CN110102322B - Preparation method of flower-shaped Ag @ AgBr/ZnO photocatalytic material - Google Patents
Preparation method of flower-shaped Ag @ AgBr/ZnO photocatalytic material Download PDFInfo
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- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
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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
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- OIWSIWZBQPTDKI-UHFFFAOYSA-N 1-butyl-3-methyl-2h-imidazole;hydrobromide Chemical compound [Br-].CCCC[NH+]1CN(C)C=C1 OIWSIWZBQPTDKI-UHFFFAOYSA-N 0.000 description 1
- KYCQOKLOSUBEJK-UHFFFAOYSA-M 1-butyl-3-methylimidazol-3-ium;bromide Chemical compound [Br-].CCCCN1C=C[N+](C)=C1 KYCQOKLOSUBEJK-UHFFFAOYSA-M 0.000 description 1
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- 229960001763 zinc sulfate Drugs 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/138—Halogens; Compounds thereof with alkaline earth metals, magnesium, beryllium, zinc, cadmium or mercury
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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
- 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
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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Abstract
The invention discloses a preparation method of a flower-shaped Ag @ AgBr/ZnO photocatalytic material, and belongs to the field of nano material preparation. The method comprises the following steps: 1) preparing a surfactant and a Zn source with certain concentration as a Zn source solution; preparing hexamethylenetetramine and an Ag source with certain concentration as an Ag source solution; 2) adding an oxidant into the Ag source solution, and dropwise adding the oxidant into the Zn source solution at a certain speed; 3) transferring the mixed solution to a high-pressure reaction kettle, and carrying out hydrothermal reaction at a certain temperature for a certain time; 4) and washing and drying the product by water and alcohol, calcining in air, and cooling to room temperature to obtain the flower-shaped Ag @ AgBr/ZnO photocatalytic material. The synthetic method adopted by the invention has the advantages of simple process, simple and convenient operation and no secondary pollution. The synthesized photocatalytic material has the characteristics of uniform appearance, excellent performance and the like. The invention belongs to the field of photocatalytic materials.
Description
Technical Field
The invention relates to a preparation method of a flower-shaped Ag @ AgBr/ZnO photocatalytic material.
Background
ZnO is a semiconductor catalyst widely applied to photocatalytic oxidation technology, and has excellent photocatalytic activity, stable chemical property and higher quantum yield, so ZnO has higher application value in the directions of sewage treatment and the like. However, ZnO is a wide bandgap semiconductor material, can only excite photocatalytic oxidation reaction by ultraviolet light, has a sunlight utilization rate of only 4%, and has the problem of high electron-hole pair recombination rate when ZnO is used as a photocatalytic material. These drawbacks limit their practical applications. To solve these defects of ZnO, a series of attempts have been made. Research shows that the Ag @ AgBr plasma catalyst can respond to visible light to perform a photocatalytic oxidation process due to the plasma resonance effect of Ag nano particles generated by decomposition of AgBr in a system, but the Ag @ AgBr plasma catalyst is directly used for photocatalytic oxidation due to a small inherent band gap and has an unsatisfactory effect. In view of the respective advantages and disadvantages of a single catalyst, Ag @ AgBr and ZnO are compounded to form the composite catalyst Ag @ AgBr/ZnO, so that the utilization rate of the photocatalyst to light is greatly improved, electron transfer can be generated among components, the compounding of electron-hole pairs is delayed, and the speed and the efficiency of photocatalytic degradation of organic matters are improved. Today, the environmental situation is severe, the research and development of efficient composite photocatalysts are urgent, and the photocatalyst has both theoretical significance and practical value.
In 2013, Lei Shi et al used a deposition-precipitation method to obtain an AgBr/ZnO photocatalytic material in a two-step method in an article, "high effective visible light-driving Ag/AgBr/ZnO composite photocatalytic for grading Rhodamine B", and then prepared a rod-shaped Ag/AgBr/ZnO nanocomposite material by a photo-reduction method. Under the condition of 1h of simulated solar irradiation, the degradation rate of 0.05g of the sample to 10mg/L of rhodamine B is 94.7%. The preparation method of combining the deposition-precipitation two-step method with the photoreduction method has the problems of complex operation, complex flow, long preparation period and the like.
