CN114130397B - 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
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
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- 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
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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 TiO 2 Sol; step 2, preparing TiO 2 ‑rGO/Fe 3 O 4 A suspension; step 3, adding zinc acetate dissolved in distilled water to the TiO 2 ‑rGO/Fe 3 O 4 In the suspension, adjusting the pH value of the suspension 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 ZnO 1‑x @TiO 2‑x ‑rGO/Fe 3 O 4 And (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 material 2‑x Nanoparticles, znO 1‑x Nanoparticles and supported Fe 3 O 4 The 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 body of water 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 material 2-x Nanoparticles, znO 1-x Nanoparticles and Fe 3 O 4 Nanoparticles wherein x =0.05 to 0.45.
Preferably, the molar ratio of Fe to Ti to Zn in the composite material is 0.5 to 2.
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 TiO 2 Sol;
step 2, preparing TiO 2 -rGO/Fe 3 O 4 A suspension;
step 3, adding zinc acetate dissolved in distilled water to the TiO 2 -rGO/Fe 3 O 4 In the suspension, adjusting the pH value of the suspension 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 ZnO 1-x @TiO 2-x /rGO-Fe 3 O 4 And (3) nano materials.
Preferably, in the step 1, tiO is prepared 2 The sol preparation method comprises 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 TiO 2 And (3) sol.
Preferably, in the step 2, tiO is prepared 2 -rGO/Fe 3 O 4 The 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 TiO 2 Adding 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 TiO 2-x /rGO-Fe 3 O 4 And (3) suspension.
More preferably, the reaction time of the second hydrothermal reaction is 8-12h, and the reaction temperature is 150-200 ℃;
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 TiO 2 -rGO/Fe 3 O 4 And (3) suspension.
Preferably, in the step 3, the reaction time of the first hydrothermal reaction is 1-2h, and the reaction temperature is 150-200 ℃.
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 @ TiO 2 -rGO/Fe 3 O 4 ；
The above-mentioned ZnO @ TiO compound 2 -rGO/Fe 3 O 4 Calcining in a tubular furnace at 300-550 ℃ under the protection of nitrogen or vacuum for 2-4h.
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 material 2-x Nanoparticles, znO 1-x Nanoparticles and Fe-supported 3 O 4 Preparation of ZnO from nanoparticles 1-x @TiO 2-x -rGO/Fe 3 O 4 A nano-material. Wherein, tiO 2 ZnO 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 prepared 2 Sol, and then mixing to a certain extentHetero-yielding ZnO @ TiO 2 -rGO/Fe 3 O 4 With simple TiO 2 In contrast, the light absorption boundary of the composite material obtained by doping is obviously red-shifted. Finally by calcining ZnO @ TiO under oxygen-free conditions 2 -rGO/Fe 3 O 4 Preparation of ZnO 1-x @TiO 2-x -rGO/Fe 3 O 4 Composite material, in which case ZnO is clearly visible 1-x @TiO 2-x -rGO/Fe 3 O 4 The 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 Fe 3 O 4 As a typical magnetic material, the addition of the magnetic material can effectively solve the problem of ZnO 1-x @TiO 2-x -separation problems and secondary pollution problems of rGO photocatalysts. Generally, the composite material is simple to prepare, has a higher visible light utilization rate, a 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 used in the invention, such as rGO, tetrabutyl titanate, ethylenediamine, ferric chloride hexahydrate and the like, are low-toxicity or even non-toxic, have wide sources and low cost, and the prepared TiO 2 The 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, fe 3 O 4 Can effectively solve the problem of ZnO 1-x @TiO 2-x -separation problems and secondary pollution problems of rGO photocatalyst, therefore the invention is easy to recycle and recyclable. (3) The preparation method is simple, has low cost and relatively mild reaction conditions, and is favorable for high-quality ZnO 1-x @TiO 2-x -rGO/Fe 3 O 4 And (3) producing the nano material.
