CN113926444A - Zinc oxide nano-rod ternary composite material and preparation method and application thereof - Google Patents
Zinc oxide nano-rod ternary composite material and preparation method and application thereof Download PDFInfo
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 140
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 70
- 239000002073 nanorod Substances 0.000 title claims abstract description 48
- 239000011206 ternary composite Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000000243 solution Substances 0.000 claims abstract description 31
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000002131 composite material Substances 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 24
- 239000000843 powder Substances 0.000 claims abstract description 19
- XMEVHPAGJVLHIG-FMZCEJRJSA-N chembl454950 Chemical compound [Cl-].C1=CC=C2[C@](O)(C)[C@H]3C[C@H]4[C@H]([NH+](C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O XMEVHPAGJVLHIG-FMZCEJRJSA-N 0.000 claims abstract description 18
- 229960004989 tetracycline hydrochloride Drugs 0.000 claims abstract description 18
- 239000000047 product Substances 0.000 claims abstract description 14
- 230000015556 catabolic process Effects 0.000 claims abstract description 12
- 238000006731 degradation reaction Methods 0.000 claims abstract description 12
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- 150000003522 tetracyclines Chemical class 0.000 claims abstract description 11
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims abstract description 9
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- 239000000463 material Substances 0.000 description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 description 4
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- YZYKBQUWMPUVEN-UHFFFAOYSA-N zafuleptine Chemical compound OC(=O)CCCCCC(C(C)C)NCC1=CC=C(F)C=C1 YZYKBQUWMPUVEN-UHFFFAOYSA-N 0.000 description 4
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- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 2
- 229960000907 methylthioninium chloride Drugs 0.000 description 2
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- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
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- OSVXSBDYLRYLIG-UHFFFAOYSA-N chlorine dioxide Inorganic materials O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 description 1
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- 229930000044 secondary metabolite Natural products 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- 150000003751 zinc Chemical class 0.000 description 1
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Images
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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- 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
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention relates to a zinc oxide nano-rod ternary composite material and a preparation method and application thereof, wherein the preparation method comprises the following steps: obtaining the biochar: removing sponge part of pericarpium Citri Grandis, drying pericarpium Citri Grandis, grinding into powder, sieving, and carbonizing in protective atmosphere; then immersing the carbonized product into an alkaline solution, heating, cooling, washing and drying to obtain biochar; preparing a composite material: dispersing the biochar in a solvent, adding zinc acetate, an alkaline reagent, polyethylene glycol and graphene oxide, uniformly mixing, putting into a high-pressure reaction kettle, heating for reaction, cooling to room temperature, filtering, washing and collecting a solid product. The zinc oxide nanorod ternary composite material has a good photocatalytic effect on tetracycline hydrochloride, is mixed with tetracycline hydrochloride four-solution, is subjected to dark adsorption for 40min and then is irradiated under a 75W mercury lamp for 80min, and the tetracycline degradation efficiency reaches 99.24%, so that a new way and a new method are provided for tetracycline wastewater degradation.
Description
Technical Field
The invention relates to a processing technology of a biochar functional material and an antibiotic, in particular to a zinc oxide nano-rod ternary composite material and a preparation method and application thereof.
Background
Antibiotics are secondary metabolites produced during the life of a living organism. They are widely used in the treatment of human and animal diseases because they interfere with the development of biological cells. China is the earliest country in which tetracycline is used, with tetracycline hydrochloride (TC-H) being the most commonly used antibiotic. TC-H in water is difficult to naturally decompose and is harmful to human health. In addition, it will increase bacterial resistance and greatly reduce the effects of tetracycline. Therefore, effective tetracycline management has been a challenge. Advanced oxidation technology has made significant progress in antibiotic wastewater treatment over the last several decades. The photocatalytic technology has been widely studied because of its clean and efficient characteristics. Among them, zinc oxide is a photocatalyst widely used.
Biochar is a material obtained by pyrolysis of biomass in an oxygen-free atmosphere. Biomass can be derived from a variety of materials, such as plants, wood, agricultural waste, food waste, and the like. The combination of ZnO and the biochar material can also effectively improve the photocatalytic performance of the biochar material, because the biochar material has a special pore structure, high specific surface area and adsorption capacity. The biological carbon material is compounded with ZnO, and the photocatalytic activity can be enhanced by utilizing the synergistic effect of the adhesion performance and ZnO photocatalysis. Meanwhile, by utilizing the conductivity of the carbon material, the band gap energy of ZnO can be reduced, and the quick separation of photo-generated electron-hole pairs is promoted, so that the photocatalytic activity of the carbon-based ZnO composite material is enhanced.