In 2014, Qi Zhang et al used bromine water to oxidize Ag/ZnO microspheres prepared by a one-pot method In situ In an article In situ oxidation of Ag/ZnO by bromine water to obtain the spherical Ag-AgBr/ZnO composite photocatalytic material. Under the condition of irradiating for 3 hours by a 300W iodine tungsten lamp, the degradation rate of 0.1g of the sample to 5mg/L rhodamine B is close to 100 percent. The preparation method has the problems of complicated preparation process and long preparation period, and the spherical Ag-AgBr/ZnO has low degradation efficiency.
In 2011, Xuyuan et al prepared Ag/AgBr @ ZnO photocatalyst by a hydrothermal method in a conference of research on preparation of Ag/AgBr @ ZnO photocatalyst and degradation of methyl orange. The degradation rate of methyl orange after 3 hours of illumination is about 95 percent. As can be seen, the degradation time as long as 3 hours can not embody the advantage of high efficiency and rapidness of the photocatalytic oxidation method.
In a patent "preparation method of porous Ag/AgBr nanomaterial" (CN108975383A), Shipeng et al prepared porous Ag/AgBr material by 2018 by a hydrothermal method. In the method, an Ag/AgCl/AgBr precursor is prepared firstly, and is washed by an ammonia water solution to remove AgCl to obtain Ag/AgBr, the preparation process does not directly point to the finally prepared nano material, and certain waste is caused to the raw material.
In 2016 (CN106111166A), Chenyun et al prepared Ag/AgBr photocatalyst by hydrothermal method with imidazolyl ionic liquid 1-butyl-3-methylimidazol bromide ([ BMIM ] Br) as a bromine source and a precursor. It is worth pointing out that the ionic liquid can absorb the moisture in the air (even though the ionic liquid is hydrophobic), greatly reducing the performance; in practical experiments, the ionic liquid has high price and low purity (limited by the preparation process), and once impurities are mixed, the performance of the ionic liquid is influenced, so that the practical application capability of the ionic liquid is limited.
In 2015 WangYong et al, CuBr microspheres were used as templates in a preparation method of AgBr/Ag porous composite microspheres for visible light catalysts (CN104815679A), and an ion exchange method was used to prepare AgBr/Ag porous composite microspheres for visible light catalysts. The degradation rate of 30mL of methyl orange with 10mg/mL under the irradiation of a 400nm filter xenon lamp (500W) is more than 90%.
Songhua et al, 2018, in a patent "preparation method of Ag/ZnO nanorod self-assemblies" (CN108745354A), prepared Ag/ZnO nanorod self-assemblies by spray drying, and then baked to obtain Ag/ZnO nanorod self-assemblies with hierarchical structures. The yield of the prepared Ag/ZnO nano-rod assembly photocatalytic material used for photocatalytic decomposition of water for hydrogen production can reach 1.07mmol/g-1h-1。
In a patent of 'a method for preparing an Ag-loaded ZnO nanorod array' (CN108970612A) by Zhaojingzhi et al in 2018, firstly a ZnO seed layer substrate is prepared, secondly a ZnO nanorod array film is prepared, and finally the prepared ZnO nanorod array film is subjected to Ag loading to obtain an Ag-loaded ZnO material.
In patent "a preparation method of hollow ZnO" (CN108002425A) of Chua Penapon et al in 2017, a spray pyrolysis method in a gas phase method is adopted to prepare the ZnO photocatalytic material. It is worth mentioning that the hollow ZnO material prepared by the method has serious fragmentation, uneven grain diameter and non-uniform appearance. This result would directly lead to an uncontrolled photocatalytic activity of the material.
In a patent "preparation method of micron/nano ZnO with controllable morphology under normal pressure and low temperature" (CN108275713A), the inventors of 2018 Yanchenjun et al prepared micron/nano ZnO with various morphologies under normal pressure and low temperature. It is worth noting that this preparation method uses oleylamine as a solvent, which is known to have an irritating odor and to burn and corrode the skin. The safety of this preparation method is to be investigated.
Although the above-mentioned methods have made outstanding contributions in the preparation of photocatalytic materials, there are a number of common problems with these preparation methods, such as: the preparation process is complicated, the requirements on raw materials are strict, and the catalytic performance of the obtained catalyst with special morphology is not strong. In comparison, the one-step hydrothermal method used in the invention has the advantages of simple process, convenient operation, easy control of various parameters, cheap and easily available raw materials, and the special morphology of the catalyst is beneficial to the promotion of catalytic activity. Besides being used as a surfactant to control the morphology, CTAB also serves as a bromine source, so that the morphology is controlled, the raw materials are saved, and the two purposes are achieved.
