CN112058251A - Degradation of plastic microspheres in wastewater by ultrasonic iron-nitrogen doped titanium dioxide - Google Patents
Degradation of plastic microspheres in wastewater by ultrasonic iron-nitrogen doped titanium dioxide Download PDFInfo
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- CN112058251A CN112058251A CN202010728171.1A CN202010728171A CN112058251A CN 112058251 A CN112058251 A CN 112058251A CN 202010728171 A CN202010728171 A CN 202010728171A CN 112058251 A CN112058251 A CN 112058251A
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 124
- 239000004005 microsphere Substances 0.000 title claims abstract description 75
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 61
- 239000004033 plastic Substances 0.000 title claims abstract description 47
- 229920003023 plastic Polymers 0.000 title claims abstract description 47
- 239000002351 wastewater Substances 0.000 title claims abstract description 45
- YYXHRUSBEPGBCD-UHFFFAOYSA-N azanylidyneiron Chemical compound [N].[Fe] YYXHRUSBEPGBCD-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000006731 degradation reaction Methods 0.000 title abstract description 28
- 230000015556 catabolic process Effects 0.000 title abstract description 24
- 239000011941 photocatalyst Substances 0.000 claims abstract description 74
- 238000000034 method Methods 0.000 claims abstract description 20
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims abstract description 15
- 239000002245 particle Substances 0.000 claims abstract description 11
- 230000000593 degrading effect Effects 0.000 claims abstract description 8
- 239000011148 porous material Substances 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 40
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 32
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 29
- 239000002243 precursor Substances 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 20
- 229910052757 nitrogen Inorganic materials 0.000 claims description 18
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 17
- 238000009210 therapy by ultrasound Methods 0.000 claims description 17
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 16
- 229910052742 iron Inorganic materials 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 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 claims description 12
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 11
- 229910052719 titanium Inorganic materials 0.000 claims description 11
- 239000010936 titanium Substances 0.000 claims description 11
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000004202 carbamide Substances 0.000 claims description 8
- 235000013877 carbamide Nutrition 0.000 claims description 8
- 239000011325 microbead Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 5
- 238000013032 photocatalytic reaction Methods 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 15
- 238000002360 preparation method Methods 0.000 description 9
- 239000013078 crystal Substances 0.000 description 6
- 230000001699 photocatalysis Effects 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- -1 polyethylene Polymers 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000001354 calcination Methods 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 239000002608 ionic liquid Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- 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—
-
- B01J35/40—
-
- B01J35/51—
-
- B01J35/615—
-
- B01J35/647—
-
- 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
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- 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
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- 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
-
- 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 provides a method for degrading plastic microspheres in wastewater by ultrasonic iron-nitrogen doped titanium dioxide, wherein a photocatalyst is an ultrasonic iron-nitrogen doped titanium dioxide hollow microsphere; the particle size of the ultrasonic iron-nitrogen doped titanium dioxide hollow microsphere is 100-600 nm, the pore diameter of the microsphere is 5-15 nm, and the specific surface area of the ultrasonic iron-nitrogen doped titanium dioxide hollow microsphere is 200-400 m2The method combines the photocatalytic reaction of the photocatalyst and the ultrasonic degradation process to carry out synergistic degradation on the plastic microspheres in the wastewater, has excellent photocatalytic degradation efficiency, and has great application value in the field of degradation treatment of the plastic microspheres in the wastewater.
Description
Technical Field
The invention relates to the technical field of photocatalyst preparation and wastewater treatment, in particular to degradation of plastic microspheres in wastewater by ultrasonic iron-nitrogen doped titanium dioxide.
Background
Plastic Microbeads (Plastic Microbeads) generally refer to water-insoluble Plastic solids with the particle size of less than 5 millimeters, generally consist of organic high-molecular polymers (such as polyethylene, polypropylene, polymethyl methacrylate, polystyrene, polyurethane and nylon), are often used as fillers, film-forming agents, thickening agents, suspending agents and the like in personal care and cosmetics, generally, the Plastic Microbeads are difficult to biodegrade, have a half-life of hundreds of years, not only pollute the environment, but also threaten marine organisms and influence ecological balance, and possibly influence human health through a food chain.