In summary, the preparation method of the ZnO-based heterojunction photocatalytic composite material of the present invention firstly prepares the TiO 2 Sol according to the prepared TiO 2 The sol, ferric chloride hexahydrate, sodium acetate, ethylenediamine and the like are taken as raw materials,preparing TiO by hydrothermal reaction 2 -rGO/Fe 3 O 4 Suspending liquid, adding zinc acetate and sodium hydroxide to form ZnO @ TiO under hydrothermal condition 2 -rGO/Fe 3 O 4 Finally obtaining ZnO by high-temperature calcination 1-x @TiO 2-x -rGO/Fe 3 O 4 And (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 invention 1-x @TiO 2-x -rGO/Fe 3 O 4 SEM image of nanoparticles;
FIG. 3 is a photograph showing TiO in example 1 of the present invention 2 、ZnO@TiO 2 、TiO 2 -rGO/Fe 3 O 4 、ZnO@TiO 2 -rGO/Fe 3 O 4 And ZnO 1-x @TiO 2-x -rGO/Fe 3 O 4 Ultraviolet diffuse reflection spectrogram of (1);
FIG. 4 shows TiO in example 1 of the present invention 2 、ZnO@TiO 2 -rGO/Fe 3 O 4 And ZnO 1-x @TiO 2-x -rGO/Fe 3 O 4 A Fourier infrared spectrum;
FIG. 5 shows TiO in Experimental example 1 of the present invention 2 、ZnO@TiO 2 、ZnO@TiO 2 -rGO/Fe 3 O 4 、TiO 2-x -rGO/Fe 3 O 4 And ZnO 1-x @TiO 2-x -rGO/Fe 3 O 4 A performance contrast chart of visible light catalytic degradation imidacloprid;
FIG. 6 shows ZnO prepared in example 1 of the present invention 1-x @TiO 2-x -rGO/Fe 3 O 4 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 base material, and TiO is grafted on the base material 2-x Nanoparticles, znO 1-x Nanoparticles and Fe 3 O 4 The nano-particles are obtained, wherein x = 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.
Wherein titanium dioxide (TiO) 2 ) And zinc oxide (ZnO) are the most widely used photocatalysts in other semiconductors, and have attractive characteristics such as non-toxicity, low cost, excellent chemical stability, corrosion resistance, and excellent photocatalytic performance. While both also have the same band gap energy (anatase TiO) 2 3.2eV, and ZnO 3.37 eV). In addition, tiO can be improved obviously after ZnO is added 2 Agglomeration of nanoparticles on the surface of rGO sheets to make TiO 2 The 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 rGO 1-x @TiO 2-x -rGO/Fe 3 O 4 Composite material, and ZnO 1-x @TiO 2-x -rGO/Fe 3 O 4 The 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, fe 3 O 4 As a typical magnetic material, its addition can effectively solve ZnO 1-x @TiO 2-x -separation problems and secondary pollution problems of rGO material. Further, fe 3 O 4 Not only can maintain unique superparamagnetism, but also can accelerate light-induced electrons to be in two oxidation states (Fe) of iron 3+ ，Fe 2+ ) 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 TiO 2 Sol;
step 2, preparing TiO 2 -rGO/Fe 3 O 4 A suspension;
step 3, adding zinc acetate dissolved in distilled water to the TiO 2 -rGO/Fe 3 O 4 In 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 ZnO 1-x @TiO 2-x /rGO-Fe 3 O 4 And (3) nano materials.
Preferably, in the step 1, tiO is prepared 2 The 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 TiO 2 And (3) sol.
In the examples of the present invention, tetrabutyl titanate was added dropwise to anhydrous ethanolIn order to inhibit the hydrolysis reaction, acetic acid is additionally dripped into the absolute ethyl alcohol, and the dripping speeds of the acetic acid and the tetrabutyl titanate are respectively 4 s/drip and 1 s/drip, and the dripping speed is carried out at the speed, so that the hydrolysis reaction speed can be effectively reduced; furthermore, by using TiO 2 Sol form to facilitate TiO in subsequent synthesis steps 2 Natural crystallization of nanoparticles to the surface of the support (rGO) resulting in the formation of TiO 2 Small particle size, high purity, good dispersibility, and effective improvement of TiO 2 Agglomeration of particles on the surface of the support (rGO).
Preferably, in the step 2, tiO is prepared 2 -rGO/Fe 3 O 4 The 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.
Sodium acetate and TiO 2 Adding 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 be used for preparing Fe with the first mixed system 3 O 4 And 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 TiO 2-x /rGO-Fe 3 O 4 And (3) suspension.
More preferably, the reaction time of the second hydrothermal reaction is 8-12h, and the reaction temperature is 150-200 ℃;
the second post-processing includes:
washing the reaction system to be neutral by using absolute ethyl alcohol;
washing the productDispersing in distilled water to obtain TiO 2 -rGO/Fe 3 O 4 And (3) suspension.
Preferably, in the step 3, the reaction time of the first hydrothermal reaction is 1-2h, and the reaction temperature is 150-200 ℃.
