CN114130397A - ZnO-based heterojunction photocatalytic composite material and preparation and application thereof - Google Patents
ZnO-based heterojunction photocatalytic composite material and preparation and application thereof Download PDFInfo
- Publication number
- CN114130397A CN114130397A CN202111428842.3A CN202111428842A CN114130397A CN 114130397 A CN114130397 A CN 114130397A CN 202111428842 A CN202111428842 A CN 202111428842A CN 114130397 A CN114130397 A CN 114130397A
- Authority
- CN
- China
- Prior art keywords
- tio
- rgo
- zno
- reaction
- composite material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 48
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 106
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 45
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000000725 suspension Substances 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 30
- 239000000463 material Substances 0.000 claims abstract description 29
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 26
- 239000002086 nanomaterial Substances 0.000 claims abstract description 22
- 239000002105 nanoparticle Substances 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000012153 distilled water Substances 0.000 claims abstract description 11
- 239000003344 environmental pollutant Substances 0.000 claims abstract description 11
- 231100000719 pollutant Toxicity 0.000 claims abstract description 7
- 239000000575 pesticide Substances 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 29
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 27
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 15
- 229910021389 graphene Inorganic materials 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 238000001354 calcination Methods 0.000 claims description 10
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 9
- 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 9
- 229940044631 ferric chloride hexahydrate Drugs 0.000 claims description 8
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims description 8
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 239000001632 sodium acetate Substances 0.000 claims description 7
- 235000017281 sodium acetate Nutrition 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 235000019441 ethanol Nutrition 0.000 claims description 6
- 238000004108 freeze drying Methods 0.000 claims description 6
- 238000003760 magnetic stirring Methods 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000012805 post-processing Methods 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 239000002356 single layer Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims 1
- 230000015556 catabolic process Effects 0.000 abstract description 16
- 238000006731 degradation reaction Methods 0.000 abstract description 16
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 7
- 239000004246 zinc acetate Substances 0.000 abstract description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 4
- 239000001301 oxygen Substances 0.000 abstract description 4
- 239000003054 catalyst Substances 0.000 abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 abstract description 3
- 238000001429 visible spectrum Methods 0.000 abstract description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 108
- 239000011787 zinc oxide Substances 0.000 description 72
- 239000000243 solution Substances 0.000 description 35
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 14
- 239000005906 Imidacloprid Substances 0.000 description 13
- YWTYJOPNNQFBPC-UHFFFAOYSA-N imidacloprid Chemical compound [O-][N+](=O)\N=C1/NCCN1CC1=CC=C(Cl)N=C1 YWTYJOPNNQFBPC-UHFFFAOYSA-N 0.000 description 13
- 229940056881 imidacloprid Drugs 0.000 description 13
- 230000031700 light absorption Effects 0.000 description 9
- 239000011941 photocatalyst Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 6
- 229910003081 TiO2−x Inorganic materials 0.000 description 5
- 239000000696 magnetic material Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000004408 titanium dioxide Substances 0.000 description 4
- 229910001868 water Inorganic materials 0.000 description 4
- 239000004809 Teflon Substances 0.000 description 3
- 229920006362 Teflon® Polymers 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000000593 degrading effect Effects 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000002114 nanocomposite Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 229910017135 Fe—O Inorganic materials 0.000 description 2
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 2
- 229910003088 Ti−O−Ti Inorganic materials 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000002917 insecticide Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 231100000956 nontoxicity Toxicity 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000011219 quaternary composite Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 208000024827 Alzheimer disease Diseases 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- 208000018737 Parkinson disease Diseases 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000001684 chronic effect Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000004064 dysfunction Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000003574 free electron Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- -1 iron cations Chemical class 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000001123 neurodevelopmental effect Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- JFINOWIINSTUNY-UHFFFAOYSA-N pyrrolidin-3-ylmethanesulfonamide Chemical compound NS(=O)(=O)CC1CCNC1 JFINOWIINSTUNY-UHFFFAOYSA-N 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000001055 reflectance spectroscopy Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Images
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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- 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
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
Abstract
The invention provides a ZnO-based heterojunction photocatalytic composite material and preparation and application thereof. The method comprises the following steps: step 1, preparing TiO2Sol; step 2, preparing TiO2‑rGO/Fe3O4A suspension; step 3, adding zinc acetate dissolved in distilled water to the TiO2‑rGO/Fe3O4In the suspension, adjusting the pH value to 12 by using a sodium hydroxide solution, and then carrying out a first hydrothermal reaction; step 4, carrying out first post-treatment on the reaction system after the first hydrothermal reaction to obtain ZnO1‑x@TiO2‑x‑rGO/Fe3O4And (3) nano materials. The visible light catalyst provided by the invention has good stability, high degradation rate on micropollutants and simple preparation method; wherein TiO with oxygen holes is attached to the surface of the rGO elementary material2‑xNanoparticles, ZnO1‑xNanoparticles and Fe-supported3O4The nano-particles have the advantages of absorbing visible light of full visible spectrum, being convenient to recycle and reuse and the like, and can be suitable for high-efficiency photocatalytic treatment of neonicotinoid pesticide pollutants.
Description
Technical Field
The invention relates to the technical field of visible light catalysis, and mainly relates to a ZnO-based heterojunction photocatalytic composite material as well as preparation and application thereof.
Background
The widespread distribution of micropollutants in aquatic environments has become an increasing concern. These contaminants enter the water body primarily through home, hospital, agricultural and industrial activities. The accumulation of neonicotinoid insecticides in the environment can not only affect the survival of pollinating insects, but also cause chronic harm to human health. Studies have shown that prolonged exposure to neonicotinoid insecticides increases the risk of neurodevelopmental dysfunction in children and parkinson's and alzheimer's disease in the elderly.