The nano titanium dioxide as the photocatalyst can utilize ultraviolet light as a light source to carry out photocatalytic reaction with pollutants such as plastics and the like to degrade the pollutants into small-molecular nontoxic substances, thereby avoiding secondary pollution to the environment, but because the forbidden band width of the titanium dioxide is only limited in an ultraviolet region (380 nm) and the defects of high density, easy sinking in water, low light source utilization rate and difficult recovery exist, the application and popularization of the titanium dioxide photocatalyst are limited, and therefore, the titanium dioxide photocatalyst needs to be modified.
The invention patent application with the application number of CN104492469A discloses a preparation method of an iron-nitrogen-doped titanium dioxide composite photocatalyst, the preparation method comprises the steps of firstly preparing titanium dioxide powder, then adding triethylamine into the titanium dioxide powder, desolventizing the mixture by a rotary evaporator, drying the mixture to obtain the nitrogen-doped titanium dioxide composite photocatalyst, and finally obtaining the product iron-nitrogen-doped titanium dioxide composite photocatalyst under the action of ferric nitrate.
The invention patent with the application number of CN201810114902.6 discloses N-TiO with a hollow structure2The preparation method of the photocatalyst comprises the steps of taking the ionic liquid of 1-butyl-3-methylimidazolium tetrafluoroborate as a solvent, a microwave wave absorbing agent, a fluorine source and a nitrogen source, synthesizing titanium dioxide with a hollow structure under the microwave-assisted thermal condition, then placing the obtained mixture in an inert gas atmosphere for calcination, and utilizing the nitrogen source in the ionic liquid to synthesize TiO2Doping modification is carried out to prepare the N-TiO with the hollow structure2However, the photocatalytic efficiency of the photocatalyst is not significantly improved.
The invention patent with the application number of CN201511030931.7 discloses a Fe and N codoped titanium dioxide mesoporous microsphere array visible light photocatalyst and a preparation method thereof, wherein the preparation method utilizes a two-step template method to prepare three-dimensional ordered Fe and N codoped mesoporous TiO2The microsphere array, but the method has the defect of low light source utilization rate in wastewater due to high density.
In view of the above, there is a need to provide a titanium dioxide photocatalyst with low density, high specific surface area and excellent photocatalytic efficiency, which can meet the requirements of practical applications.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide ultrasonic iron-nitrogen doped titanium dioxide for degrading plastic microspheres in wastewater.
In order to realize the aim, the invention provides a photocatalyst which is an iron-nitrogen doped titanium dioxide hollow microsphere; the particle size of the iron-nitrogen doped titanium dioxide hollow microsphere is 100-600 nm, the pore diameter of the microsphere is 5-15 nm, and the specific surface area of the iron-nitrogen doped titanium dioxide hollow microsphere is 200-400 m2/g。
Preferably, in the iron-nitrogen doped titanium dioxide hollow microsphere, the atomic ratio of iron to titanium is (1-3): 100, respectively; the atomic ratio of nitrogen to titanium is (2-5): 100.
in order to achieve the above object, the present invention further provides a method for preparing the photocatalyst, comprising the steps of:
s1, slowly dripping tetrabutyl titanate into absolute ethyl alcohol, fully stirring to mix the tetrabutyl titanate and the absolute ethyl alcohol uniformly, adding a predetermined amount of acetic acid, and stirring to prepare a titanium dioxide precursor solution;
s2, adding ferric nitrate and carbamide into absolute ethyl alcohol according to a preset proportion, adding a preset amount of water, and stirring to fully dissolve to prepare an iron-nitrogen precursor solution;
s3, slowly dripping the iron-nitrogen precursor solution prepared in the step S2 into the titanium dioxide precursor solution prepared in the step S1, adjusting the pH value to 3-4, stirring for 30-40 min to prepare a mixed solution, transferring the mixed solution into a hydrothermal reaction kettle, adding a predetermined amount of water, simultaneously assisting with ultrasonic treatment, and carrying out hydrothermal reaction for 8-24 h at 150-170 ℃;
s4, after the hydrothermal reaction in the step S3 is finished, taking out a product, centrifugally washing, fully grinding, and roasting at 400-500 ℃ for 1-3 hours to prepare the iron-nitrogen doped titanium dioxide hollow microsphere, namely the photocatalyst.