Preferably, in the step 4, the first post-processing includes:
centrifuging the residue after hydrothermal reaction for 5-7 times and freeze drying to obtain ZnO @ TiO 2 -rGO/Fe 3 O 4 ；
The above-mentioned ZnO @ TiO 2 -rGO/Fe 3 O 4 Calcining in a tubular furnace at 300-550 ℃ under the protection of nitrogen or vacuum for 2-4h.
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 light 2 The hole is formed by TiO 2 The 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 body 2 The 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 CO as pollutant substances 2 、H 2 O, 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: take 20mL ofAqueous ethanol was put into 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 with 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 TiO 2 And (3) sol.
And 2, step: 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 for 8-12h at 150-200 ℃, naturally cooling to room temperature, washing with ethanol to neutrality, and finally dispersing into 100mL of distilled water to obtain TiO 2 -rGO/Fe 3 O 4 (ii) a 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 2 2 -rGO/Fe 3 O 4 In suspension. The solution was adjusted to pH 12 with 0.1M NaOH solution. Then, the mixture was heated in an autoclave at 150 to 200 ℃ for 1 to 2 hours.
And 4, step 4: centrifuging the residue after hydrothermal reaction for 5-7 times, and freeze drying to obtain ZnO @ TiO 2 -rGO/Fe 3 O 4 (ii) a Calcining the prepared precursor in a tubular furnace at the temperature of 300-550 ℃ for 2-4h under the protection of nitrogen to obtain ZnO 1-x @TiO 2-x -rGO/Fe 3 O 4 And (3) nano materials. Repeating the above operation to obtain the nanocomposite material with the molar ratio of Fe to Ti to Zn being 0.5 1-x @TiO 2-x -rGO/Fe 3 O 4 -1。
Example 2
Step 1: 20mL of absolute ethyl alcohol is taken and put intoIn the beaker, 1.5mL of acetic acid and 5mL of tetrabutyltitanate 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 are added into a beaker, and the pH of the solution is adjusted to 2 by dilute nitric acid to prepare a solution B. Slowly adding the solution B into the solution A, and continuously stirring for 30min to obtain TiO 2 And (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 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 for 8-12h at 150-200 ℃, naturally cooling to room temperature, washing with ethanol to neutrality, and finally dispersing into 100mL of distilled water to obtain TiO 2 -rGO/Fe 3 O 4 (ii) a suspension.
And 3, step 3: 200mg of zinc acetate was dissolved in 50ml of distilled water and added to the 100ml of TiO described in step 2 2 -rGO/Fe 3 O 4 In suspension. The solution was adjusted to pH 12 with 0.1M NaOH solution. Then, the mixture was heated in an autoclave at 150 to 200 ℃ for 1 to 2 hours.
And 4, step 4: centrifuging the residue after hydrothermal reaction for 5-7 times, and freeze drying to obtain ZnO @ TiO 2 -rGO/Fe 3 O 4 (ii) a Calcining the prepared precursor in a tubular furnace at 300-550 ℃ under the protection of nitrogen for 2-4h to obtain ZnO 1-x @TiO 2-x -rGO/Fe 3 O 4 And (3) nano materials. Repeating the above operations to obtain the nanocomposite material with the molar ratio of Fe to Ti to Zn of 1 1-x @TiO 2-x -rGO/Fe 3 O 4 -2。
Example 3
Step 1: 20mL of absolute ethyl alcohol is taken and put into a beakerUnder magnetic stirring, 1.5mL of acetic acid and 5mL of tetrabutyltitanate were added dropwise at 4 s/drop and 1 s/drop rates. The resulting mixed liquid was labeled as solution a. 17ml of absolute ethyl alcohol and 3ml of deionized water are added into a beaker, and the pH of the solution is adjusted to 2 by dilute nitric acid to prepare a solution B. Slowly adding the solution B into the solution A, and continuously stirring for 30min to obtain TiO 2 And (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 for 8-12h at 150-200 ℃, naturally cooling to room temperature, washing with ethanol to neutrality, and finally dispersing into 100mL of distilled water to obtain TiO 2 -rGO/Fe 3 O 4 (ii) a 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 2 2 -rGO/Fe 3 O 4 In suspension. The solution was adjusted to pH 12 with 0.1M NaOH solution. Then, the mixture was heated in an autoclave at 150 to 200 ℃ for 1 to 2 hours.