At present, methods for degrading the pollutants by microorganisms exist, but the traditional technology is complex, low in efficiency and easy to influence by environmental factors. The photocatalysis technology is more and more concerned by people due to the advantages of simple operation, rapid reaction, green and high efficiency and the like. However, due to the physicochemical properties of the semiconductor material, the energy band of the semiconductor material is wide, the semiconductor material can only respond to the ultraviolet interval in sunlight, and the photogenerated electrons and holes are easy to recombine, so that the semiconductor material is not beneficial to degrading pollutants under the condition of visible light.
Therefore, developing a visible light catalytic nano material which has the advantages of simple preparation method, higher visible light utilization rate, higher micro-pollutant degradation rate, better stability and convenient recovery and reuse is a key research target of the technology in the field.
Disclosure of Invention
In order to solve the problems, the invention provides a ZnO-based heterojunction photocatalytic composite material and preparation and application thereof, so as to achieve the aims of preparing a visible light photocatalytic nano material which has higher visible light utilization rate, higher micro-pollutant degradation rate and better stability and is convenient to recycle.
In a first aspect, the invention provides a ZnO-based heterojunction photocatalytic composite material, which takes a single layer of rGO as a basic material, and TiO is grafted on the basic material2-xNanoparticles, ZnO1-xNanoparticles and Fe3O4Nanoparticles, wherein x is 0.05 to 0.45.
Preferably, the molar ratio of Fe to Ti to Zn in the composite material is 0.5-2: 1: 1.
In a second aspect, the present invention provides a method for preparing a ZnO-based heterojunction photocatalytic composite material, for preparing the composite material of the first aspect, the method comprising:
step 1, preparing TiO2Sol;
step 2, preparing TiO2-rGO/Fe3O4A suspension;
step 3, adding zinc acetate dissolved in distilled water to the TiO2-rGO/Fe3O4In the suspension, adjusting the pH value to 12 by using a sodium hydroxide solution, and then carrying out a first hydrothermal reaction;
step 4, carrying out first post-treatment on the reaction system after the first hydrothermal reaction to obtain ZnO1-x@TiO2-x/rGO-Fe3O4And (3) nano materials.
Preferably, in the step 1, TiO is prepared2The sol process includes the following steps:
under magnetic stirring, dropwise adding acetic acid and tetrabutyl titanate into anhydrous ethanol at the speed of 4 s/drop and 1 s/drop to obtain a solution A;
adding absolute ethyl alcohol and deionized water into a beaker, and adjusting the pH of the solution to 2 by using dilute nitric acid to prepare a solution B;
slowly adding the solution B into the solution A, and continuously stirring for 30min to obtain TiO2And (3) sol.
Preferably, in the step 2, TiO is prepared2-rGO/Fe3O4The suspension procedure was as follows:
adding the single-layer graphene oxide suspension into ethylene glycol or isopropanol, and dispersing uniformly by using ultrasonic waves to obtain a graphene oxide mixed system;
and adding an organic alcohol solution of ferric chloride hexahydrate into the graphene oxide mixed system, and uniformly mixing to obtain a first mixed system.
Mixing sodium acetate and TiO2Adding the sol and ethylenediamine into the first mixed system in sequence to obtain a second mixed system;
placing the second mixed system in a reaction container to perform a second hydrothermal reaction;
carrying out second post-treatment on the reaction system after the second hydrothermal reaction to obtain TiO2-x/rGO-Fe3O4And (3) suspension.
More preferably, the reaction time of the second hydrothermal reaction is 8-12h, and the reaction temperature is 150-;
the second post-processing includes:
washing the reaction system to be neutral by using absolute ethyl alcohol;
dispersing the washed product into distilled water to obtain TiO2-rGO/Fe3O4And (3) suspension.
Preferably, in the step 3, the reaction time of the first hydrothermal reaction is 1-2h, and the reaction temperature is 150-.
Preferably, in the step 4, the first post-processing includes:
centrifuging the residue after the first hydrothermal reaction for 5-7 times and freeze-drying to obtain ZnO @ TiO2-rGO/Fe3O4；
Mixing the aboveZnO@TiO2-rGO/Fe3O4Calcining for 2-4h in a tubular furnace at the temperature of 300 ℃ and 550 ℃ under the protection of nitrogen or vacuum.
In a third aspect, the invention provides an application of a ZnO-based heterojunction photocatalytic composite material, wherein the application comprises the following steps:
the composite material is used for high-efficiency photocatalytic treatment of neonicotinoid pesticide pollutants.
The invention attaches TiO with oxygen cavity on the surface of rGO elementary material2-xNanoparticles, ZnO1-xNanoparticles and Fe-supported3O4Preparation of ZnO from nanoparticles1-x@TiO2-x-rGO/Fe3O4And (3) nano materials. Wherein, TiO2ZnO is the most widely used photocatalyst in semiconductors, has the attractive characteristics of no toxicity, low cost, excellent chemical stability, corrosion resistance, excellent photocatalytic performance and the like, and is a preferred material for preparing the photocatalyst. First of all, TiO is prepared2Sol, and doping to obtain ZnO @ TiO2-rGO/Fe3O4With simple TiO2In contrast, the light absorption boundary of the composite obtained by doping is obviously red-shifted. Finally calcining ZnO @ TiO under the condition of no oxygen2-rGO/Fe3O4Preparation of ZnO1-x@TiO2-x-rGO/Fe3O4Composite material, in which case ZnO can be clearly seen1-x@TiO2-x-rGO/Fe3O4The light absorption range of the composite material is widened to the full visible spectrum, and the light capture efficiency of the composite material is obviously improved. And Fe3O4As a typical magnetic material, the addition of the magnetic material can effectively solve the problem of ZnO1-x@TiO2-x-separation problems and secondary pollution problems of rGO photocatalysts. In general, the composite material is simple to prepare, has higher visible light utilization rate, higher micro-pollutant degradation rate and better stability, and is convenient to recycle.