Patent application CN 111974374A discloses a preparation method of biochar modified nano ZnO composite powder, which comprises the step of carrying out hydrothermal reaction on a mixed solution of biochar and zinc salt at the temperature of 100-160 ℃ under an alkaline condition to obtain the biochar modified nano ZnO composite photocatalyst. The biochar modified nano ZnO composite photocatalyst has the advantages of large specific surface area, strong adsorption capacity and response to visible light, and the efficiency of degrading Methylene Blue (MB) pollutants under ultraviolet-visible light for 100min reaches 98.71%. The treatment process of the dye wastewater is relatively mature at present, and comprises a plurality of methods such as a biological method, a chemical coagulation method, an adsorption method, an oxidation method and the like, wherein the biological method has a good treatment effect and is lower in cost. The tetracycline four-waste water containing hydrochloric acid belongs to antibiotic waste water, the existing biological method, adsorption method and other methods have the defects of poor biodegradability or higher cost, and the like, and the photocatalytic oxidation method has the advantages of high efficiency and environmental protection when treating antibiotic waste water, so that the development of a novel photocatalyst capable of efficiently degrading antibiotics is particularly necessary.
Disclosure of Invention
The invention aims to overcome the problem of limited treatment effect of the existing wastewater containing tetracycline hydrochloride, and provides a preparation method of a zinc oxide nanorod ternary composite material. The method takes zinc acetate as a ZnO crystal generation raw material, and the ZnO nano-rod prepared by controlling the molar ratio of the zinc acetate to sodium hydroxide has better photoresponse characteristic compared with the nano-microsphere.
On the basis, the inventor utilizes the characteristics of cheap and easily obtained shaddock peel and loose and porous material to compound the biochar obtained by processing the shaddock peel and the ZnO nano-rod, thereby achieving the purposes of improving the adsorption performance of the material, promoting the separation of electron-hole pairs in the photocatalytic reaction process and improving the effect of degrading target pollutants by photocatalysis. In order to reduce the photoreaction band gap and widen the photoresponse interval of the material, the inventor introduces graphene oxide and synchronously compounds the graphene oxide with ZnO nanorods and biochar under the conditions of high temperature and high pressure hydrothermal to obtain a ternary composite material, and the ternary composite material has high degradation efficiency on tetracycline hydrochloride wastewater, good reusability and better application effect.
The specific scheme is as follows:
a preparation method of a zinc oxide nanorod ternary composite material comprises the following steps:
obtaining the biochar: removing sponge part of pericarpium Citri Grandis, drying pericarpium Citri Grandis, grinding into powder, sieving, and carbonizing in protective atmosphere; then immersing the carbonized product into an alkaline solution, heating, cooling, washing and drying to obtain biochar;
preparing a composite material: dispersing the biochar in a solvent, adding zinc acetate, an alkaline reagent, polyethylene glycol and graphene oxide, uniformly mixing, putting into a high-pressure reaction kettle, heating for reaction, cooling to room temperature, filtering, washing and collecting a solid product to obtain the zinc oxide nanorod ternary composite material.
Further, in the step of obtaining the biochar, the shaddock peel is dried at the temperature of 80-100 ℃ for 50-80h, ground into powder, sieved by a 50-100 mesh sieve, carbonized in the nitrogen atmosphere at the temperature of 400-600 ℃ for 1-5 h.
Further, in the step of obtaining the biochar, the carbonized product is soaked in an alkaline solution for 0.5-1h, then activated for 1-2h at the temperature of 400-.
Further, in the step of preparing the composite material, the mass ratio of the biochar to the zinc acetate is 1:8-12, and the mass ratio of the biochar to the graphene oxide is 20-25: 2.
Further, in the step of preparing the composite material, the graphene oxide is prepared by the following method: adding concentrated H2SO4And concentrated H3PO4Mixing, adding graphite powder into the solution and stirring; adding potassium permanganate into the solution, magnetically stirring at 50-60 deg.C for 10-12 hr to obtain brown solution, cooling, and adding H2O2And stirring for 1-2h, washing and drying the product to obtain the graphene oxide.
Further, in the step of preparing the composite material, the biochar is dispersed in a solvent by utilizing ultrasound, zinc acetate, an alkaline reagent and polyethylene glycol are added for ultrasonic treatment, then, an ultrasonically dispersed graphene oxide solution is added, and after uniform mixing, the mixture is filled into a high-pressure reaction kettle.