And 4, step 4: centrifuging the residue after hydrothermal reaction for 5-7 times, and freeze drying to obtain ZnO @ TiO 2 -rGO/Fe 3 O 4 (ii) a Calcining the prepared precursor in a tubular furnace at 300-550 ℃ under the protection of nitrogen for 2-4h to obtain ZnO 1-x @TiO 2-x -rGO/Fe 3 O 4 And (3) nano materials. Repeating the above operations to obtain the nanocomposite material with the molar ratio of Fe to Ti to Zn of 2 1-x @TiO 2-x -rGO/Fe 3 O 4 -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 invention 2 Sol and further preparation of TiO 2 -rGO/Fe 3 O 4 Adding zinc acetate and sodium hydroxide into the suspension, and obtaining ZnO through hydrothermal reaction and post-treatment 1-x @TiO 2-x -rGO/Fe 3 O 4 And (3) nano materials.
FIG. 2 shows ZnO prepared in example 1 of the present invention 1-x @TiO 2-x -rGO/Fe 3 O 4 SEM 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 TiO 2 、ZnO@TiO 2 、TiO 2 -rGO/Fe 3 O 4 、ZnO@TiO 2 -rGO/Fe 3 O 4 And ZnO 1-x @TiO 2-x -rGO/Fe 3 O 4 The ultraviolet absorption spectrum of (2) was analyzed by an ultraviolet diffuse reflectance spectroscopy. As can be seen, the light absorption boundaries of the above materials are all around 390 nm. With TiO 2 In contrast, the light absorption boundaries of the composite materials with different doping ratios are all obviously red-shifted. To in ZnO @ TiO 2 -rGO/Fe 3 O 4 Further increasing the visible light absorption range of the composite material by calcining ZnO @ TiO under vacuum condition 2 -rGO/Fe 3 O 4 Prepare ZnO 1-x @TiO 2-x -rGO/Fe 3 O 4 A 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 C 1-x @TiO 2-x -rGO/Fe 3 O 4 The 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 TiO 2-x -rGO/Fe 3 O 4 And the visible light absorption range of the new material is not easy to see compared with that of TiO 2-x -rGO/Fe 3 O 4 The method has the advantages of remarkably improving the light utilization efficiency of the photocatalyst, and improving mutual evidence with the subsequent degradation efficiency.
FIG. 4 shows TiO in example 1 of the present invention 2 、ZnO@TiO 2 -rGO/Fe 3 O 4 And ZnO 1-x @TiO 2-x -rGO/Fe 3 O 4 Fourier 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 -1 And 3423cm -1 The nearby absorption peak corresponds to the stretching vibration of the O-H bond on the surface of the material and is 590cm -1 The absorption peak is caused by the stretching vibration of the Fe-O bond. Below 800cm -1 The 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 TiO 2 H of the surface 2 Bending and stretching vibration of O-H bond of O or-OH. In addition, for Fe 3 O 4 590cm of Fe-O band vibration -1 The bands around generally correspond to iron cations at tetrahedral sites, while another strong peak appears at 800cm -1 Below, 510cm due to Ti-O-Ti groups -1 The presence of zinc oxide is confirmed by the peak at which the presence of ZnO, fe is confirmed 3 O 4 And TiO 2 Nanoparticles have been successfully grafted onto rGO sheets in hydrothermal processes. Furthermore, in ZnO 1-x @TiO 2-x -rGO/Fe 3 O 4 In the composite catalyst, tiO 2 Characteristic peaks for rGO and ZnO are clearly visible, while Fe 3 O 4 Is mainly due to Fe 3 O 4 Too 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 1 1-x @TiO 2-x -rGO/Fe 3 O 4 Photocatalytic nano material and common TiO 2 Nanoparticles, znO @ TiO 2 、ZnO@TiO 2 -rGO/Fe 3 O 4 、TiO 2-x -rGO/Fe 3 O 4 And ZnO 1-x @TiO 2-x -rGO/Fe 3 O 4 Visible light catalytic reductionA performance comparison graph for imidacloprid is shown. Ordinary TiO 2 Nanoparticles with ZnO @ TiO 2 Can only remove 20 percent of imidacloprid within 30 minutes, znO @ TiO 2 -rGO/Fe 3 O 4 The photocatalytic nano material can only remove imidacloprid by about 40 percent within 30 minutes, and TiO 2-x -rGO/Fe 3 O 4 The removal rate of the photocatalytic nano material to imidacloprid can reach about 80 percent within 30 minutes, and ZnO can reach 1-x @TiO 2-x -rGO/Fe 3 O 4 The 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 invention 1-x @TiO 2-x -rGO/Fe 3 O 4 The degradation efficiency of the photocatalytic nano material to imidacloprid is considerable, and related data are successfully mutually verified with the previous effective improvement of the ultraviolet light absorption range.