The method of the invention can achieve the following advantages: (1) the raw materials of rGO, tetrabutyl titanate, ethylenediamine, ferric chloride hexahydrate and the like used in the inventionThe materials are all low-toxic or even non-toxic, the source is wide, the cost is low, and the prepared TiO2The quaternary composite material obtained by subsequent hydrothermal reaction and high-temperature calcination has excellent photocatalytic performance, greatly improves the utilization rate of sunlight, and has obvious effect on the degradation of micro pollutants. (2) As a typical magnetic material, Fe3O4Can effectively solve the problem of ZnO1-x@TiO2-xSeparation problems and secondary pollution problems of rGO photocatalysts, therefore the present invention is conveniently recyclable and recyclable. (3) The preparation method is simple, has low cost and relatively mild reaction conditions, and is favorable for high-quality ZnO1-x@TiO2-x-rGO/Fe3O4And (4) producing the nano material.
In summary, the preparation method of the ZnO-based heterojunction photocatalytic composite material of the present invention firstly prepares the TiO2Sol according to the prepared TiO2The sol, ferric chloride hexahydrate, sodium acetate, ethylenediamine and the like are taken as raw materials to prepare TiO through hydrothermal reaction2-rGO/Fe3O4Suspending the mixture, adding zinc acetate and sodium hydroxide into the suspension, and generating ZnO @ TiO under hydrothermal conditions2-rGO/Fe3O4Finally obtaining ZnO by high-temperature calcination1-x@TiO2-x-rGO/Fe3O4And (3) nano materials. The method has mild reaction conditions in each step, is simple to operate and low in cost, and greatly improves the preparation efficiency.
Drawings
Fig. 1 shows a flow chart of a method for preparing a ZnO-based heterojunction photocatalytic composite material in an embodiment of the present invention;
FIG. 2 shows ZnO prepared in example 1 of the present invention1-x@TiO2-x-rGO/Fe3O4SEM images of nanoparticles;
FIG. 3 shows TiO in example 1 of the present invention2、ZnO@TiO2、TiO2-rGO/Fe3O4、 ZnO@TiO2-rGO/Fe3O4And ZnO1-x@TiO2-x-rGO/Fe3O4Diffuse reflection of ultraviolet lightA spectrogram;
FIG. 4 shows TiO in example 1 of the present invention2、ZnO@TiO2-rGO/Fe3O4And ZnO1-x@TiO2-x-rGO/Fe3O4A Fourier infrared spectrum;
FIG. 5 shows TiO in Experimental example 1 of the present invention2、ZnO@TiO2、ZnO@TiO2-rGO/Fe3O4、 TiO2-x-rGO/Fe3O4And ZnO1-x@TiO2-x-rGO/Fe3O4A performance contrast chart of visible light catalytic degradation imidacloprid;
FIG. 6 shows ZnO prepared in example 1 of the present invention1-x@TiO2-x-rGO/Fe3O4And (3) a performance contrast diagram of the nano material for degrading imidacloprid under visible light catalysis under different environmental conditions of pure illumination, PS and PMS.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, preferred embodiments accompanied with examples are described in detail below. It is to be understood that the following examples are given for illustrative purposes only and are not intended to limit the scope of the present invention. Various modifications and alterations of this invention will become apparent to those skilled in the art without departing from the spirit and scope of this invention. Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
In a first aspect, embodiments of the present invention provide a ZnO-based heterojunction photocatalytic composite material, in which a single layer rGO is used as a basic material, and TiO is grafted on the basic material2-xNanoparticles, ZnO1-xNanoparticles and Fe3O4The nano-particles are obtained, wherein x is 0.05-0.45, and the molar ratio of Fe to Ti to Zn in the quaternary composite visible-light-driven photocatalyst is 0.5-2: 1: 1.
Wherein titanium dioxide (TiO)2) And zinc oxide (ZnO) are the most widely used photocatalysts in other semiconductors, and have the advantages of no toxicity, low cost, excellent chemical stability, corrosion resistance and high yieldThe photocatalytic performance of the color and the like. While both also have the same band gap energy (anatase TiO)23.2eV, ZnO 3.37 eV). In addition, TiO can be improved obviously after ZnO is added2Agglomeration of nanoparticles on the surface of rGO sheets to make TiO2The crystal grains are uniform in size, the dispersity among the crystal grains is enhanced, and the effective contact specific surface area of the composite material and the degraded substance is effectively increased.
The rGO has good conductivity, adsorption capacity and large specific surface area. In addition, rGO can also reduce electron-hole pair recombination due to its excellent interlayer interactions, increasing the catalyst and contaminant contact area.
Based on the method, the embodiment of the invention provides the method for preparing ZnO by doping rGO1-x@TiO2-x-rGO/Fe3O4Composite material, and ZnO1-x@TiO2-x-rGO/Fe3O4The composite material has excellent electron mobility (200000 cm)2·V-1·s-1) And large specific surface area, and has the advantages of large capacity, large effective catalytic surface area of reaction, high mass transfer rate of liquid to photocatalyst, and the like.
Further, Fe3O4As a typical magnetic material, the addition of the magnetic material can effectively solve the problem of ZnO1-x@TiO2-x-separation problems and secondary pollution problems of rGO material. Further, Fe3O4Not only can maintain unique superparamagnetism, but also can accelerate photoinduced electrons to be in two oxidation states (Fe) of iron3+，Fe2+) Thereby improving the photocatalytic activity of the composite material.
In a second aspect, an embodiment of the present invention provides a method for preparing a ZnO-based heterojunction photocatalytic composite material, for preparing the composite material according to the first aspect, the method including:
step 1, preparing TiO2Sol;
step 2, preparing TiO2-rGO/Fe3O4A suspension;
step 3, dissolving B in distilled waterZinc salt to the above TiO2-rGO/Fe3O4In the suspension, adjusting the pH value to 12 by using a sodium hydroxide solution, and then carrying out a first hydrothermal reaction;
step 4, carrying out first post-treatment on the reaction system after the first hydrothermal reaction to obtain ZnO1-x@TiO2-x/rGO-Fe3O4And (3) nano materials.