Preferably, in step S1, the volume ratio of the tetrabutyl titanate to the absolute ethyl alcohol is 1: (2-3).
Preferably, in step S2, the molar mass ratio of the iron nitrate to the carbamide is (1-5): (1-3).
Preferably, in the ultrasonic treatment of step S3, the ultrasonic power is set to 200-400W.
Preferably, in the mixed solution of step S3, the ratio of the molar mass of iron to the molar mass of nitrogen to the molar mass of titanium is (1 to 3): (2-5): 100.
preferably, in step S3, the volume ratio of the iron nitrogen precursor solution to the titanium dioxide precursor solution is 1: (2-3).
In order to achieve the purpose, the invention also provides application of the photocatalyst in degrading the waste water plastic microspheres.
Preferably, the application comprises the following steps:
a1, performing filtration concentration treatment on the wastewater containing the plastic microspheres with the particle size of less than 5mm, wherein the filtration precision is less than or equal to 5 microns, so as to obtain concentrated wastewater; in the concentrated wastewater, the abundance of the plastic microspheres is 105～1010Per liter;
a2, adding the photocatalyst into the concentrated wastewater prepared in the step A1, and stirring for 10-30 min for fully mixing to obtain a pretreatment solution; in the pretreatment solution, the addition amount of the photocatalyst is 10-100 mg/L;
a3, placing the pretreatment solution obtained in the step A2 at a light intensity of 1-5 mW/cm2Irradiating for 10-30 days under an ultraviolet lamp, and then simultaneously assisting with ultrasonic treatment to carry out ultrasonic-enhanced photocatalytic degradation reaction on the plastic microspheres; the power of ultrasonic treatment is 400-600 w;
a4, and after the ultrasonic-enhanced photocatalytic degradation reaction in the step A3 is finished, recovering the photocatalyst.
Compared with the prior art, the invention has the beneficial effects that:
1. the iron-nitrogen doped titanium dioxide hollow microsphere photocatalyst provided by the invention has a nano hollow microsphere structure, has low density, high specific surface area, high stability, high light-capturing efficiency and special nano-size physical properties, the characteristic of high specific surface area can provide more active sites for photocatalytic degradation reaction between the photocatalyst and plastic microspheres in wastewater, and the higher crystallinity can reduce the recombination rate of photo-generated electrons and active holes, so that the catalytic activity is improved, the characteristic of low density can enable the photocatalyst to be in a stable suspension state in the wastewater, and the defect that the light source utilization rate is low due to the fact that the photocatalyst easily sinks in the wastewater is effectively overcome; meanwhile, the suspended photocatalyst obtains more contact area with suspended plastic microspheres, and is beneficial to the photocatalytic degradation reaction.
2. The iron-nitrogen doped titanium dioxide hollow microsphere photocatalyst provided by the invention is characterized in that iron and nitrogen are also doped on the structure of hollow microsphere titanium dioxide; iron doping can enable iron ions to enter titanium dioxide crystal lattices to replace partial titanium ions, crystal lattice distortion is generated, strain energy is generated due to distortion, oxygen atoms in the crystal lattices can easily escape, and therefore the recombination probability of hole-electron pairs is reduced, and the photocatalytic performance of the titanium dioxide crystal lattices is improved; a new valence band can be formed after nitrogen doping, and meanwhile, stable oxygen vacancies can be formed on the surface of titanium dioxide by nitrogen doping, so that the photocatalytic performance of the photocatalyst in the visible light range is greatly improved, iron and nitrogen can generate a synergistic effect when the iron and the nitrogen are co-doped, the absorption of the photocatalyst on light is promoted, so that more hole-electron pairs are generated, and the photocatalytic performance of the titanium dioxide is obviously improved.