In summary, the flower-like Ag @ AgBr/ZnO material with excellent photocatalytic performance is synthesized by a simple one-step hydrothermal method, and the material meets the relevant requirements on the material in practical application.
Disclosure of Invention
The invention aims to solve the problems of high price of raw materials, complex and fussy process flow, long preparation time, unsuitable mass production of production efficiency, poor photocatalytic activity of a photocatalyst and the like of the existing preparation method of the Ag @ AgBr/ZnO photocatalytic material, and provides a preparation method of a flower-shaped Ag @ AgBr/ZnO photocatalytic material.
The preparation method of the flower-shaped Ag @ AgBr/ZnO photocatalytic material comprises the following steps:
firstly, preparing a Zn source and a surfactant with certain concentration in 30mL of distilled water according to a certain ratio of the quantity of Zn element, Ag element, hexamethylenetetramine and the surfactant to obtain a Zn source solution; preparing an Ag source and hexamethylenetetramine with certain concentration in 20mL of distilled water, and adding an oxidant to obtain an Ag source solution;
and secondly, dropwise adding the Ag source solution into the Zn source solution at a certain dropwise adding speed, transferring the mixed solution to a high-pressure reaction kettle for hydrothermal reaction, wherein the mixed solution accounts for about 50% of the volume of the reaction kettle, and keeping the hydrothermal temperature for a certain hydrothermal time.
And thirdly, washing with alcohol and drying the product, transferring the product into a muffle furnace, calcining the product at a certain temperature for a certain time in the air atmosphere, and cooling the product to room temperature to obtain the flower-shaped Ag @ AgBr/ZnO photocatalytic material.
The ratio of the Zn element, the Ag element, the hexamethylenetetramine and the surfactant in the first step is 1 (0.01-0.4): 1: (0.1 to 1).
The concentrations of the Zn source, the surfactant, the Ag source and the hexamethylenetetramine in the first step are respectively 0.3333mol/L, (0.03333-0.3333) mol/L, (0.05-0.2) mol/L and 0.5 mol/L.
The Zn source in the first step is zinc sulfate (ZnSO)4) Zinc acetate dihydrate (C)4H6O4Zn·2H2O), zinc nitrate hexahydrate (Zn (NO)3)2·6H2O) or zinc sulfate heptahydrate (ZnSO)4·7H2O) compound.
The surfactant in the first step is Cetyl Trimethyl Ammonium Bromide (CTAB)
The oxidant in the step one is H2O2(30％)。
The dropping speed in the second step is 1-3 seconds per drop; setting the hydrothermal temperature to be 100-180 ℃; the hydrothermal time is 1-5 hours.
The calcining temperature in the third step is 500-800 ℃; the calcination time is 1-3 h.
The invention has the following beneficial effects:
according to the invention, zinc salt and silver nitrate are used as silver sources, so that the raw material components are mixed at a molecular level, and the synthesized flower-shaped Ag @ AgBr/ZnO photocatalytic material consisting of porous lamellar layers has uniform chemical components; according to the invention, CTAB is used as a surfactant, so that the morphology and particle size of the catalyst can be effectively controlled, and the synthesized flower-shaped Ag @ AgBr/ZnO photocatalytic material has uniform morphology and uniform particle size; meanwhile, CTAB also participates in the reaction as a Br source, other Br sources are not required to be additionally selected, the cost is saved, the preparation difficulty of the Ag @ AgBr/ZnO photocatalyst is effectively reduced, and the prepared flower-shaped Ag @ AgBr/ZnO composed of porous sheets has extremely strong photocatalytic activity and meets the relevant requirements on materials in practical application.
Drawings
FIG. 1 is SEM photograph of flower-like Ag @ AgBr/ZnO material prepared by the method of the invention
FIG. 2 shows XRD spectrogram of flower-like Ag @ AgBr/ZnO material prepared by the method of the invention
FIG. 3 is a graph showing the relationship between the degradation efficiency of the flower-like Ag @ AgBr/ZnO material (embodiment one) prepared by the method of the present invention to rhodamine B and the photocatalytic time, wherein the amount of the catalyst is 1 g.L-1Rhodamine B concentration 5 mg. L-1. In the figure, (a) the degradation efficiency of rhodamine B when an Ag @ AgBr/ZnO material (a first embodiment) is catalyzed under simulated sunlight; (b) the natural degradation efficiency of rhodamine B under simulated sunlight is realized without using Ag @ AgBr/ZnO material for catalysis; (c) the degradation efficiency of rhodamine B is realized by catalyzing an Ag @ AgBr/ZnO material (specific embodiment I) under the dark condition.
FIG. 4 is a graph showing the relationship between the degradation efficiency and the photocatalytic time of the flower-like Ag @ AgBr/ZnO material (embodiment one) prepared by the method of the present invention, wherein the amount of the catalyst is 1 g.L-1Concentration of methylene blue 10 mg.L-1。
FIG. 5 is a graph showing the relationship between the degradation efficiency and the photocatalytic time of the flower-like Ag @ AgBr/ZnO material (embodiment one) prepared by the method of the present invention, wherein the amount of the catalyst is 1 g.L-1The concentration of cefuroxime sodium is 20 mg.L-1。
Detailed Description
The technical solution of the present invention is not limited to the following specific embodiments, but includes any combination of the specific embodiments.
The first embodiment is as follows: the preparation method of the flower-shaped Ag @ AgBr/ZnO material photocatalytic material in the embodiment comprises the following steps:
firstly, according to the mass ratio of Zn element, Ag element, hexamethylenetetramine and surfactant being 1: 0.2: 1: weighing zinc acetate dihydrate, silver nitrate, hexamethylenetetramine and CTAB according to the proportion of 0.55, and preparing 0.3333mol/L and 0.1833mol/L Zn source and surfactant in 30mL of distilled water to obtain Zn source solution; preparing 0.1mol/L and 0.5mol/L Ag source and hexamethylenetetramine in 20mL of distilled water, and adding an oxidant and an Ag source solution;
dropwise adding the Ag source solution into the Zn source solution at a dropping rate of 1 second/drop, transferring the mixed solution to a high-pressure reaction kettle for hydrothermal reaction, wherein the mixed solution accounts for about 50% of the volume of the reaction kettle, the set hydrothermal temperature is 140 ℃, and the hydrothermal time is maintained at the temperature for 3 hours;
and thirdly, washing with alcohol and drying the product, transferring the product into a muffle furnace, calcining the product for 2 hours at the temperature of 650 ℃ in the air atmosphere, and cooling the product to room temperature to obtain the flower-shaped Ag @ AgBr/ZnO photocatalytic material.
The beneficial effects of the embodiment are as follows: the flower-shaped Ag @ AgBr/ZnO material synthesized by the embodiment has a flower-shaped structure formed by clustering porous sheet layers, and the growth direction and clustering mode of a catalyst crystal can be effectively controlled by using CTAB (cetyl trimethyl ammonium bromide), so that the appearance of the catalyst crystal is as follows: the flower-shaped Ag @ AgBr/ZnO material is assembled by porous sheets in a cluster mode, and the diameter of the flower-shaped Ag @ AgBr/ZnO material is about 4-6 mu m, as shown in figure 1. The larger size is beneficial to the free electron transfer in the photocatalyst photocatalysis process, and the XRD result (figure 2) shows that the composite material prepared by the invention has high crystallization property, and the characteristic is also beneficial to the free electron transfer in the photocatalyst photocatalysis process. The high-efficiency transmission of free electrons can reduce the recombination probability of electron holes to a certain extent, so that the Ag @ AgBr/ZnO composite photocatalytic material shows extremely excellent photocatalytic activity.
1 g.L of prepared flower-shaped Ag @ AgBr/ZnO material-1Degradation is 5 mg.L-1The rhodamine B solution is stirred for 30min under simulated sunlight, and the degradation rate reaches 99.11 percent.
1 g.L of prepared flower-shaped Ag @ AgBr/ZnO material-1Degradation is 10 mg.L-1The methylene blue solution is stirred for 30min under simulated sunlight, and the degradation rate reaches 99.99 percent.
1 g.L of prepared flower-shaped Ag @ AgBr/ZnO material-1Degradation is 20 mg.L-1The cefuroxime sodium solution is stirred for 30min under simulated sunlight,the degradation rate is 74.77%; stirring for 150min, and the degradation rate reaches 95.09%.
The second embodiment is as follows:
firstly, according to the mass ratio of Zn element, Ag element, hexamethylenetetramine and surfactant being 1: 0.2: 1: weighing zinc acetate dihydrate, silver nitrate, hexamethylenetetramine and CTAB according to the proportion of 0.55, and preparing 0.3333mol/L and 0.1833mol/L Zn source and surfactant in 30mL of distilled water to obtain Zn source solution; preparing 0.1mol/L and 0.5mol/L Ag source and hexamethylenetetramine in 20mL of distilled water, and adding an oxidant and an Ag source solution;
dropwise adding the Ag source solution into the Zn source solution at the dropping rate of 3 seconds per drop, transferring the mixed solution to a high-pressure reaction kettle for hydrothermal reaction, wherein the mixed solution accounts for about 50% of the volume of the reaction kettle, the set hydrothermal temperature is 160 ℃, and the hydrothermal time is maintained at the temperature for 2.5 hours;
and thirdly, washing with alcohol and drying the product, transferring the product into a muffle furnace, calcining the product for 2.5 hours at the temperature of 500 ℃ in the air atmosphere, and cooling the product to room temperature to obtain the flower-shaped Ag @ AgBr/ZnO photocatalytic material.
The third concrete implementation mode:
firstly, according to the mass ratio of Zn element, Ag element, hexamethylenetetramine and surfactant being 1: 0.2: 1: weighing zinc acetate dihydrate, silver nitrate, hexamethylenetetramine and CTAB according to the proportion of 0.55, and preparing 0.3333mol/L and 0.1833mol/L Zn source and surfactant in 30mL of distilled water to obtain Zn source solution; preparing 0.1mol/L and 0.5mol/L Ag source and hexamethylenetetramine in 20mL of distilled water, and adding an oxidant and an Ag source solution;
dropwise adding the Ag source solution into the Zn source solution at the dropping rate of 2 seconds/drop, transferring the mixed solution to a high-pressure reaction kettle for hydrothermal reaction, wherein the mixed solution accounts for about 50% of the volume of the reaction kettle, the set hydrothermal temperature is 130 ℃, and the hydrothermal time is maintained at the temperature for 4 hours;
and thirdly, washing with alcohol and drying the product, transferring the product into a muffle furnace, calcining the product for 3 hours at the temperature of 700 ℃ in the air atmosphere, and cooling the product to room temperature to obtain the flower-shaped Ag @ AgBr/ZnO photocatalytic material.
The flower-shaped Ag @ AgBr/ZnO powder disclosed by the invention can be used for photocatalytic decomposition of organic pollutants, and takes sunlight or ultraviolet light as a light source. During the photocatalytic reaction, a certain amount of catalyst (0.5-1 g/L) is added under the stirring condition, and the aqueous solution of organic pollutants such as rhodamine B, methylene blue, cefuroxime sodium and the like with a certain concentration (5-20 mg/L) is degraded within a certain time (0.5-3 h). For example: catalyzing and degrading 5mg/L rhodamine B solution, taking 100ml rhodamine B solution, adding a catalyst (0.5-1 g/L), carrying out catalytic reaction under sunlight or ultraviolet light, sampling 3-5 ml solution samples at intervals of 7.5-30 min, filtering, and measuring the absorbance of the solution by using an ultraviolet-visible spectrophotometer to detect the change of the solution concentration so as to calculate the degradation rate of organic pollutants.
Claims (2)
1. The preparation method of the flower-shaped Ag @ AgBr/ZnO photocatalytic material is characterized by comprising the following steps of:
firstly, Zn element, Ag element, hexamethylenetetramine and hexadecyl trimethyl ammonium bromide according to the mass ratio of 1 (0.01-0.4): 1: (0.1-1), adding a Zn source and hexadecyl trimethyl ammonium bromide solution into 30mL of distilled water to obtain a Zn source solution; the Ag source and hexamethylenetetramine were added to 20mL of distilled water, and oxidant H was added2O2Obtaining Ag source solution;
dropwise adding the Ag source solution into the Zn source solution at the speed of 1-3 seconds per drop, transferring the mixed solution to a high-pressure reaction kettle for hydrothermal reaction, wherein the mixed solution accounts for 50% of the volume of the reaction kettle, and carrying out hydrothermal reaction for 1-5 hours at the temperature of 100-180 ℃;
and thirdly, washing with alcohol and drying the product, transferring the product into a muffle furnace, calcining for 1-3 h at 500-800 ℃ in the air atmosphere, and cooling to room temperature to obtain the flower-shaped Ag @ AgBr/ZnO photocatalytic material.
2. The preparation method of the flower-like Ag @ AgBr/ZnO photocatalytic material as claimed in claim 1, wherein the Zn source in the first step is zinc acetate dihydrate, zinc nitrate hexahydrate or zinc sulfate heptahydrate, and the Ag source is silver nitrate.
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