Preferably, in the step 1, TiO is prepared2The sol process includes the following steps:
under magnetic stirring, dropwise adding acetic acid and tetrabutyl titanate into anhydrous ethanol at the speed of 4 s/drop and 1 s/drop to obtain a solution A;
adding absolute ethyl alcohol and deionized water into a beaker, and adjusting the pH of the solution to 2 by using dilute nitric acid to prepare a solution B;
slowly adding the solution B into the solution A, and continuously stirring for 30min to obtain TiO2And (3) sol.
In the embodiment of the invention, hydrolysis reaction can also occur when tetrabutyl titanate is dripped into absolute ethyl alcohol, in order to inhibit the generation of hydrolysis reaction, acetic acid is additionally dripped into absolute ethyl alcohol, and the dripping speeds of the acetic acid and the tetrabutyl titanate are respectively 4 s/drop and 1 s/drop, and the dripping is carried out at the speed, so that the hydrolysis reaction speed can be effectively reduced; furthermore, by using TiO2Sol form to facilitate TiO in subsequent synthesis steps2Natural crystallization of nanoparticles to the surface of the support (rGO) resulting in the formation of TiO2Small particle size, high purity, good dispersibility, and effective improvement of TiO2Agglomeration of particles on the surface of the support (rGO).
Preferably, in the step 2, TiO is prepared2-rGO/Fe3O4The suspension procedure was as follows:
adding the single-layer graphene oxide suspension into ethylene glycol or isopropanol, and dispersing uniformly by using ultrasonic waves to obtain a graphene oxide mixed system;
and adding an organic alcohol solution of ferric chloride hexahydrate into the graphene oxide mixed system, and uniformly mixing to obtain a first mixed system.
Mixing sodium acetate and TiO2Adding the sol and ethylenediamine into the first mixed system in sequence to obtain a second mixed system;
in the embodiment of the invention, the addition of the ethylenediamine can not only prepare Fe with the first mixed system3O4And the particle size of the composite material can be effectively improved, and a nano material with smaller particle size can be formed.
Placing the second mixed system in a reaction container to perform a second hydrothermal reaction;
carrying out second post-treatment on the reaction system after the second hydrothermal reaction to obtain TiO2-x/rGO-Fe3O4And (3) suspension.
More preferably, the reaction time of the second hydrothermal reaction is 8-12h, and the reaction temperature is 150-;
the second post-processing includes:
washing the reaction system to be neutral by using absolute ethyl alcohol;
dispersing the washed product into distilled water to obtain TiO2-rGO/Fe3O4And (3) suspension.
Preferably, in the step 3, the reaction time of the first hydrothermal reaction is 1-2h, and the reaction temperature is 150-.
Preferably, in the step 4, the first post-processing includes:
centrifuging the residue after the hydrothermal reaction for 5-7 times and freeze-drying to obtain ZnO @ TiO2-rGO/Fe3O4；
The ZnO @ TiO is mixed2-rGO/Fe3O4Calcining for 2-4h in a tubular furnace at the temperature of 300 ℃ and 550 ℃ under the protection of nitrogen or vacuum.
The above-described preferred conditions may be combined with each other to obtain a specific embodiment, in accordance with common knowledge in the art.
In a third aspect, the embodiments of the present invention provide applications of the ZnO-based heterojunction photocatalytic composite material of the first aspect.
The composite material is used for high-efficiency photocatalytic treatment of neonicotinoid pesticide pollutants.
The ZnO-based heterojunction photocatalytic composite material is excited by electrons to move from the conduction band of ZnO to TiO under the irradiation of light2The hole is formed by TiO2The valence band of the material is transferred to the valence band of ZnO, so that the recombination rate of current carriers is reduced, the catalytic activity of the composite photocatalyst is improved, and free electrons excited on the surface of the material and H in a water body2The reaction of O produces hydroxyl radicals, which react with dissolved oxygen in water to produce superoxide radicals. Because the material has a large number of cavities and the combined action of the active oxidation substances (hydroxyl free radicals and superoxide free radicals), the neonicotinoid pesticide can be oxidized into small molecular substances or mineralized into CO2、H2O, and the like.
In order to make the present invention better understood by those skilled in the art, the following examples are provided to illustrate the preparation method of the ZnO-based heterojunction photocatalytic composite material provided by the present invention.
Example 1
Step 1: 20mL of absolute ethanol was placed in a beaker, and 1.5mL of acetic acid and 5mL of tetrabutyl titanate were added dropwise at a rate of 4 s/drop and 1 s/drop under magnetic stirring. The resulting mixed liquid was labeled as solution a. 17ml of absolute ethyl alcohol and 3ml of deionized water were added to a beaker, and the pH of the solution was adjusted to 2 with dilute nitric acid to obtain a solution B. Slowly adding the solution B into the solution A, and continuously stirring for 30min to obtain TiO2And (3) sol.
Step 2: 150g of the graphene oxide suspension was added to 150mL of ethylene glycol, and dispersed into the homogeneous mixed solution using ultrasonic waves. Meanwhile, 1g of ferric chloride hexahydrate is dissolved in 10mL of ethylene glycol, the mixture is added into a dispersed graphene oxide mixed system after complete dissolution, the first mixed system is obtained by stirring at a constant speed, then 3g of sodium acetate, 2mL of titanium dioxide sol and 10mL of ethylenediamine are sequentially added into the first mixed system, and the second mixed system is obtained by continuously stirring for 30 minutes. Transferring the second mixed system into a Teflon stainless steel reaction vessel, heating at 150-200 ℃ for 8-12h, naturally cooling to room temperature, washing with ethanol to neutrality, and finally dispersing into 100mL of distilled water to obtain the productTiO2-rGO/Fe3O4And (3) suspension.