Further, in the step of preparing the composite material, the reaction temperature of the high-pressure reaction kettle is 100-130 ℃, and the reaction time is 5-12 h.
The invention also provides a preparation method of the zinc oxide nano rod ternary composite material, and the prepared zinc oxide nano rod ternary composite material is gray powder, wherein the mass ratio of zinc oxide to graphene oxide to biochar is 75-86:1-5: 13-24; in the microstructure, the graphene oxide is in a single-layer sheet shape, the biochar is in a porous irregular granular shape, the zinc oxide is in a nano-rod shape and is randomly stacked on the surfaces of the graphene oxide and the biochar, and the three are tightly combined and uniformly dispersed.
Further, the zinc oxide nanorod ternary composite material powder is added into a tetracycline hydrochloride solution in an adding amount of 0.3g/L, dark adsorption is carried out for 40min, irradiation is carried out for 80min under a 75W mercury lamp, and the tetracycline degradation efficiency is more than or equal to 99.24%.
The invention also protects the application of the zinc oxide nano-rod ternary composite material in degrading tetracycline hydrochloride.
Has the advantages that:
according to the preparation method of the zinc oxide nanorod ternary composite material, the biological carbon is prepared from the shaddock peel, the specific surface area is large, the adsorbability is good, the number of active sites is large, the raw material is shaddock peel waste, a new application idea of the shaddock peel waste is provided, and waste is turned into wealth.
Moreover, the zinc oxide nanorod ternary composite material prepared by the method disclosed by the invention is uniformly dispersed and has a good photoresponse effect, can be excited by only a 75W mercury lamp, and is more energy-saving and economical compared with a conventional ZnO photocatalyst.
Furthermore, the preparation method of the zinc oxide nanorod ternary composite material provided by the invention innovatively compounds ZnO with two carbon materials, namely biochar and RGO, so that the band gap energy and the recombination rate of photoproduction electron holes are reduced, the photocatalytic performance of the zinc oxide nanorod ternary composite material is greatly improved, and a new thought is provided for doping modification of ZnO.
In a word, the zinc oxide nanorod ternary composite material has a good photocatalytic effect on tetracycline hydrochloride, the tetracycline degradation efficiency reaches 99.24% in 80min, and a new way and a new method are provided for tetracycline wastewater degradation.
Drawings
In order to illustrate the technical solution of the present invention more clearly, the drawings will be briefly described below, and it is apparent that the drawings in the following description relate only to some embodiments of the present invention and are not intended to limit the present invention.
FIG. 1 is a composite XRD characterization pattern provided by one embodiment of the present invention;
FIG. 2 is an electron microscope image of a zinc oxide nanorod/biochar composite provided by an embodiment of the invention;
fig. 3 is an electron microscope image of a zinc oxide nanorod/biochar/RGO composite provided by an embodiment of the invention;
FIG. 4 is a graph of photocatalytic efficiency of a zinc oxide nanorod/biochar composite provided by an embodiment of the invention;
fig. 5 is a graph of photocatalytic efficiency of zinc oxide nanorods/biochar/RGO composite materials provided by an embodiment of the present invention.
Detailed Description
Preferred embodiments of the present invention will be described in more detail below. While the following describes preferred embodiments of the present invention, it should be understood that the present invention may be embodied in various forms and should not be limited by the embodiments set forth herein. The examples do not specify particular techniques or conditions, and are performed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available. In the following examples, "%" means weight percent, unless otherwise specified.
Example 1 preparation of graphene oxide (hereinafter referred to as RGO)
RGO is synthesized using a modified Hummer method. The method comprises mixing 360ml of concentrated H2SO4And 40ml of concentrated H3PO4With appropriate mixing, 3g of graphite powder was slowly added to the solution and stirring was continued for 3 h. Subsequently, 18g of potassium permanganate were suitably ground and slowly added to the solution, and the solution was stirred continuously for 12h at 50 ℃ with a magnetic stirrer. During this reaction, the solution turned dark purple, green, then dark brown in color. The dark brown solution was poured into a beaker with a capacity of 400ml and held with a frozen stick, to which was added 3ml of H2O2And stirred for 2 h. The residual particles were then washed three times with HCl and several times with ethanol and distilled water. Finally, the granules were dried in a hot air oven at 60 ℃ for 48 hours to obtain RGO.