3. The iron-nitrogen doped titanium dioxide hollow microsphere photocatalyst provided by the invention is prepared by adopting a method combining ultrasound and hydrothermal, and in the hydrothermal reaction process, ultrasound treatment is assisted, and the two are cooperated with each other to synthesize the titanium dioxide hollow microsphere with high crystallinity, wherein the cooperation mechanism is as follows: the ultrasonic wave can generate a cavitation effect, generate local high temperature and high pressure, release a large amount of energy, accelerate mass transfer and heat transfer processes among hydrothermal reaction systems, remarkably increase collision opportunities among solute molecules in the hydrothermal reaction systems, enable new crystal nucleus particles to be more stable, obtain titanium dioxide crystals with better crystallinity, and meanwhile, assist ultrasonic treatment in the hydrothermal reaction, and the shock wave generated by the ultrasonic wave can effectively prevent reactants from agglomerating, so that the dispersion performance of the photocatalyst is better.
4. According to the iron-nitrogen-doped titanium dioxide hollow microsphere photocatalyst provided by the invention, tetrabutyl titanate is used as a titanium source, ferric nitrate and carbamide are used as an iron source and a nitrogen source, and the iron-nitrogen-doped titanium dioxide hollow microsphere photocatalyst is prepared by two steps of processes of an ultrasonic hydrothermal method and a calcining method.
5. The application method of the iron-nitrogen doped titanium dioxide hollow microsphere photocatalyst in degrading the waste water plastic microspheres, which is provided by the invention, adopts the operation process of filtering concentration pretreatment, ultrasonic wave combined photocatalytic degradation and photocatalyst recycling, combines the ultrasonic degradation and photocatalytic degradation technologies, and synergistically degrades the plastic microspheres with high efficiency, and has the advantage of high degradation efficiency, which is mainly due to the following reasons: the ultrasonic wave can promote the generation of oxidation free radicals in the solution, and the increase of the oxidation free radicals is beneficial to the improvement of the photocatalytic activity; the method can promote the medium migration, increase the number of oxidation free radicals on the surface of the photocatalyst and improve the activity of the photocatalyst to a certain extent.
Detailed Description
The technical solutions of the embodiments of the present invention will be described clearly and completely below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, rather than all embodiments, and all other embodiments obtained by those skilled in the art without creative efforts based on the embodiments of the present invention belong to the protection scope of the present invention.
The invention provides a preparation method of a photocatalyst, which comprises the following steps:
s1, slowly dripping tetrabutyl titanate into absolute ethyl alcohol, fully stirring to mix the tetrabutyl titanate and the absolute ethyl alcohol uniformly, adding a predetermined amount of acetic acid, and stirring to prepare a titanium dioxide precursor solution;
s2, adding ferric nitrate and carbamide into absolute ethyl alcohol according to a preset proportion, adding a preset amount of water, and stirring to fully dissolve to prepare an iron-nitrogen precursor solution;
s3, slowly dripping the iron-nitrogen precursor solution prepared in the step S2 into the titanium dioxide precursor solution prepared in the step S1, adjusting the pH value to 3-4, stirring for 30-40 min to prepare a mixed solution, transferring the mixed solution into a hydrothermal reaction kettle, adding a predetermined amount of water, simultaneously assisting with ultrasonic treatment, and carrying out hydrothermal reaction for 8-24 h at 150-170 ℃;
s4, after the hydrothermal reaction in the step S3 is finished, taking out a product, centrifugally washing, fully grinding, and roasting at 400-500 ℃ for 1-3 hours to prepare the iron-nitrogen doped titanium dioxide hollow microsphere, namely the photocatalyst.
Further, in step S1, the volume ratio of the tetrabutyl titanate to the absolute ethyl alcohol is 1: (2-3).
Further, in step S2, the molar mass ratio of the iron nitrate to the carbamide is (1-5): (1-3).
Further, in the ultrasonic processing of step S3, the ultrasonic power is set to 200-400W.
Further, in the mixed solution described in step S3, the ratio of the molar mass of iron, the molar mass of nitrogen, and the molar mass of titanium is (1 to 3): (2-5): 100.
further, in step S3, the volume ratio of the iron nitrogen precursor solution to the titanium dioxide precursor solution is 1: (2-3).