And step 3: 200mg of zinc acetate was dissolved in 50ml of distilled water and added to the 100ml of TiO described in step 22-rGO/Fe3O4In suspension. The solution was adjusted to pH 12 with 0.1M NaOH solution. Thereafter, the mixture was heated in a high-pressure reaction vessel at 150 ℃ and 200 ℃ for 1-2 hours.
And 4, step 4: centrifuging the residue after the hydrothermal reaction for 5-7 times and freeze-drying to obtain ZnO @ TiO2-rGO/Fe3O4(ii) a Calcining the prepared precursor in a tubular furnace for 2-4h under the protection of nitrogen at the temperature of 300-550 ℃ to obtain ZnO1-x@TiO2-x-rGO/Fe3O4And (3) nano materials. Repeating the above operations to obtain the nano composite material with the molar ratio of Fe to Ti to Zn of 0.5:1:1 respectively, and marking as ZnO1-x@TiO2-x-rGO/Fe3O4-1。
Example 2
Step 1: 20mL of absolute ethanol was placed in a beaker, and 1.5mL of acetic acid and 5mL of tetrabutyl titanate were added dropwise at a rate of 4 s/drop and 1 s/drop under magnetic stirring. The resulting mixed liquid was labeled as solution a. 17ml of absolute ethyl alcohol and 3ml of deionized water were added to a beaker, and the pH of the solution was adjusted to 2 with dilute nitric acid to obtain a solution B. Slowly adding the solution B into the solution A, and continuously stirring for 30min to obtain TiO2And (3) sol.
Step 2: 150g of the graphene oxide suspension was added to 150mL of ethylene glycol, and dispersed into the homogeneous mixed solution using ultrasonic waves. Meanwhile, 1g of ferric chloride hexahydrate is dissolved in 10mL of ethylene glycol, the mixture is added into a dispersed graphene oxide mixed system after complete dissolution, the first mixed system is obtained by stirring at a constant speed, then 3g of sodium acetate, 2mL of titanium dioxide sol and 10mL of ethylenediamine are sequentially added into the first mixed system, and the second mixed system is obtained by continuously stirring for 30 minutes. Transferring the second mixed system into a Teflon stainless steel reaction vessel, heating at 150-200 ℃ for 8-12h, naturally cooling to room temperature, washing with ethanol to neutrality, and finally dispersing into 100mL of distilled water to obtain TiO2-rGO/Fe3O4And (3) suspension.
And step 3: 200mg of zinc acetate was dissolved in 50ml of distilled water and added to the 100ml of TiO described in step 22-rGO/Fe3O4In suspension. The solution was adjusted to pH 12 with 0.1M NaOH solution. Thereafter, the mixture was heated in a high-pressure reaction vessel at 150 ℃ and 200 ℃ for 1-2 hours.
And 4, step 4: centrifuging the residue after the hydrothermal reaction for 5-7 times and freeze-drying to obtain ZnO @ TiO2-rGO/Fe3O4(ii) a Calcining the prepared precursor in a tubular furnace for 2-4h under the protection of nitrogen at the temperature of 300-550 ℃ to obtain ZnO1-x@TiO2-x-rGO/Fe3O4And (3) nano materials. Repeating the operation to obtain the nano composite material with the molar ratio of Fe to Ti to Zn being 1:1:1 respectively, and marking as ZnO1-x@TiO2-x-rGO/Fe3O4-2。
Example 3
Step 1: 20mL of absolute ethanol was placed in a beaker, and 1.5mL of acetic acid and 5mL of tetrabutyl titanate were added dropwise at a rate of 4 s/drop and 1 s/drop under magnetic stirring. The resulting mixed liquid was labeled as solution a. 17ml of absolute ethyl alcohol and 3ml of deionized water were added to a beaker, and the pH of the solution was adjusted to 2 with dilute nitric acid to obtain a solution B. Slowly adding the solution B into the solution A, and continuously stirring for 30min to obtain TiO2And (3) sol.
Step 2: 150g of the graphene oxide suspension was added to 150mL of ethylene glycol, and dispersed into the homogeneous mixed solution using ultrasonic waves. Meanwhile, 1g of ferric chloride hexahydrate is dissolved in 10mL of ethylene glycol, the mixture is added into a dispersed graphene oxide mixed system after complete dissolution, the first mixed system is obtained by stirring at a constant speed, then 3g of sodium acetate, 2mL of titanium dioxide sol and 10mL of ethylenediamine are sequentially added into the first mixed system, and the second mixed system is obtained by continuously stirring for 30 minutes. Transferring the second mixed system into a Teflon stainless steel reaction vessel, heating at 150-200 ℃ for 8-12h, naturally cooling to room temperature, washing with ethanol to neutrality, and finally dispersing into 100mL of distilled water to obtain TiO2-rGO/Fe3O4And (3) suspension.
And step 3: 200mg of zinc acetate was dissolved in 50ml of distilled water and added to the 100ml of TiO described in step 22-rGO/Fe3O4In suspension. The solution was adjusted to pH 12 with 0.1M NaOH solution. Thereafter, the mixture was heated in a high-pressure reaction vessel at 150 ℃ and 200 ℃ for 1-2 hours.