Concentrated sulfuric acid (H) used in the conventional Hummers method2SO4) Potassium permanganate (KMnO)4) Sodium nitrate (NaNO)3) The product of the mixed reaction of 3 substances contains toxic gas NO2、N2O4Or ClO2And the reaction temperature control is divided into low, middle and high 3 sections, the operation is difficult, and the prepared RGO has single surface functional group, thereby limiting the application range of the RGO. According to the invention, the improved Hummers method is adopted to prepare the graphene oxide, so that the emission of toxic gas can be reduced in the preparation process, the reaction temperature is maintained at a medium temperature (50 ℃), the control is easy, and the prepared RGO surface functional groups are rich.
Example 2 biochar preparation
Separating white sponge part of pericarpium Citri Grandis, drying the rest pericarpium Citri Grandis at 80 deg.C for 72 hr, grinding into powder, and sieving with 100 mesh sieve. Thereafter, the powder was carbonized in a quartz tube furnace at 400 ℃ under a nitrogen atmosphere. The carbonized product was immersed in a KOH solution in a nickel crucible for 1h, then activated at 400 ℃ for 2h, and slowly pyrolyzed at 800 ℃ for 2 h. After cooling to room temperature, the final product was washed thoroughly with 0.1mol/L HCl and deionized water, and finally dried at 80 ℃ for 24 hours to obtain charcoal powder for use after grinding.
EXAMPLE 3ZnO nanorod/biochar composite preparation
0.115g (10%) of the biochar prepared in example 2 was dispersed in 30ml of ethanol and sonicated for 40min, then 1.15g of zinc acetate dihydrate was added, 3g of NaOH and 7.5ml of PEG 400 were added to the solution and sonicated for 40 min. The solution was then transferred to a teflon lined stainless steel autoclave and heated in an oven at 120 ℃ for 12h and allowed to cool to room temperature. The product ZnO/biochar nanocomposite was washed several times with distilled water and ethanol and dried at 60 ℃ for 48 hours for subsequent studies.
ZnO/biochar nanocomposites were prepared as described above using 0.0575g (5 wt.%), 0.1150g (10 wt.%), and 0.1725g (15 wt.%) of the biochar prepared in example 2, respectively, and the samples were referred to as ZB, respectively5、ZB10And ZB15。
EXAMPLE 4ZnO nanorod/biochar/RGO composite preparation
To an ultrasonication solution containing 1.15g zinc acetate dihydrate/3 g NaOH/7.5ml PEG 400 was added 0.115g biochar prepared in example 2 (10 wt.%) followed by ultrasonication for 30 min. Subsequently, various amounts of RGO prepared in example 1 (x ═ 10, 20, 30, and 40mg) were added and sonicated for 30 min. The solution was then transferred to a teflon lined stainless steel autoclave and heated at 120 ℃ for 12h, the collected particles were washed several times with distilled water and ethanol and dried at 60 ℃ for 48 h.
10 mg, 20mg, 30 mg and 40mg of RGO are respectively added in the synthesis process, and the ZnO nanorod/biochar/RGO composite material is respectively marked as ZB10G10、ZB10G20、ZB10G30And ZB10G40。
Example 5
Separating white sponge part of pericarpium Citri Grandis, drying the rest pericarpium Citri Grandis at 100 deg.C for 60 hr, grinding into powder, and sieving with 100 mesh sieve. Thereafter, the powder was carbonized in a quartz tube furnace at 500 ℃ under a nitrogen atmosphere. The carbonized product was immersed in a KOH solution in a nickel crucible for 1h, then activated at 450 ℃ for 2h, and then slowly pyrolyzed at 850 ℃ for 1 h. After cooling to room temperature, the final product was washed thoroughly with 0.1mol/L HCl and deionized water, and finally dried at 80 ℃ for 24 hours to obtain charcoal powder for use after grinding.
To an ultrasonication solution containing 1.15g zinc acetate dihydrate/3 g NaOH/7.5ml PEG 400 was added 0.115g of the biochar prepared above (10 wt.%) followed by ultrasonication for 30 min. Subsequently, 30 mg of RGO prepared in example 1 was added and sonicated for 30 min. The solution was then transferred to a teflon lined stainless steel autoclave and heated at 130 ℃ for 6h, the collected particles were washed several times with distilled water and ethanol and dried at 60 ℃ for 48 h.