The invention also provides an application of the photocatalyst in degrading waste water plastic microspheres, which comprises the following steps:
a1, performing filtration concentration treatment on the wastewater containing the plastic microspheres with the particle size of less than 5mm, wherein the filtration precision is less than or equal to 5 microns, so as to obtain concentrated wastewater; in the concentrated wastewater, the abundance of the plastic microspheres is 105～1010Per liter;
a2, adding the photocatalyst into the concentrated wastewater prepared in the step A1, and stirring for 10-30 min for fully mixing to obtain a pretreatment solution; in the pretreatment solution, the addition amount of the photocatalyst is 10-100 mg/L;
a3, placing the pretreatment solution obtained in the step A2 at a light intensity of 1-5 mW/cm2Irradiating for 10-30 days under an ultraviolet lamp, and then simultaneously assisting with ultrasonic treatment to carry out ultrasonic-enhanced photocatalytic degradation reaction on the plastic microspheres; the power of ultrasonic treatment is 400-600 w;
a4, and after the ultrasonic-enhanced photocatalytic degradation reaction in the step A3 is finished, recovering the photocatalyst.
The present invention is described in further detail below with reference to specific examples.
Example 1
Embodiment 1 of the present invention provides a method for preparing a photocatalyst, including the steps of:
s1, slowly dripping 20mL of tetrabutyl titanate into 50mL of absolute ethyl alcohol, fully stirring to mix the tetrabutyl titanate and the absolute ethyl alcohol uniformly, adding 10mL of acetic acid, and stirring to prepare a titanium dioxide precursor solution;
s2, mixing the components in a molar mass ratio of 1: adding the ferric nitrate and the carbamide of the 1 into 30mL of absolute ethyl alcohol, adding 10mL of water, stirring until the mixture is fully dissolved, and preparing an iron-nitrogen precursor solution; wherein the ratio of the molar mass of iron, the molar mass of nitrogen and the molar mass of titanium is 2: 4: 100, respectively;
s3, slowly and dropwise adding the iron-nitrogen precursor solution prepared in the step S2 into the titanium dioxide precursor solution prepared in the step S1, adjusting the pH value to 3-4, stirring for 30-40 min to prepare a mixed solution, transferring the mixed solution into a hydrothermal reaction kettle, adding 20mL of water, assisting with ultrasonic treatment of 300W, and carrying out hydrothermal reaction for 12 hours at 160 ℃;
s4, after the hydrothermal reaction in the step S3 is finished, taking out a product, centrifugally washing, fully grinding, and roasting at 450 ℃ for 2 hours to prepare the iron-nitrogen doped titanium dioxide hollow microsphere, namely the photocatalyst, wherein the average particle size is 500nm, and the average specific surface area reaches 352m2/g。
The photocatalyst prepared in example 1 is applied to the degradation of waste water plastic microbeads, and comprises the following steps:
a1, filtering and concentrating the wastewater containing the plastic microspheres with the particle size of less than 5mm with the filtering precision of 5 microns to obtain concentrated wastewater; in the concentrated wastewater, the abundance of the plastic microspheres is 108Per liter;
a2, adding the photocatalyst into the concentrated wastewater prepared in the step A1, stirring for 30min, and fully mixing to obtain a pretreatment solution; in the pretreatment solution, the addition amount of the photocatalyst is 20 mg/L;
a3, placing the pretreatment solution obtained in the step A2 at a light intensity of 3mW/cm2Irradiating for 25 days under an ultraviolet lamp, and then simultaneously assisting ultrasonic treatment to carry out ultrasonic-enhanced photocatalytic degradation reaction on the plastic microspheres; the power of ultrasonic treatment is 500w, and ultrasonic treatment is carried out for 0.5h every 1 h;
a4, and after the ultrasonic-enhanced photocatalytic degradation reaction in the step A3 is finished, recovering the photocatalyst.
After the degradation reaction of the plastic microspheres is finished, the degradation rate of the plastic microspheres in the concentrated wastewater reaches 86% through detection.
Comparative example 1
The difference from example 1 is that: the degradation of the plastic microspheres in the wastewater is carried out by using pure titanium dioxide hollow microspheres as a catalyst, and the rest is the same as that in example 1, and is not described again.
Comparative example 2
The difference from example 1 is that: in step a3, only photocatalytic degradation is performed, ultrasonic-assisted degradation is not performed, and degradation of plastic beads in wastewater is performed, which are the same as those in example 1, and thus, details are not repeated herein.
Comparative example 3
The difference from example 1 is that: the degradation of the plastic microspheres in the wastewater is carried out by only ultrasonic degradation without adopting photocatalyst degradation, and the rest is the same as that of the embodiment 1, and the details are not repeated.
Comparative example 4
The difference from example 1 is that: the iron-nitrogen doped titanium dioxide powder is used as a catalyst to degrade the plastic microspheres in the wastewater, and the rest is the same as that in example 1, and is not described again.
Comparative example 5
The difference from example 1 is that: the iron-doped carbon dioxide hollow microspheres are used as a catalyst to degrade the plastic microspheres in the wastewater, and the rest is the same as that in example 1, and the details are not repeated.
Comparative example 6
The difference from example 1 is that: the degradation of the plastic microspheres in the wastewater is carried out by using nitrogen-doped carbon dioxide hollow microspheres as a catalyst, and the rest is the same as that in example 1, and is not repeated herein.
Table 1 shows the performance parameters of example 1 and comparative examples 1 to 6
| Examples | Degradation Properties |
| Example 1 | 86％ |
| Comparative example 1 | 41％ |
| Comparative example 2 | 76％ |
| Comparative example 3 | 22％ |
| Comparative example 4 | 51％ |
| Comparative example 5 | 80％ |
| Comparative example 6 | 77％ |
Example 1 and comparative examples 1-6 were analyzed in conjunction with table 1: the degradation efficiency of the iron-nitrogen doped titanium dioxide hollow microsphere photocatalyst adopted in the embodiment 1 on the plastic microspheres in the wastewater reaches 86 percent and is higher than that of the comparative examples 1-6.
Examples 2 to 5
The difference from example 1 is that: the preparation process parameters of the photocatalyst are set differently, and the rest are the same as those of the example 1, and are not described again.
Table 2 shows the process parameter settings and their performance parameters of examples 1-6
Examples 1-5 were analyzed in conjunction with Table 2: as can be seen from table 2, the doping amount of both iron and nitrogen and the change of the ultrasonic power have a certain influence on the degradation performance of the photocatalyst.
In the present invention, the molar mass ratio of iron, nitrogen and titanium is preferably 2: 4: 100, respectively; the ultrasonic power is preferably 300W.
Examples 6 to 8
The difference from example 1 is that: the parameters of the degradation process are set differently, and the rest are the same as those of the example 1, and are not described again.
Table 3 shows the process parameter settings and performance parameters of examples 1 and 6-8
| Examples | Amount of photocatalyst used | Light intensity | Ultrasonic power | Degradation Properties |
| Example 1 | 20mg/L | 3mW/cm2 | 500W | 86％ |
| Example 6 | 50mg/L | 3mW/cm2 | 500W | 87％ |
| Example 7 | 20mg/L | 4mW/cm2 | 500W | 88％ |
| Example 8 | 20mg/L | 3mW/cm2 | 400W | 83％ |
Example 1 and examples 6-8 were analyzed in conjunction with table 3: in the degradation of the waste water plastic microspheres, the dosage of the photocatalyst, the light intensity and the ultrasonic power are improved, so that the degradation efficiency of the plastic microspheres can be improved to a certain extent.
In conclusion, the invention provides a photocatalyst, a preparation method thereof and application thereof in degrading waste water plastic microspheres, wherein the photocatalyst is iron-nitrogen doped titanium dioxide hollow microspheres; the particle size of the iron-nitrogen doped titanium dioxide hollow microsphere is 100-600 nm, the pore diameter of the microsphere is 5-15 nm, and the specific surface area of the iron-nitrogen doped titanium dioxide hollow microsphere is 200-400 m2The method combines the photocatalytic reaction of the photocatalyst and the ultrasonic degradation process to carry out synergistic degradation on the plastic microspheres in the wastewater, has excellent photocatalytic degradation efficiency, and has great application value in the field of degradation treatment of the plastic microspheres in the wastewater.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions deviate from the technical solutions of the embodiments of the present invention.
Claims (10)
1. A photocatalyst, characterized in that: the photocatalyst is an iron-nitrogen doped titanium dioxide hollow microsphere; the particle size of the iron-nitrogen doped titanium dioxide hollow microsphere is 100-600 nm, the pore diameter of the microsphere is 5-15 nm, and the specific surface area of the iron-nitrogen doped titanium dioxide hollow microsphere is 200-400 m2/g。
2. The photocatalyst as set forth in claim 1, wherein: in the iron-nitrogen doped titanium dioxide hollow microsphere, the atomic ratio of iron to titanium is (1-3): 100, respectively; the atomic ratio of nitrogen to titanium is (2-5): 100.
3. a method for preparing the photocatalyst as set forth in any one of claims 1 to 2, characterized in that: the method comprises the following steps:
s1, slowly dripping tetrabutyl titanate into absolute ethyl alcohol, fully stirring to mix the tetrabutyl titanate and the absolute ethyl alcohol uniformly, adding a predetermined amount of acetic acid, and stirring to prepare a titanium dioxide precursor solution;
s2, adding ferric nitrate and carbamide into absolute ethyl alcohol according to a preset proportion, adding a preset amount of water, and stirring to fully dissolve to prepare an iron-nitrogen precursor solution;
s3, slowly dripping the iron-nitrogen precursor solution prepared in the step S2 into the titanium dioxide precursor solution prepared in the step S1, adjusting the pH value to 3-4, stirring for 30-40 min to prepare a mixed solution, transferring the mixed solution into a hydrothermal reaction kettle, adding a predetermined amount of water, simultaneously assisting with ultrasonic treatment, and carrying out hydrothermal reaction for 8-24 h at 150-170 ℃;
s4, after the hydrothermal reaction in the step S3 is finished, taking out a product, centrifugally washing, fully grinding, and roasting at 400-500 ℃ for 1-3 hours to prepare the iron-nitrogen doped titanium dioxide hollow microsphere, namely the photocatalyst.
4. The method for producing a photocatalyst according to claim 3, characterized in that: in step S1, the volume ratio of the tetrabutyl titanate to the absolute ethyl alcohol is 1: (2-3).
5. The method for producing a photocatalyst according to claim 3, characterized in that: in step S2, the molar mass ratio of the iron nitrate to the carbamide is (1-5): (1-3).
6. The method for producing a photocatalyst according to claim 3, characterized in that: in the ultrasonic treatment of the step S3, the ultrasonic power is set to be 200-400W.
7. The method for producing a photocatalyst according to claim 3, characterized in that: in the mixed solution described in step S3, the ratio of the molar mass of iron, the molar mass of nitrogen, and the molar mass of titanium is (1 to 3): (2-5): 100.
8. the method for producing a photocatalyst according to claim 3, characterized in that: in step S3, the volume ratio of the iron-nitrogen precursor solution to the titanium dioxide precursor solution is 1: (2-3).
9. Use of the photocatalyst according to any one of claims 1 to 2 or the photocatalyst prepared by the method for preparing the photocatalyst according to any one of claims 3 to 8 for degrading waste water plastic microbeads.
10. The use of the photocatalyst in degrading waste water plastic microbeads according to claim 9, wherein: the application comprises the following steps:
a1, performing filtration concentration treatment on the wastewater containing the plastic microspheres with the particle size of less than 5mm, wherein the filtration precision is less than or equal to 5 microns, so as to obtain concentrated wastewater; in the concentrated wastewater, the abundance of the plastic microspheres is 105～1010Per liter;
a2, adding the photocatalyst into the concentrated wastewater prepared in the step A1, and stirring for 10-30 min for fully mixing to obtain a pretreatment solution; in the pretreatment solution, the addition amount of the photocatalyst is 10-100 mg/L;
a3, placing the pretreatment solution obtained in the step A2 at a light intensity of 1-5 mW/cm2Irradiating for 10-30 days under an ultraviolet lamp, and then simultaneously assisting with ultrasonic treatment to carry out ultrasonic-enhanced photocatalytic degradation reaction on the plastic microspheres; the power of ultrasonic treatment is 400-600 w;
a4, and after the ultrasonic-enhanced photocatalytic degradation reaction in the step A3 is finished, recovering the photocatalyst.
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