And 4, step 4: centrifuging the residue after the hydrothermal reaction for 5-7 times and freeze-drying to obtain ZnO @ TiO2-rGO/Fe3O4(ii) a Calcining the prepared precursor in a tubular furnace for 2-4h under the protection of nitrogen at the temperature of 300-550 ℃ to obtain ZnO1-x@TiO2-x-rGO/Fe3O4And (3) nano materials. Repeating the operation to obtain the nano composite material with the molar ratio of Fe to Ti to Zn of 2:1:1 respectively, and marking as ZnO1-x@TiO2-x-rGO/Fe3O4-3。
In order to further illustrate that the ZnO-based heterojunction photocatalytic composite material prepared by the invention has the superior performances of high visible light utilization rate and high micro-pollutant degradation rate, the ZnO-based heterojunction photocatalytic composite material is analyzed by combining a specific figure.
Fig. 1 shows a flow chart of a method for preparing a ZnO-based heterojunction photocatalytic composite material in an embodiment of the present invention. As can be seen from the figure, TiO is first prepared in the present invention2Sol and further preparation of TiO2-rGO/Fe3O4Adding zinc acetate and sodium hydroxide into the suspension, and obtaining ZnO through hydrothermal reaction and post-treatment1-x@TiO2-x-rGO/Fe3O4And (3) nano materials.
FIG. 2 shows ZnO prepared in example 1 of the present invention1-x@TiO2-x-rGO/Fe3O4SEM image of nanoparticles. The flakes in the figure are rGO, and the remaining three particles are uniformly coated on the surface of the rGO flakes.
FIG. 3 is TiO2、ZnO@TiO2、TiO2-rGO/Fe3O4、ZnO@TiO2-rGO/Fe3O4And ZnO1-x@TiO2-x-rGO/Fe3O4The ultraviolet absorption spectrum of (2) was analyzed by ultraviolet diffuse reflectance spectroscopy. As can be seen, the light absorption boundaries of the above materials are all around 390 nm. With TiO2In contrast, the light absorption boundaries of the composite materials with different doping ratios are all significantly red-shifted. To in ZnO @ TiO2-rGO/Fe3O4Further increasing the visible light absorption range of the composite material by calcining ZnO @ TiO under vacuum condition2-rGO/Fe3O4Preparing ZnO1-x@TiO2-x-rGO/Fe3O4A composite material. The visible light absorption boundaries of the composite material are red-shifted to different degrees before and after calcination, and ZnO has a red shift at a calcination temperature of 500 DEG C1-x@TiO2-x-rGO/Fe3O4The light absorption range of the composite material is obviously widened to the full visible spectrum, the light capture efficiency of the composite material is obviously improved, and meanwhile, the TiO is compared with the TiO2-x-rGO/Fe3O4And the visible light absorption range of the new material is not easy to see compared with that of TiO2-x-rGO/Fe3O4The improvement is remarkable, the light utilization efficiency of the photocatalyst is effectively improved, and the mutual evidence is improved with the subsequent degradation efficiency.
FIG. 4 shows TiO in example 1 of the present invention2、ZnO@TiO2-rGO/Fe3O4And ZnO1-x@TiO2-x-rGO/Fe3O4Fourier infrared spectrum, mainly using Fourier transform infrared spectrum (FT-IR) to research the structural functional group of the composite nanometer material. The sample is 1633cm-1And 3423cm-1The nearby absorption peak corresponds to the stretching vibration of the O-H bond on the surface of the material and is 590cm-1The absorption peak is caused by the stretching vibration of the Fe-O bond. Below 800cm-1The absorption peaks in (1) are due to stretching vibration of Ti-O-Ti bond, and the absorption peaks at 3415cm-1 and 1633cm-1 are probably due to adsorption on TiO2H of the surface2O-H bonds of O or-OH are caused by bending and stretching vibration. In addition, for Fe3O4590cm of Fe-O band vibration-1The left and right bands generally correspond to iron cations at tetrahedral sites, with a strong peak appearing at the other800cm-1Below, 510cm due to Ti-O-Ti groups-1The presence of zinc oxide is confirmed by the peak at which the presence of ZnO, Fe is confirmed3O4And TiO2Nanoparticles have been successfully grafted onto rGO sheets in hydrothermal processes. Furthermore, in ZnO1-x@TiO2-x-rGO/Fe3O4In a composite catalyst, TiO2Characteristic peaks for rGO and ZnO are clearly visible, while Fe3O4Is mainly due to Fe3O4Too low doping content.
Organic matter degradation experiments are carried out on the materials prepared by the specific examples, and the experimental environment is under a PMS system. FIG. 5 shows ZnO prepared in example 11-x@TiO2-x-rGO/Fe3O4Photocatalytic nano material and common TiO2Nanoparticles, ZnO @ TiO2、ZnO@TiO2-rGO/Fe3O4、TiO2-x-rGO/Fe3O4And ZnO1-x@TiO2-x-rGO/Fe3O4A performance contrast chart of visible light catalytic degradation imidacloprid. Ordinary TiO2Nanoparticles and ZnO @ TiO2The imidacloprid can be removed by about 20 percent within 30 minutes, and ZnO @ TiO2-rGO/Fe3O4The removal rate of the photocatalytic nano material to imidacloprid can only reach about 40 percent within 30 minutes, and TiO2-x-rGO/Fe3O4The removal rate of the photocatalytic nano material to imidacloprid can reach about 80 percent within 30 minutes, and ZnO can reach1-x@TiO2-x-rGO/Fe3O4The degradation efficiency of the photocatalytic nano material to imidacloprid within 30 minutes is as high as 99%. It can be seen that ZnO prepared in example 1 of the present invention1-x@TiO2-x-rGO/Fe3O4The degradation efficiency of the photocatalytic nano material to imidacloprid is considerable, and related data are mutually verified with the effective improvement and improvement of the ultraviolet light absorption range.
FIG. 6 shows ZnO prepared in example 1 of the present invention1-x@TiO2-x-rGO/Fe3O4The nanometer material is prepared under different environmental conditions of pure illumination, PS and PMSA performance contrast chart of visible light catalytic degradation imidacloprid reflects the degradation capability of the photocatalytic nano degradation material to imidacloprid organic pollutants under different environmental conditions, and can be seen that the degradation rate constant of imidacloprid molecules under pure illumination is 0.003 which is obviously smaller than that under PMS, and the concentration change of the imidacloprid molecules is small after the imidacloprid molecules are illuminated by pure light.