Example 6
Separating white sponge part of pericarpium Citri Grandis, drying the rest pericarpium Citri Grandis at 100 deg.C for 60 hr, grinding into powder, and sieving with 100 mesh sieve. Thereafter, the powder was carbonized in a quartz tube furnace at 600 ℃ under a nitrogen atmosphere. The carbonized product was immersed in a KOH solution in a nickel crucible for 1 hour, then activated at 400 ℃ for 2 hours, and then slowly pyrolyzed at 830 ℃ for 1 hour. After cooling to room temperature, the final product was washed thoroughly with 0.1mol/L HCl and deionized water, and finally dried at 80 ℃ for 24 hours to obtain charcoal powder for use after grinding.
To an ultrasonication solution containing 1.15g zinc acetate dihydrate/3 g NaOH/7.5ml PEG 400 was added 0.115g of the biochar prepared above (10 wt.%) followed by ultrasonication for 30 min. Subsequently, 30 mg of RGO prepared in example 1 was added and sonicated for 30 min. The solution was then transferred to a teflon lined stainless steel autoclave and heated at 110 ℃ for 10h, the collected particles were washed several times with distilled water and ethanol and dried at 60 ℃ for 48 h.
Performance detection
Taking the ZB prepared in example 310And ZB prepared in example 410 G10XRD characterization was performed and the results are shown in FIG. 1, from which it can be seen that ZB10And ZB10G10The peak shapes are basically similar, wherein the diffraction peak intensity of the zinc oxide is higher, no obvious impurity peak exists, the hexagonal wurtzite structure of the zinc oxide is met, and the biochar and RGO peak are overlapped with part of zinc oxide peaks. Due to the addition of the graphene, the carbon element content of the composite material is higher, so that ZB is caused10G10The peak signal is stronger.
Taking the ZB prepared in example 310And ZB prepared in example 410 G10SEM characterization was performed and the results are shown in figures 2 and 3.
As can be seen from FIG. 2, the zinc oxide has a nanorod-like morphology with a uniform size, a diameter of about 100-150nm and a length of about 400-600 nm. The biochar is in a porous granular shape, the surface of the biochar is provided with folds, and the zinc oxide nano rods are uniformly stacked on the surface of the biochar.
As can be seen from FIG. 3, the zinc oxide has a nanorod-like morphology with a uniform size, a diameter of about 100-150nm and a length of about 200-300 nm. The biochar is in a porous granular shape, pores are formed in the surface of the biochar, and graphene oxide is in a single-layer sheet shape. The zinc oxide nano-rods are uniformly stacked on the surfaces of the graphene oxide sheets and the biochar particles.
Degradation experiments
The photodegradation reaction is carried out in a quartz reactor, and in order to eliminate the temperature influence, circulating flowing water is introduced into the outer wall of the reactor to keep constant temperature. A 75W mercury lamp was used as the visible light source. 50ml of a 20mg/L prepared tetracycline hydrochloride solution (TC) were taken and the pH adjusted to 5 with hydrochloric acid. 0.01g (0.2g/L) of the ZnO nanorod material prepared in example 2 and ZB prepared in example 3 were added to the reaction solution10、ZB20And ZB30(binary ZB Material for short), and ZB prepared in example 410G10、ZB10G20、ZB10G30And ZB10G40(ZBG ternary material for short) and putting into a quartz reactor.
Dark reaction for 40min to reach adsorption equilibrium of the catalyst material, and sampling every 10 min. And starting photodegradation after the light source is switched on and is stabilized. And sampling the ZB binary material every 15min, and reacting for 120 min. Sampling ZBG ternary material every 10minThe reaction was carried out for 80 min. Detecting by a spectrophotometer, and recording the concentration as C and the initial concentration of tetracycline as C0Calculating C/C0And the degradation curves are plotted, and the results are shown in fig. 4 and fig. 5.
As can be seen from FIG. 4, compared with the single-phase ZnO nanorod material, the efficiency of photocatalytic degradation of tetracycline hydrochloride by the ZnO/biochar composite material is remarkably improved, wherein ZB is10The material degradation efficiency is highest, the 120min tetracycline hydrochloride degradation rate reaches 88.63%, and compared with other structural materials, the first-order reaction kinetic constant is the largest, and the reaction rate is the fastest. And the highest degradation efficiency of the single-phase ZnO nanorod material is only about 25 percent.