FIG. 6 shows ZnO prepared in example 1 of the present invention 1-x @TiO 2-x -rGO/Fe 3 O 4 A performance contrast diagram of the nano material for degrading imidacloprid by visible light catalysis under different environmental conditions of pure illumination, PS and PMS reflects the degradation capability of the photocatalytic nano degradation material on imidacloprid organic pollutants under different environmental conditions, and the degradation rate constant of imidacloprid molecules under the pure illumination condition is obviously less than that under the PMS condition, and the concentration change of the imidacloprid molecules under the visible pure illumination is small.
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, the specific implementation manner and the application scope may be changed, and in summary, the content of the present specification should not be construed as a limitation to the present application.
Claims (7)
1. A ZnO-based heterojunction photocatalytic composite material is characterized in that the composite material isTaking single layer rGO as a basic material, and grafting TiO on the basic material 2-x Nanoparticles, znO 1-x Nanoparticles and Fe 3 O 4 Nanoparticle derived ZnO 1-x @TiO 2-x -rGO/Fe 3 O 4 Nanomaterial, wherein x = 0.05-0.45;
the ZnO 1-x @TiO 2-x -rGO/Fe 3 O 4 The molar ratio of Fe to Ti to Zn in the nano material is 0.5;
wherein the method for preparing the composite material comprises the following steps:
step 1, preparation of TiO 2 Sol;
step 2, preparing TiO 2 -rGO/Fe 3 O 4 A suspension;
step 3, adding zinc acetate dissolved in distilled water to the TiO 2 -rGO/Fe 3 O 4 In 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 ZnO 1-x @TiO 2-x -rGO/Fe 3 O 4 A nanomaterial;
in the step 2, tiO is prepared 2 -rGO/Fe 3 O 4 The 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;
adding an organic alcohol solution of ferric chloride hexahydrate into the graphene oxide mixed system, and uniformly mixing to obtain a first mixed system;
sodium acetate and TiO 2 Adding 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 TiO 2 -rGO/Fe 3 O 4 A suspension;
in 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 @ TiO 2 -rGO/Fe 3 O 4 ；
The above-mentioned ZnO @ TiO 2 -rGO/Fe 3 O 4 Calcining in a tubular furnace at 300-550 ℃ under the protection of nitrogen or vacuum for 2-4h.
2. A method for preparing the composite material of claim 1, wherein the method comprises:
step 1, preparation of TiO 2 Sol;
step 2, preparing TiO 2 -rGO/Fe 3 O 4 A suspension;
step 3, adding zinc acetate dissolved in distilled water to the TiO 2 -rGO/Fe 3 O 4 In 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 ZnO 1-x @TiO 2-x -rGO/Fe 3 O 4 A nanomaterial;
in the step 2, tiO is prepared 2 -rGO/Fe 3 O 4 The 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;
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 TiO 2 Adding 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 TiO 2 -rGO/Fe 3 O 4 Suspended in waterLiquid;
in 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 @ TiO 2 -rGO/Fe 3 O 4 ；
The above-mentioned ZnO @ TiO 2 -rGO/Fe 3 O 4 Calcining in a tubular furnace at 300-550 ℃ under the protection of nitrogen or vacuum for 2-4h.
3. The method of claim 2, wherein in step 1, tiO is prepared 2 The 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 TiO 2 And (3) sol.
4. The method according to claim 2, characterized in that the reaction time of the second hydrothermal reaction is 8-12h and the reaction temperature is 150-200 ℃.
5. The method of claim 2, 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 TiO 2 -rGO/Fe 3 O 4 (ii) a suspension.
6. The method according to claim 2, wherein in the step 3, the reaction time of the first hydrothermal reaction is 1-2h, and the reaction temperature is 150-200 ℃.
7. The application of the ZnO-based heterojunction photocatalytic composite material is characterized in that the application comprises the following steps:
the composite material of claim 1 is used for high-efficiency photocatalytic treatment of neonicotinoid pesticide pollutants; the neonicotinoid pesticide pollutant is imidacloprid; the degradation efficiency of the ZnO-based heterojunction photocatalytic composite material to imidacloprid within 30 minutes is 99%.
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