The ZnO-based heterojunction photocatalytic composite material provided by the invention and the preparation and application thereof are described in detail, a specific example is applied in the text to explain the principle and the implementation mode of the application, and the description of the example is only used for helping to understand the method and the core idea of the application; meanwhile, for a person skilled in the art, according to the idea of the present application, there may be variations in the specific embodiments and the application scope, and in summary, the content of the present specification should not be construed as a limitation to the present application.
Claims (10)
1. The ZnO-based heterojunction photocatalytic composite material is characterized in that a single layer of rGO is used as a basic material, and TiO is grafted on the basic material2-xNanoparticles, ZnO1-xNanoparticles and Fe3O4Nanoparticle derived ZnO1-x@TiO2-x-rGO/Fe3O4The nano material, wherein x is 0.05-0.45.
2. Composite material according to claim 1, characterized in that the ZnO1-x@TiO2-x-rGO/Fe3O4The molar ratio of Fe to Ti to Zn in the nano material is 0.5-2: 1: 1.
3. A method for preparing the composite material according to any one of claims 1 to 2, wherein the preparation method comprises:
step 1, preparing TiO2Sol;
step 2, preparing TiO2-rGO/Fe3O4A suspension;
step 3, dissolving in distilled waterZinc acetate is added to the above TiO2-rGO/Fe3O4In the suspension, adjusting the pH value to 12 by using a sodium hydroxide solution, and then carrying out a first hydrothermal reaction;
step 4, carrying out first post-treatment on the reaction system after the first hydrothermal reaction to obtain ZnO1-x@TiO2-x-rGO/Fe3O4And (3) nano materials.
4. The method according to claim 3, wherein TiO is prepared in the step 12The sol process includes the following steps:
under magnetic stirring, dropwise adding acetic acid and tetrabutyl titanate into anhydrous ethanol at the speed of 4 s/drop and 1 s/drop to obtain a solution A;
adding absolute ethyl alcohol and deionized water into a beaker, and adjusting the pH of the solution to 2 by using dilute nitric acid to prepare a solution B;
slowly adding the solution B into the solution A, and continuously stirring for 30min to obtain TiO2And (3) sol.
5. The method according to claim 3, wherein in the step 2, TiO is prepared2-rGO/Fe3O4The suspension procedure was as follows:
adding the single-layer graphene oxide suspension into ethylene glycol or isopropanol, and dispersing uniformly by using ultrasonic waves to obtain a graphene oxide mixed system;
and adding an organic alcohol solution of ferric chloride hexahydrate into the graphene oxide mixed system, and uniformly mixing to obtain a first mixed system.
Mixing sodium acetate and TiO2Adding the sol and ethylenediamine into the first mixed system in sequence to obtain a second mixed system;
placing the second mixed system in a reaction container to perform a second hydrothermal reaction;
carrying out second post-treatment on the reaction system after the second hydrothermal reaction to obtain TiO2-rGO/Fe3O4And (3) suspension.
6. The method as claimed in claim 5, wherein the reaction time of the second hydrothermal reaction is 8-12h, and the reaction temperature is 150-200 ℃.
7. The method of claim 5, wherein the second post-processing comprises:
washing the reaction system to be neutral by using absolute ethyl alcohol;
dispersing the washed product into distilled water to obtain TiO2-rGO/Fe3O4And (3) suspension.
8. The method as claimed in claim 4, wherein in the step 3, the reaction time of the first hydrothermal reaction is 1-2h, and the reaction temperature is 150-200 ℃.
9. The method according to claim 4, wherein in the step 4, the first post-processing comprises:
centrifuging the residue after the first hydrothermal reaction for 5-7 times and freeze-drying to obtain ZnO @ TiO2-rGO/Fe3O4；
The ZnO @ TiO is mixed2-rGO/Fe3O4Calcining for 2-4h in a tubular furnace at the temperature of 300 ℃ and 550 ℃ under the protection of nitrogen or vacuum.