As can be seen from FIG. 5, compared with the two composite materials, the efficiency of the three-phase composite material in photocatalytic degradation of tetracycline hydrochloride is remarkably improved, wherein ZB is10G10The material degradation efficiency is highest, the degradation rate of tetracycline hydrochloride reaches 99.24 percent in 80min and exceeds ZB10At least 10 percentage points of the material. Compared with other structural materials, the material has the largest first-order reaction kinetic constant and the fastest reaction rate.
Meanwhile, in a dark environment, the three-phase composite material can also rapidly degrade tetracycline hydrochloride, which is not possessed by ZnO/biochar composite materials, which shows that the ternary composite material reduces the requirements of the catalyst on light, and shows that the catalytic activity of the ternary composite material is better and the applicability is wider.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (10)
1. A preparation method of a zinc oxide nanorod ternary composite material is characterized by comprising the following steps: the method comprises the following steps:
obtaining the biochar: removing sponge part of pericarpium Citri Grandis, drying pericarpium Citri Grandis, grinding into powder, sieving, and carbonizing in protective atmosphere; then immersing the carbonized product into an alkaline solution, heating, cooling, washing and drying to obtain biochar;
preparing a composite material: dispersing the biochar in a solvent, adding zinc acetate, an alkaline reagent, polyethylene glycol and graphene oxide, uniformly mixing, putting into a high-pressure reaction kettle, heating for reaction, cooling to room temperature, filtering, washing and collecting a solid product to obtain the zinc oxide nanorod ternary composite material.
2. The method for preparing the zinc oxide nanorod ternary composite material according to claim 1, which is characterized in that: in the step of obtaining the biochar, the shaddock peel is dried at the temperature of 80-100 ℃ for 50-80h, ground into powder, sieved by a 50-100 mesh sieve, carbonized in the nitrogen atmosphere at the temperature of 400-600 ℃ for 1-5 h.
3. The method for preparing the zinc oxide nanorod ternary composite material according to claim 1 or 2, characterized in that: in the step of obtaining the biochar, the carbonized product is soaked in an alkaline solution for 0.5-1h, then activated for 1-2h at the temperature of 400-.
4. The method for preparing the zinc oxide nanorod ternary composite material according to claim 1, which is characterized in that: in the step of preparing the composite material, the mass ratio of the biochar to the zinc acetate is 1:8-12, and the mass ratio of the biochar to the graphene oxide is 20-25: 2.
5. The zinc oxide according to claim 1 or 4The preparation method of the nano-rod ternary composite material is characterized by comprising the following steps: in the step of preparing the composite material, the adopted graphene oxide is prepared by the following method: adding concentrated H2SO4And concentrated H3PO4Mixing, adding graphite powder into the solution and stirring; adding potassium permanganate into the solution, magnetically stirring at 50-60 deg.C for 10-12 hr to obtain brown solution, cooling, and adding H2O2And stirring for 1-2h, washing and drying the product to obtain the graphene oxide.
6. The method for preparing the zinc oxide nanorod ternary composite material according to claim 1 or 4, characterized in that: in the step of preparing the composite material, the biochar is dispersed in a solvent by utilizing ultrasound, zinc acetate, an alkaline reagent and polyethylene glycol are added for ultrasonic treatment, then, an ultrasonically dispersed graphene oxide solution is added, and the mixture is uniformly mixed and then is put into a high-pressure reaction kettle.
7. The method for preparing the zinc oxide nanorod ternary composite material according to claim 1, which is characterized in that: in the step of preparing the composite material, the reaction temperature of the high-pressure reaction kettle is 100-.
8. The preparation method of the zinc oxide nanorod ternary composite material as defined in any one of claims 1-7, wherein the zinc oxide nanorod ternary composite material is prepared by the following steps: the zinc oxide nanorod ternary composite material is gray powder, wherein the mass ratio of zinc oxide to graphene oxide to biochar is 75-86:1-5: 13-24; in the microstructure, the graphene oxide is in a single-layer sheet shape, the biochar is in a porous irregular granular shape, the zinc oxide is in a nano-rod shape and is randomly stacked on the surfaces of the graphene oxide and the biochar, and the three are tightly combined and uniformly dispersed.
9. The zinc oxide nanorod ternary composite material of claim 8, wherein: adding zinc oxide nanorod ternary composite material powder into tetracycline hydrochloride solution at a dosage of 0.3g/L, carrying out dark adsorption for 40min, and then carrying out irradiation for 80min under a 75W mercury lamp, wherein the tetracycline degradation efficiency is more than or equal to 99.24%.
10. The use of the zinc oxide nanorod ternary composite material of claim 8 or 9 for degrading tetracycline hydrochloride.
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