C, is pulverized last,
Afterwards, powder is put into tube furnace, calcine 4 hours for 500 DEG C, obtain Co doping TiO2.
(3) molecular engram Co doping TiO2Preparation：
At a certain temperature, appropriate microsphere and p-phenylenediamine are dissolved in a certain amount of deionized water, will after dissolving
Mixture continues stirring certain time, then uses the HCl solution of 1mol/L that pH is modulated 2, successively will add appropriate Co doping
TiO2With appropriate Ammonium persulfate. add mixed solution in, ultrasonic certain time, ultrasonic after the completion of continue to react at a certain temperature
Certain time, after reaction terminates, by gained solid Na2CO3Solution and deionized water wash are extremely neutral, finally by gained material
Put into and dry under baking oven uniform temperature, obtain molecular engram Co doping TiO2.
(4) molecular engram Co doping TiO2Photocatalyst for degrading target organic pollution：
200mg molecular engram Co doping TiO2Photocatalyst adds 250mL concentration for 10mg/L in trace thing solution, black
Stir 30min in the dark, under 400W Metal halogen lamp, then carry out degradation experiment, solution is 15cm away from light source distance, and every 30min pipettes
5mL solution, degradation time is 120min, and centrifugation carries out degradation effect detection to supernatant.Result shows：Molecular engram Co mixes
Miscellaneous TiO2Catalytic degradation ability be Co doping TiO23.37 times, centrifugation gained catalyst through ethanol, water washing post-drying, weight
Newly it is used for the catalytic degradation of trace thing, equally carries out degradation effect detection, catalyst is reused 5 times, catalytic degradation ability is
Co doping TiO23.10 times.
The technological merit of the present invention：The doping TiO of Co element2, so that catalyst is substantially improved for the utilization rate of visible ray,
There is preferable catalytic degradation performance, the introducing of molecular imprinting under visible light, make the suction to target contaminant for the catalyst
Attached amount increases, thus making it have preferable selectivity.Preparation process is relatively easy, and application is high.
Specific embodiment
Example below can make those skilled in the art be fully understood by the present invention, but limits this never in any form
Bright.
Embodiment 1：
(1)TiO2Preparation：
7mL butyl titanate is mixed with 40mL glacial acetic acid as solution A, will be molten as B for 40mL saturated nacl aqueous solution
B solution is added dropwise over solution A by liquid under agitation, after completion of dropping, continue stirring 30 minutes, after then reacting its
Add ptfe autoclave, put into baking oven, 150 DEG C are reacted 24 hours, and reaction finishes, products therefrom centrifugation will be reacted, use
Deionized water and washing with alcohol for several times, gained solid are dried at 80 DEG C, are pulverized last, finally, powder is put into tubular type
Stove, calcines 2～4 hours for 400 DEG C, obtains Co doping TiO2.
(2) Co doping TiO2Preparation：
7mL butyl titanate is mixed as solution A with 40mL glacial acetic acid, 0.09g cobalt nitrate is dissolved in 40mL saturation
B solution, as B solution, is added dropwise over solution A by sodium chloride solution under agitation, after completion of dropping, continues 30 points of stirring
Clock, after then reacting, it adds ptfe autoclave, puts into baking oven, and 150 DEG C are reacted 24 hours, and reaction finishes, will be anti-
Products therefrom is answered to be centrifuged, deionized water and washing with alcohol for several times, gained solid are dried at 80 DEG C, is pulverized last,
Afterwards, powder is put into tube furnace, calcine 4 hours for 400 DEG C, obtain Co doping TiO2.
(3) molecular engram Co doping TiO2Preparation：
Microsphere rhodamine B and 0.2g p-phenylenediamine are dissolved in deionized water, continue to stir by mixture after dissolving
Mix 10min, then modulate pH value with HCl solution, successively will add 0.5gCo doping TiO2Add mixing with 0.5g Ammonium persulfate.
In solution, ultrasonic 10min, ultrasonic after the completion of continue at 60 DEG C react 3h, reaction terminate after, by gained solid Na2CO3Molten
Gained material, to neutral, finally put into and is dried at 60 DEG C of baking oven, obtain molecular engram Co doping by liquid and deionized water wash
TiO2.
(4) molecular engram Co doping TiO2Photocatalyst for degrading target organic pollution：
200mg molecular engram Co doping TiO2Photocatalyst adds in the rhodamine B solution that 250mL concentration is 10mg/L,
Stir 30min in dark, under 400W Metal halogen lamp, then carry out degradation experiment, solution is 15cm away from light source distance, every 30min moves
Take 5mL solution, degradation time is 120min, centrifugation carries out degradation effect detection to supernatant.Result shows：Molecular engram Co
Doping TiO2Catalytic degradation ability be Co doping TiO22.96 times, centrifugation gained catalyst through ethanol, water washing post-drying,
It is reused for the catalytic degradation of paranitrophenol, equally carries out degradation effect detection, catalyst is reused 5 times, catalytic degradation
Ability is Co doping TiO22.73 times.
Embodiment 2：
(1)TiO2Preparation：
7mL butyl titanate is mixed with 40mL glacial acetic acid as solution A, will be molten as B for 40mL saturated nacl aqueous solution
B solution is added dropwise over solution A by liquid under agitation, after completion of dropping, continue stirring 30 minutes, after then reacting its
Add ptfe autoclave, put into baking oven, 150 DEG C are reacted 24 hours, and reaction finishes, products therefrom centrifugation will be reacted, use
Deionized water and washing with alcohol for several times, gained solid are dried at 80 DEG C, are pulverized last, finally, powder is put into tubular type
Stove, calcines 2～4 hours for 500 DEG C, obtains Co doping TiO2.
(2) Co doping TiO2Preparation：
7mL butyl titanate is mixed as solution A with 40mL glacial acetic acid, 0.09g cobalt nitrate is dissolved in 40mL saturation
B solution, as B solution, is added dropwise over solution A by sodium chloride solution under agitation, after completion of dropping, continues 30 points of stirring
Clock, after then reacting, it adds ptfe autoclave, puts into baking oven, and 150 DEG C are reacted 24 hours, and reaction finishes, will be anti-
Products therefrom is answered to be centrifuged, deionized water and washing with alcohol for several times, gained solid are dried at 80 DEG C, is pulverized last,
Afterwards, powder is put into tube furnace, calcine 4 hours for 500 DEG C, obtain Co doping TiO2.
(3) molecular engram Co doping TiO2Preparation：
Microsphere paranitrophenol and 0.1g p-phenylenediamine are dissolved in deionized water, after dissolving, mixture are continued
Stirring 10min, then modulates pH value with HCl solution, successively will add 0.6g Co doping TiO2Add with 0.5g Ammonium persulfate. and mix
Close solution in, ultrasonic 20min, ultrasonic after the completion of continue at 70 DEG C react 4h, reaction terminate after, by gained solid Na2CO3
Gained material, to neutral, finally put into and is dried at 60 DEG C of baking oven, obtain molecular engram Co doping by solution and deionized water wash
TiO2.
(4) molecular engram Co doping TiO2Photocatalyst for degrading target organic pollution：
200mg molecular engram Co doping TiO2It is in 10mg/L p-nitrophenyl phenol solution that photocatalyst adds 250mL concentration,
Stir 30min in dark, under 400W Metal halogen lamp, then carry out degradation experiment, solution is 15cm away from light source distance, every 30min moves
Take 5mL solution, degradation time is 120min, centrifugation carries out degradation effect detection to supernatant.Result shows：Molecular engram Co
Doping TiO2Catalytic degradation ability be Co doping TiO23.16 times, centrifugation gained catalyst through ethanol, water washing post-drying,
It is reused for the catalytic degradation of paranitrophenol, equally carries out degradation effect detection, catalyst is reused 5 times, catalytic degradation
Ability is Co doping TiO23.93 times.
Embodiment 3：
(1)TiO2Preparation：
7mL butyl titanate is mixed with 40mL glacial acetic acid as solution A, will be molten as B for 40mL saturated nacl aqueous solution
B solution is added dropwise over solution A by liquid under agitation, after completion of dropping, continue stirring 30 minutes, after then reacting its
Add ptfe autoclave, put into baking oven, 150 DEG C are reacted 24 hours, and reaction finishes, products therefrom centrifugation will be reacted, use
Deionized water and washing with alcohol for several times, gained solid are dried at 80 DEG C, are pulverized last, finally, powder is put into tubular type
Stove, calcines 2～4 hours for 600 DEG C, obtains Co doping TiO2.
(2) Co doping TiO2Preparation：
7mL butyl titanate is mixed as solution A with 40mL glacial acetic acid, 0.09g cobalt nitrate is dissolved in 40mL saturation
B solution, as B solution, is added dropwise over solution A by sodium chloride solution under agitation, after completion of dropping, continues 30 points of stirring
Clock, after then reacting, it adds ptfe autoclave, puts into baking oven, and 150 DEG C are reacted 24 hours, and reaction finishes, will be anti-
Products therefrom is answered to be centrifuged, deionized water and washing with alcohol for several times, gained solid are dried at 80 DEG C, is pulverized last,
Afterwards, powder is put into tube furnace, calcine 4 hours for 600 DEG C, obtain Co doping TiO2.
(3) molecular engram Co doping TiO2Preparation：
Microsphere paranitrophenol and 0.3g p-phenylenediamine are dissolved in deionized water, after dissolving, mixture are continued
Stirring 20min, then modulates pH value with HCl solution, successively will add 0.5g Co doping TiO2Add with 0.6g Ammonium persulfate. and mix
Close solution in, ultrasonic 20min, ultrasonic after the completion of continue at 60 DEG C react 5h, reaction terminate after, by gained solid Na2CO3
Gained material, to neutral, finally put into and is dried at 70 DEG C of baking oven, obtain molecular engram Co doping by solution and deionized water wash
TiO2.
(4) molecular engram Co doping TiO2Photocatalyst for degrading target organic pollution：
200mg molecular engram Co doping TiO2It is in 10mg/L p-nitrophenyl phenol solution that photocatalyst adds 250mL concentration,
Stir 30min in dark, under 400W Metal halogen lamp, then carry out degradation experiment, solution is 15cm away from light source distance, every 30min moves
Take 5mL solution, degradation time is 120min, centrifugation carries out degradation effect detection to supernatant.Result shows：Molecular engram Co
Doping TiO2Catalytic degradation ability be Co doping TiO22.83 times, centrifugation gained catalyst through ethanol, water washing post-drying,
It is reused for the catalytic degradation of paranitrophenol, equally carries out degradation effect detection, catalyst is reused 5 times, catalytic degradation
Ability is Co doping TiO22.69 times.
Embodiment 4：
(1)TiO2Preparation：
7mL butyl titanate is mixed with 40mL glacial acetic acid as solution A, will be molten as B for 40mL saturated nacl aqueous solution
B solution is added dropwise over solution A by liquid under agitation, after completion of dropping, continue stirring 30 minutes, after then reacting its
Add ptfe autoclave, put into baking oven, 200 DEG C are reacted 24 hours, and reaction finishes, products therefrom centrifugation will be reacted, use
Deionized water and washing with alcohol for several times, gained solid are dried at 80 DEG C, are pulverized last, finally, powder is put into tubular type
Stove, calcines 2～4 hours for 400 DEG C, obtains Co doping TiO2.
(2) Co doping TiO2Preparation：
7mL butyl titanate is mixed as solution A with 40mL glacial acetic acid, 0.09g cobalt nitrate is dissolved in 40mL saturation
B solution, as B solution, is added dropwise over solution A by sodium chloride solution under agitation, after completion of dropping, continues 30 points of stirring
Clock, after then reacting, it adds ptfe autoclave, puts into baking oven, and 200 DEG C are reacted 24 hours, and reaction finishes, will be anti-
Products therefrom is answered to be centrifuged, deionized water and washing with alcohol for several times, gained solid are dried at 80 DEG C, is pulverized last,
Afterwards, powder is put into tube furnace, calcine 4 hours for 400 DEG C, obtain Co doping TiO2.
(3) molecular engram Co doping TiO2Preparation：
Microsphere rhodamine B and 0.2g p-phenylenediamine are dissolved in deionized water, continue to stir by mixture after dissolving
Mix 30min, then modulate pH value with HCl solution, successively will add 0.7g Co doping TiO2Add mixing with 0.6g Ammonium persulfate.
In solution, ultrasonic 20min, ultrasonic after the completion of continue at 80 DEG C react 3h, reaction terminate after, by gained solid Na2CO3Molten
Gained material, to neutral, finally put into and is dried at 70 DEG C of baking oven, obtain molecular engram Co doping by liquid and deionized water wash
TiO2.
(4) molecular engram Co doping TiO2Photocatalyst for degrading target organic pollution：
200mg molecular engram Co doping TiO2It is in 10mg/L rhodamine B solution that photocatalyst adds 250mL concentration, black
Stir 30min in the dark, under 400W Metal halogen lamp, then carry out degradation experiment, solution is 15cm away from light source distance, and every 30min pipettes
5mL solution, degradation time is 120min, and centrifugation carries out degradation effect detection to supernatant.Result shows：Molecular engram Co mixes
Miscellaneous TiO2Catalytic degradation ability be Co doping TiO23.07 times, centrifugation gained catalyst through ethanol, water washing post-drying, weight
Newly it is used for the catalytic degradation of rhodamine B, equally carries out degradation effect detection, catalyst is reused 5 times, catalytic degradation ability is
Co doping TiO22.82 times.
Embodiment 5：
(1)TiO2Preparation：
7mL butyl titanate is mixed with 40mL glacial acetic acid as solution A, will be molten as B for 40mL saturated nacl aqueous solution
B solution is added dropwise over solution A by liquid under agitation, after completion of dropping, continue stirring 30 minutes, after then reacting its
Add ptfe autoclave, put into baking oven, 200 DEG C are reacted 24 hours, and reaction finishes, products therefrom centrifugation will be reacted, use
Deionized water and washing with alcohol for several times, gained solid are dried at 80 DEG C, are pulverized last, finally, powder is put into tubular type
Stove, calcines 2～4 hours for 500 DEG C, obtains Co doping TiO2.
(2) Co doping TiO2Preparation：
7mL butyl titanate is mixed as solution A with 40mL glacial acetic acid, 0.09g cobalt nitrate is dissolved in 40mL saturation
B solution, as B solution, is added dropwise over solution A by sodium chloride solution under agitation, after completion of dropping, continues 30 points of stirring
Clock, after then reacting, it adds ptfe autoclave, puts into baking oven, and 200 DEG C are reacted 24 hours, and reaction finishes, will be anti-
Products therefrom is answered to be centrifuged, deionized water and washing with alcohol for several times, gained solid are dried at 80 DEG C, is pulverized last,
Afterwards, powder is put into tube furnace, calcine 4 hours for 500 DEG C, obtain Co doping TiO2.
(3) molecular engram Co doping TiO2Preparation：
Microsphere onitrophenol and 0.1g p-phenylenediamine are dissolved in deionized water, after dissolving, mixture are continued
Stirring 20min, then modulates pH value with HCl solution, successively will add 0.5g Co doping TiO2Add with 0.7g Ammonium persulfate. and mix
Close solution in, ultrasonic 30min, ultrasonic after the completion of continue at 70 DEG C react 3h, reaction terminate after, by gained solid Na2CO3
Gained material, to neutral, finally put into and is dried at 80 DEG C of baking oven, obtain molecular engram Co doping by solution and deionized water wash
TiO2.
(4) molecular engram Co doping TiO2Photocatalyst for degrading target organic pollution：
200mg molecular engram Co doping TiO2It is in 10mg/L ortho-nitrophenyl phenol solution that photocatalyst adds 250mL concentration,
Stir 30min in dark, under 400W Metal halogen lamp, then carry out degradation experiment, solution is 15cm away from light source distance, every 30min moves
Take 5mL solution, degradation time is 120min, centrifugation carries out degradation effect detection to supernatant.Result shows：Molecular engram Co
Doping TiO2Catalytic degradation ability be Co doping TiO23.23 times, centrifugation gained catalyst through ethanol, water washing post-drying,
It is reused for the catalytic degradation of onitrophenol, equally carries out degradation effect detection, catalyst is reused 5 times, catalytic degradation
Ability is Co doping TiO23.98 times.
Embodiment 6：
(1)TiO2Preparation：
7mL butyl titanate is mixed with 40mL glacial acetic acid as solution A, will be molten as B for 40mL saturated nacl aqueous solution
B solution is added dropwise over solution A by liquid under agitation, after completion of dropping, continue stirring 30 minutes, after then reacting its
Add ptfe autoclave, put into baking oven, 200 DEG C are reacted 24 hours, and reaction finishes, products therefrom centrifugation will be reacted, use
Deionized water and washing with alcohol for several times, gained solid are dried at 80 DEG C, are pulverized last, finally, powder is put into tubular type
Stove, calcines 2～4 hours for 500 DEG C, obtains Co doping TiO2.
(2) Co doping TiO2Preparation：
7mL butyl titanate is mixed as solution A with 40mL glacial acetic acid, 0.09g cobalt nitrate is dissolved in 40mL saturation
B solution, as B solution, is added dropwise over solution A by sodium chloride solution under agitation, after completion of dropping, continues 30 points of stirring
Clock, after then reacting, it adds ptfe autoclave, puts into baking oven, and 200 DEG C are reacted 24 hours, and reaction finishes, will be anti-
Products therefrom is answered to be centrifuged, deionized water and washing with alcohol for several times, gained solid are dried at 80 DEG C, is pulverized last,
Afterwards, powder is put into tube furnace, calcine 4 hours for 500 DEG C, obtain Co doping TiO2.
(3) molecular engram Co doping TiO2Preparation：
Microsphere onitrophenol and 0.2g p-phenylenediamine are dissolved in deionized water, after dissolving, mixture are continued
Stirring 10min, then modulates pH value with HCl solution, successively will add 0.6g Co doping TiO2Add with 0.7g Ammonium persulfate. and mix
Close solution in, ultrasonic 10min, ultrasonic after the completion of continue at 60 DEG C react 4h, reaction terminate after, by gained solid Na2CO3
Gained material, to neutral, finally put into and is dried at 80 DEG C of baking oven, obtain molecular engram Co doping by solution and deionized water wash
TiO2.
(4) molecular engram Co doping TiO2Photocatalyst for degrading target organic pollution：
200mg molecular engram Co doping TiO2It is in 10mg/L ortho-nitrophenyl phenol solution that photocatalyst adds 250mL concentration,
Stir 30min in dark, under 400W Metal halogen lamp, then carry out degradation experiment, solution is 15cm away from light source distance, every 30min moves
Take 5mL solution, degradation time is 120min, centrifugation carries out degradation effect detection to supernatant.Result shows：Molecular engram Co
Doping TiO2Catalytic degradation ability be Co doping TiO23.37 times, centrifugation gained catalyst through ethanol, water washing post-drying,
It is reused for the catalytic degradation of onitrophenol, equally carries out degradation effect detection, catalyst is reused 5 times, catalytic degradation
Ability is Co doping TiO23.10 times.
Embodiment 7：
(1)TiO2Preparation：
7mL butyl titanate is mixed with 40mL glacial acetic acid as solution A, will be molten as B for 40mL saturated nacl aqueous solution
B solution is added dropwise over solution A by liquid under agitation, after completion of dropping, continue stirring 30 minutes, after then reacting its
Add ptfe autoclave, put into baking oven, 250 DEG C are reacted 24 hours, and reaction finishes, products therefrom centrifugation will be reacted, use
Deionized water and washing with alcohol for several times, gained solid are dried at 80 DEG C, are pulverized last, finally, powder is put into tubular type
Stove, calcines 2～4 hours for 400 DEG C, obtains Co doping TiO2.
(2) Co doping TiO2Preparation：
7mL butyl titanate is mixed as solution A with 40mL glacial acetic acid, 0.09g cobalt nitrate is dissolved in 40mL saturation
B solution, as B solution, is added dropwise over solution A by sodium chloride solution under agitation, after completion of dropping, continues 30 points of stirring
Clock, after then reacting, it adds ptfe autoclave, puts into baking oven, and 250 DEG C are reacted 24 hours, and reaction finishes, will be anti-
Products therefrom is answered to be centrifuged, deionized water and washing with alcohol for several times, gained solid are dried at 80 DEG C, is pulverized last,
Afterwards, powder is put into tube furnace, calcine 4 hours for 400 DEG C, obtain Co doping TiO2.
(3) molecular engram Co doping TiO2Preparation：
Microsphere paranitrophenol and 0.3g p-phenylenediamine are dissolved in deionized water, after dissolving, mixture are continued
Stirring 20min, then modulates pH value with HCl solution, successively will add 0.6g Co doping TiO2Add with 0.5g Ammonium persulfate. and mix
Close solution in, ultrasonic 30min, ultrasonic after the completion of continue at 70 DEG C react 4h, reaction terminate after, by gained solid Na2CO3
Gained material, to neutral, finally put into and is dried at 60 DEG C of baking oven, obtain molecular engram Co doping by solution and deionized water wash
TiO2.
(4) molecular engram Co doping TiO2Photocatalyst for degrading target organic pollution：
200mg molecular engram Co doping TiO2It is in 10mg/L p-nitrophenyl phenol solution that photocatalyst adds 250mL concentration,
Stir 30min in dark, under 400W Metal halogen lamp, then carry out degradation experiment, solution is 15cm away from light source distance, every 30min moves
Take 5mL solution, degradation time is 120min, centrifugation carries out degradation effect detection to supernatant.Result shows：Molecular engram Co
Doping TiO2Catalytic degradation ability be Co doping TiO23.03 times, centrifugation gained catalyst through ethanol, water washing post-drying,
It is reused for the catalytic degradation of paranitrophenol, equally carries out degradation effect detection, catalyst is reused 5 times, catalytic degradation
Ability is Co doping TiO22.81 times.
Embodiment 8：
(1)TiO2Preparation：
7mL butyl titanate is mixed with 40mL glacial acetic acid as solution A, will be molten as B for 40mL saturated nacl aqueous solution
B solution is added dropwise over solution A by liquid under agitation, after completion of dropping, continue stirring 30 minutes, after then reacting its
Add ptfe autoclave, put into baking oven, 250 DEG C are reacted 24 hours, and reaction finishes, products therefrom centrifugation will be reacted, use
Deionized water and washing with alcohol for several times, gained solid are dried at 80 DEG C, are pulverized last, finally, powder is put into tubular type
Stove, calcines 2～4 hours for 500 DEG C, obtains Co doping TiO2.
(2) Co doping TiO2Preparation：
7mL butyl titanate is mixed as solution A with 40mL glacial acetic acid, 0.09g cobalt nitrate is dissolved in 40mL saturation
B solution, as B solution, is added dropwise over solution A by sodium chloride solution under agitation, after completion of dropping, continues 30 points of stirring
Clock, after then reacting, it adds ptfe autoclave, puts into baking oven, and 250 DEG C are reacted 24 hours, and reaction finishes, will be anti-
Products therefrom is answered to be centrifuged, deionized water and washing with alcohol for several times, gained solid are dried at 80 DEG C, is pulverized last,
Afterwards, powder is put into tube furnace, calcine 4 hours for 500 DEG C, obtain Co doping TiO2.
(3) molecular engram Co doping TiO2Preparation：
Microsphere rhodamine B and 0.1g p-phenylenediamine are dissolved in deionized water, continue to stir by mixture after dissolving
Mix 30min, then modulate pH value with HCl solution, successively will add 0.7g Co doping TiO2Add mixing with 0.6g Ammonium persulfate.
In solution, ultrasonic 20min, ultrasonic after the completion of continue at 80 DEG C react 5h, reaction terminate after, by gained solid Na2CO3Molten
Gained material, to neutral, finally put into and is dried at 70 DEG C of baking oven, obtain molecular engram Co doping by liquid and deionized water wash
TiO2.
(4) molecular engram Co doping TiO2Photocatalyst for degrading target organic pollution：
200mg molecular engram Co doping TiO2It is in 10mg/L rhodamine B solution that photocatalyst adds 250mL concentration, black
Stir 30min in the dark, under 400W Metal halogen lamp, then carry out degradation experiment, solution is 15cm away from light source distance, and every 30min pipettes
5mL solution, degradation time is 120min, and centrifugation carries out degradation effect detection to supernatant.Result shows：Molecular engram Co mixes
Miscellaneous TiO2Catalytic degradation ability be Co doping TiO22.92 times, centrifugation gained catalyst through ethanol, water washing post-drying, weight
Newly it is used for the catalytic degradation of rhodamine B, equally carries out degradation effect detection, catalyst is reused 5 times, catalytic degradation ability is
Co doping TiO22.77 times.
Embodiment 9：
(1)TiO2Preparation：
7mL butyl titanate is mixed with 40mL glacial acetic acid as solution A, will be molten as B for 40mL saturated nacl aqueous solution
B solution is added dropwise over solution A by liquid under agitation, after completion of dropping, continue stirring 30 minutes, after then reacting its
Add ptfe autoclave, put into baking oven, 250 DEG C are reacted 24 hours, and reaction finishes, products therefrom centrifugation will be reacted, use
Deionized water and washing with alcohol for several times, gained solid are dried at 80 DEG C, are pulverized last, finally, powder is put into tubular type
Stove, calcines 2～4 hours for 600 DEG C, obtains Co doping TiO2.