10. The application of the ZnO-based heterojunction photocatalytic composite material is characterized in that the application comprises the following steps:
the composite material of any one of the claims 1-2 is used for high-efficiency photocatalytic treatment of neonicotinoid pesticide pollutants.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111428842.3A CN114130397B (en) | 2021-11-26 | 2021-11-26 | ZnO-based heterojunction photocatalytic composite material and preparation and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111428842.3A CN114130397B (en) | 2021-11-26 | 2021-11-26 | ZnO-based heterojunction photocatalytic composite material and preparation and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114130397A true CN114130397A (en) | 2022-03-04 |
| CN114130397B CN114130397B (en) | 2022-10-21 |
Family
ID=80388692
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111428842.3A Active CN114130397B (en) | 2021-11-26 | 2021-11-26 | ZnO-based heterojunction photocatalytic composite material and preparation and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114130397B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116393171A (en) * | 2023-03-24 | 2023-07-07 | 哈尔滨工业大学（深圳） | Cu (copper) alloy 9 S 5 Base composite photocatalysis nano material, preparation method and application |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104128183A (en) * | 2014-06-27 | 2014-11-05 | 南开大学 | Nanoscale magnetic graphene composite material for efficient degradation of microcystic toxins and preparation and application thereof |
| CN112516978A (en) * | 2020-11-20 | 2021-03-19 | 哈尔滨工业大学（深圳） | Graphene nanocomposite and preparation method and application thereof |
| CN112916045A (en) * | 2021-01-31 | 2021-06-08 | 胡国强 | Load ZnO-TiO2Preparation method of magnetic graphene oxide/chitosan composite material |
| WO2021118459A1 (en) * | 2019-12-12 | 2021-06-17 | National University Of Singapore | Porous composites, scaffolds, foams, methods of fabrication and uses thereof |
-
2021
- 2021-11-26 CN CN202111428842.3A patent/CN114130397B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104128183A (en) * | 2014-06-27 | 2014-11-05 | 南开大学 | Nanoscale magnetic graphene composite material for efficient degradation of microcystic toxins and preparation and application thereof |
| WO2021118459A1 (en) * | 2019-12-12 | 2021-06-17 | National University Of Singapore | Porous composites, scaffolds, foams, methods of fabrication and uses thereof |
| CN112516978A (en) * | 2020-11-20 | 2021-03-19 | 哈尔滨工业大学（深圳） | Graphene nanocomposite and preparation method and application thereof |
| CN112916045A (en) * | 2021-01-31 | 2021-06-08 | 胡国强 | Load ZnO-TiO2Preparation method of magnetic graphene oxide/chitosan composite material |
Non-Patent Citations (2)
| Title |
|---|
| ANILA GOPALAKRISHNAN ET AL.: "Excellent photocatalytic activity of titania–grapheme nanocomposites prepared by a facile route", 《J SOL-GEL SCI TECHNOL》 * |
| GULZAR AHMED ET AL.: "Defect engineering of ZnO nanoparticles by graphene oxide leading to enhanced visible light photocatalysis", 《JOURNAL OF MOLECULAR CATALYSIS A: CHEMICAL》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116393171A (en) * | 2023-03-24 | 2023-07-07 | 哈尔滨工业大学（深圳） | Cu (copper) alloy 9 S 5 Base composite photocatalysis nano material, preparation method and application |
| CN116393171B (en) * | 2023-03-24 | 2024-05-14 | 哈尔滨工业大学（深圳） | Cu (copper) alloy9S5Base composite photocatalysis nano material, preparation method and application |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114130397B (en) | 2022-10-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Leong et al. | Ni (OH) 2 decorated rutile TiO2 for efficient removal of tetracycline from wastewater | |
| Wu et al. | Piezotronic effect boosted photocatalytic performance of heterostructured BaTiO3/TiO2 nanofibers for degradation of organic pollutants | |
| AU2020102258A4 (en) | MIXED CRYSTAL TiO2/BiOBr COMPOSITE AND PREPARATION METHOD AND APPLICATION THEREOF | |
| Ma et al. | Photocatalytic degradation of MB dye by the magnetically separable 3D flower-like Fe3O4/SiO2/MnO2/BiOBr-Bi photocatalyst | |
| Liu et al. | Graphene facilitated visible light photodegradation of methylene blue over titanium dioxide photocatalysts | |
| Sun et al. | Facile sonochemical synthesis of CdS/COF heterostructured nanocomposites and their enhanced photocatalytic degradation of Bisphenol-A | |
| Wang et al. | Visible-light driven ZnIn2S4/TiO2-x heterostructure for boosting photocatalytic H2 evolution | |
| Wu et al. | Bimetallic silver/bismuth-MOFs derived strategy for Ag/AgCl/BiOCl composite with extraordinary visible light-driven photocatalytic activity towards tetracycline | |
| Yang et al. | Petal-biotemplated synthesis of two-dimensional Co3O4 nanosheets as photocatalyst with enhanced photocatalytic activity | |
| Guo et al. | An oxygen-vacancy-rich Z-scheme g-C3N4/Pd/TiO2 heterostructure for enhanced visible light photocatalytic performance | |
| Xu et al. | Ternary system of ZnO nanorods/reduced graphene oxide/CuInS2 quantum dots for enhanced photocatalytic performance | |
| Huang et al. | In situ fabrication of ultrathin-g-C3N4/AgI heterojunctions with improved catalytic performance for photodegrading rhodamine B solution | |
| Liu et al. | The synergistic effect of graphene oxide and silver vacancy in Ag3PO4-based photocatalysts for rhodamine B degradation under visible light | |
| Ghafuri et al. | Synthesis and characterization of magnetic nanocomposite Fe3O4@ TiO2/Ag, Cu and investigation of photocatalytic activity by degradation of rhodamine B (RhB) under visible light irradiation | |
| Zhao et al. | Construction of diatomite/ZnFe layered double hydroxides hybrid composites for enhanced photocatalytic degradation of organic pollutants | |
| Li et al. | Bi2Ti2O7/TiO2/RGO composite for the simulated sunlight-driven photocatalytic degradation of ciprofloxacin | |
| Hejazi et al. | Novel visible-light-responsive rGO-ZnO@ Bi2MoO6 nanocomposite with enhanced light harvesting and Z-scheme charge transfer for photodegradation and detoxification of RhB | |
| Jie et al. | Preparation of LaMnO3/graphene thin films and their photocatalytic activity | |
| Naing et al. | Enhanced visible-light-driven photocatalysis of in-situ reduced of bismuth on BiOCl nanosheets and montmorillonite loading: Synergistic effect and mechanism insight | |
| Zhang et al. | Enhanced visible-light photocatalytic activity of ZnS/BiOBr/graphene oxide ternary composite | |
| Zhu et al. | Rapid sonochemical synthesis of novel PbSe–graphene–TiO2 composite sonocatalysts with enhanced on decolorization performance and generation of ROS | |
| Li et al. | Fabrication of porous TiO2 nanosheets assembly for improved photoreactivity towards X3B dye degradation and NO oxidation | |
| CN112516978A (en) | Graphene nanocomposite and preparation method and application thereof | |
| CN114130397B (en) | ZnO-based heterojunction photocatalytic composite material and preparation and application thereof | |
| Chen et al. | One-dimensional magnetic flower-like CoFe2O4@ Bi2WO6@ BiOBr composites for visible-light catalytic degradation of Rhodamine B |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |