阅读说明：本技术 一种四环素光催化降解材料及其制备方法 (Tetracycline photocatalytic degradation material and preparation method thereof ) 是由 赖小勇 暴彦吉 王晓中 郭茹 杨庆凤 于 2019-09-18 设计创作，主要内容包括：本发明涉及一种四环素光催化降解材料及其制备方法,其特点是：由三氧化二铁螺旋纳米线立方周期性排列而成,该纳米线的直径为3-7nm,具有12nm的均一大介孔。本发明提供的高比表面有序大介孔三氧化二铁四环素催化材料在四环素的降解过程中表现出优良的降解性能,可以实现在很高程度对四环素的高效降解。(The invention relates to a tetracycline photocatalytic degradation material and a preparation method thereof, and the material is characterized in that: the nano-wire is formed by cubic periodic arrangement of ferric oxide spiral nano-wires, the diameter of the nano-wires is 3-7nm, and the nano-wires have uniform large mesopores of 12 nm. The high-specific-surface-area ordered large-mesopore ferric oxide tetracycline catalytic material provided by the invention shows excellent degradation performance in the degradation process of tetracycline, and can realize high-efficiency degradation of tetracycline to a very high degree.)

1. A tetracycline photocatalytic degradation material is characterized in that: the nano-wire is formed by cubic periodic arrangement of ferric oxide spiral nano-wires, the diameter of the nano-wires is 3-7nm, and the nano-wires have uniform large mesopores of 12 nm.

2. The tetracycline photocatalytic degradation material of claim 1, characterized in that: wherein the specific surface area of the material is up to 176m².g^-1。

3. A preparation method of a tetracycline photocatalytic degradation material is characterized by comprising the following steps:

a. mixing 9g of surfactant P123, 325ml of deionized water and 15ml of hydrochloric acid with the concentration of 37 wt% at 35 ℃, stirring for 1-12h until the surfactant is completely dissolved and uniformly dispersed, then adding 9g of n-butyl alcohol, stirring for 2h, adding 19.4g of tetraethyl orthosilicate TEOS, stirring in a water bath for 24h, transferring solid particles and a reaction solution into a polytetrafluoroethylene lining, carrying out hydrothermal reaction at 35-140 ℃ for 24h, naturally cooling to room temperature, washing with deionized water to be neutral, and drying at 70 ℃ overnight to obtain mesoporous silicon oxide containing the surfactant;

b. calcining the obtained mesoporous silica containing the surfactant for 6h at 550 ℃ in the air to obtain mesoporous silica without the surfactant;

c. taking 2g of the mesoporous silicon oxide obtained in the step b as a hard template, dispersing the mesoporous silicon oxide into a 50ml centrifuge tube, adding 0.1733-1.7338g of ferric nitrate into the centrifuge tube to be dissolved in a 70-120 ℃ forced air drying oven, adding the ferric nitrate into the template after the nitrate is completely melted into liquid, oscillating the centrifuge tube so that the nitrate solution fully enters the pore channel of the mesoporous silicon oxide, continuously heating and oscillating the mesoporous silicon oxide within the temperature range of 70-100 ℃ for 1-2h, calcining the mesoporous silicon oxide in the air at 500 ℃ for 2-10 h, and controlling the calcining temperature rise rate to be 0.5-2.5 ℃/min;

d. and adding 50-200ml of NaOH solution with the concentration of 2-10M into the calcined product, stirring, and then carrying out centrifugal filtration to remove the mesoporous silica template, thus obtaining the ordered large mesoporous ferric oxide of the tetracycline photocatalytic degradation material.

4. The method for preparing the tetracycline photocatalytic degradation material as claimed in claim 3, wherein the method comprises the following steps: the hydrothermal reaction temperature in the step a is 40-100 ℃.

5. The method for preparing the tetracycline photocatalytic degradation material of claim 3, wherein the method comprises the following steps: in the step c, the dissolving temperature is 70 ℃, the heating rate is 1 ℃/min, and the calcining time is 6 h.

6. The method for preparing the tetracycline photocatalytic degradation material of claim 3, wherein the method comprises the following steps: the concentration of the sodium hydroxide solution in step d was 2M.

Technical Field

The invention relates to a tetracycline photocatalytic degradation material and a preparation method thereof.

Background

Since the discovery of penicillin in 1929, the class of antibiotics has been growing at a dramatic rate, from the first few to the thousands of this day. Particularly, with the continuous development of society, antibiotics play an increasingly important role in the production and life of society, particularly have irreplaceable effects on promoting the growth of organisms and inhibiting the growth of parasites, even on the treatment of cardiovascular diseases and the inhibition of the immune response of human bodies, and in addition, research shows that the antibiotics also have certain effects on transplantation operations of some organs. However, the development of society is influenced by the use of antibiotics in large quantities, abuse and abandonment. In particular, some antibiotics are not completely absorbed by the body, and most of the antibiotics are discharged into the environment along with urine and excrement. Waste or unmetabolized antibiotics enter natural water bodies to cause pollution and cause increasingly severe adverse effects on the environment. Especially antibiotics like some tetracyclines are more environmentally hazardous and more durable. Therefore, new challenges are brought to the environmental management, and if the new challenges are not taken care of, the new challenges will bring great threats to the human life and health. Therefore, removal of antibiotics is imminent.

At present, methods for removing tetracycline antibiotics mainly include adsorption methods, coagulation sedimentation methods, biotechnological treatment methods and the like. But has the defects of higher treatment cost, long treatment period, complex operation, lower treatment efficiency and the like. The photocatalysis technology is a green and environment-friendly advanced oxidation organic wastewater treatment technology and has wide application in many aspects. Common photocatalysts are mainly transition metal oxides, non-metal nitrides or sulfides. Zhang et al synthesized an iron-containing mesoporous silica (Fe-SBA15) as an adsorbent to adsorb tetracycline in water with a maximum adsorption capacity of 155.76mmol kg in 24 hours^-1(Zhang Z,Lan H,Liu H,et al.Iron-incorporated mesoporous silicafor enhanced adsorption of tetracycline in aqueous solution[J].2015.)，Furthermore Hui zar-F elix et al used RGO/Fe₂O₃The maximum adsorption capacity of the complex as an adsorbent was 44.23mg/g (Hui zar-Filix A M, Agairar-Flores C, Martinez-de-la Cruz A, ethyl, remove of Tetracycline polutants by adsorption and Magnetic separation using Reduced Graphene Oxide adsorbed with alpha-Fe) in a 25mg/L Tetracycline aqueous solution₂O₃Nanoparticles[J]Nanomaterials,2019,9(3): 313.); chen et al Ag-AgVO₃/g-C₃N₄The tetracycline degradation efficiency of the compound serving as a catalyst can reach 83.6 percent (Chen, D, B.Li, Q.Pu, X.Chen, G.Wen, and Z.Li.preparation of Ag-AgVO) in 2.5 hours₃/g-C₃N₄Synthesis of MoO type Z from Composite Photo-Catalyst and DegradationCharacteriscs of antibiotics J Hazard Mater,2019,4(21):303-12) Xie et al₃/g-C₃N₄The compound is used as a catalyst to degrade tetracycline, and the degradation efficiency can reach 88.4 percent within 3 hours (Xie Z, FengY, Wang F, et al₃/g-C₃N₄Z-schemephotocatalyst with enhanced visible-light photocatalytic activity for thedegradation oftetracycline[J]Applied Catalysis B: Environmental,2018,229: 96-104.). However, catalysts with shorter time and higher degradation efficiency are still under further development.

Disclosure of Invention

The invention aims to provide a tetracycline photocatalytic degradation material which can show excellent degradation performance in the degradation process of tetracycline and realize high-efficiency degradation of the tetracycline to a high degree;

the second purpose of the present invention is to provide a method for preparing the ferric oxide material.

A tetracycline photocatalytic degradation material, which is characterized in that: the nano-wire is formed by cubic periodic arrangement of ferric oxide spiral nano-wires, the diameter of the nano-wires is 3-7nm, and the nano-wires have uniform large mesopores of 12 nm.

Wherein the specific surface area of the material is up to 176m².g^-1。

A preparation method of a tetracycline photocatalytic degradation material is characterized by comprising the following steps:

a. mixing 9g of surfactant P123, 325ml of deionized water and 15ml of hydrochloric acid with the concentration of 37 wt% at 35 ℃, stirring for 1-12h until the surfactant is completely dissolved and uniformly dispersed, then adding 9g of n-butyl alcohol, stirring for 2h, adding 19.4g of tetraethyl orthosilicate TEOS, stirring in a water bath for 24h, transferring solid particles and a reaction solution into a polytetrafluoroethylene lining, carrying out hydrothermal reaction at 35-140 ℃ for 24h, naturally cooling to room temperature, washing with deionized water to be neutral, and drying at 70 ℃ overnight to obtain mesoporous silicon oxide containing the surfactant;

b. calcining the obtained mesoporous silica containing the surfactant for 6h at 550 ℃ in the air to obtain mesoporous silica without the surfactant;

c. taking 2g of the mesoporous silicon oxide obtained in the step b as a hard template, dispersing the mesoporous silicon oxide into a 50ml centrifuge tube, adding 0.1733-1.7338g of ferric nitrate into the centrifuge tube to be dissolved in a 70-120 ℃ forced air drying oven, adding the ferric nitrate into the template after the nitrate is completely melted into liquid, oscillating the centrifuge tube so that the nitrate solution fully enters the pore channel of the mesoporous silicon oxide, continuously heating and oscillating the mesoporous silicon oxide within the temperature range of 70-100 ℃ for 1-2h, calcining the mesoporous silicon oxide in the air at 500 ℃ for 2-10 h, and controlling the calcining temperature rise rate to be 0.5-2.5 ℃/min;

d. and adding 50-200ml of NaOH solution with the concentration of 2-10M into the calcined product, stirring, and then carrying out centrifugal filtration to remove the mesoporous silica template, thus obtaining the ordered large mesoporous ferric oxide of the tetracycline photocatalytic degradation material.

The hydrothermal reaction temperature in the step a is 40-100 ℃.

In the step c, the dissolving temperature is 70 ℃, the heating rate is 1 ℃/min, and the calcining time is 6 h.

The concentration of the sodium hydroxide solution in step d was 2M.

The material of the invention has the following beneficial technical effects: 1) unique material, mesoporous Fe₂O₃The pore diameter is uniform and 12nm, and the specific surface area is 176m².g^-1In the catalytic reaction process, the large mesoporous aperture is beneficial to the transmission of molecules, and the high specific surface area can beThe reaction provides more active sites. 2) The ordered mesoporous Fe provided by the invention₂O₃Is formed by cubic periodic arrangement of ferric oxide spiral nano wires, and the nano wires are connected with each other with the length of 3-7 nm. 3) The diameter of the nanowires is predominantly 12 nm. The high-specific-surface-area ordered large-mesopore ferric oxide tetracycline catalytic material provided by the invention shows excellent degradation performance in the degradation process of tetracycline, and can realize high-efficiency degradation of tetracycline to a very high degree.

Drawings

FIG. 1 shows the large mesoporous Fe obtained in example 1₂O₃XRD pictures of (1);

FIG. 2 shows the large mesoporous Fe obtained in example 1₂O₃The pore size distribution picture of (a);

FIG. 3 shows the large mesoporous Fe obtained in example 1₂O₃A TEM picture of (4);

FIG. 4 shows the large mesoporous Fe obtained in example 1₂O₃The picture of the photocatalytic degradation performance of the tetracycline.

Detailed Description