(2) Co doping TiO2Preparation：
7mL butyl titanate is mixed as solution A with 40mL glacial acetic acid, 0.09g cobalt nitrate is dissolved in 40mL saturation
B solution, as B solution, is added dropwise over solution A by sodium chloride solution under agitation, after completion of dropping, continues 30 points of stirring
Clock, after then reacting, it adds ptfe autoclave, puts into baking oven, and 250 DEG C are reacted 24 hours, and reaction finishes, will be anti-
Products therefrom is answered to be centrifuged, deionized water and washing with alcohol for several times, gained solid are dried at 80 DEG C, is pulverized last,
Afterwards, powder is put into tube furnace, calcine 4 hours for 600 DEG C, obtain Co doping TiO2.
(3) molecular engram Co doping TiO2Preparation：
Microsphere salicylic acid and 0.3g p-phenylenediamine are dissolved in deionized water, after dissolving, mixture are continued stirring
30min, then modulates pH value with HCl solution, successively will add 0.7g Co doping TiO2Add mixing molten with 0.7g Ammonium persulfate.
In liquid, ultrasonic 30min, ultrasonic after the completion of continue at 80 DEG C react 5h, reaction terminate after, by gained solid Na2CO3Solution
With deionized water wash to neutral, finally gained material is put into and dry at 80 DEG C of baking oven, obtain molecular engram Co doping TiO2.
(4) molecular engram Co doping TiO2Photocatalyst for degrading target organic pollution：
200mg molecular engram Co doping TiO2It is in 10mg/L salicylic acid solution that photocatalyst adds 250mL concentration, dark
Middle stirring 30min, then carries out degradation experiment under 400W Metal halogen lamp, and solution is 15cm away from light source distance, and every 30min pipettes
5mL solution, degradation time is 120min, and centrifugation carries out degradation effect detection to supernatant.Result shows：Molecular engram Co mixes
Miscellaneous TiO2Catalytic degradation ability be Co doping TiO22.73 times, centrifugation gained catalyst through ethanol, water washing post-drying, weight
Newly it is used for salicylic catalytic degradation, equally carries out degradation effect detection, catalyst is reused 5 times, catalytic degradation ability is
Co doping TiO22.51 times.
Claims (9)
1. one kind has high catalytic degradation activity and selective molecular engram Co doping TiO under visible light2Preparation method, it is special
Levy and be to follow the steps below：Microsphere and p-phenylenediamine are dissolved in deionized water, after dissolving, mixture continue
Continuous stirring, then modulates pH value with HCl solution, successively will add Co doping TiO2Add in mixed solution with Ammonium persulfate., surpass
Sound, ultrasonic after the completion of continue at 60-80 DEG C reaction, after reaction terminates, by gained solid Na2CO3Solution and deionization washing
Wash to neutrality, finally gained material is put into and dry under baking oven, obtain molecular engram Co doping TiO2.
2. according to claim 1 method it is characterised in that microsphere can be rhodamine B, paranitrophenol, adjacent nitro
Phenol, salicylic acid.
3. according to claim 1 method it is characterised in that p-phenylenediamine consumption be 0.1-0.3g；The consumption of Ammonium persulfate.
For 0.5-0.7g.
4. according to claim 1 method it is characterised in that Co doping TiO2Consumption be 0.5-0.7g.
5. according to claim 1 method it is characterised in that sonication treatment time be 10-30min.
6. according to claim 1 method it is characterised in that p-phenylenediamine dissolving after continue mixing time be 10-30min, instead
It is 3-5h between seasonable.
7. according to claim 1 method it is characterised in that reaction temperature be 60-80 DEG C, drying temperature be 60-80 DEG C.
8. according to claim 1 method it is characterised in that prepared molecular engram Co doping TiO2, have under visible light
There are preferable catalytic degradation performance and selectivity, after repeating experiment for 5 times, still there is higher catalysis activity.
9. according to claim 1 method it is characterised in that preparing catalyst using solvent thermal process, preparation process is relatively simple
Single, feasibility is high.
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| CN107649101A (en) * | 2017-09-29 | 2018-02-02 | 湖南大学 | Mercapto-functionalized titania molecule trace composite and its aqueous phase preparation method and application |
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