阅读说明：本技术 一种可见光响应型纳米复合微粒催化剂及其制备方法 (Visible light response type nano composite particle catalyst and preparation method thereof ) 是由 余晓皎 刘宗斌 杨朦 郭碧琦 赵晨 张健 钮金芬 赵洁 余中 姚秉华 于 2020-12-24 设计创作，主要内容包括：本发明公开了一种可见光响应型纳米复合微粒催化剂及其制备方法,向Cu-2O微粒中加入蒸馏水和SnCl-2后超声,抽滤,干燥,其中Cu-2O微粒和SnCl-2的质量比为1～5：1。本发明催化剂,制备方法简单,成本低,可以更好地利用太阳光,具有较好的稳定性,其光生电子-空穴复合几率低,光催化活性高。(The invention discloses a visible light response type nano composite particle catalyst and a preparation method thereof, and aims to provide a Cu-based composite particle catalyst 2 Adding distilled water and SnCl into O particles 2 Post-ultrasonic treatment, suction filtration and drying, wherein Cu 2 Fine particles of O and SnCl 2 The mass ratio of (A) to (B) is 1-5: 1. the catalyst has the advantages of simple preparation method, low cost, better utilization of sunlight, better stability, low probability of photo-induced electron-hole recombination and high photocatalytic activity.)

1. A visible light response type nano composite particle catalyst is characterized in that the catalyst is Cu₂Adding distilled water and SnCl into O particles₂Then carrying out ultrasonic treatment, carrying out suction filtration and drying to obtain the product.

2. The visible-light-responsive nanocomposite particulate catalyst according to claim 1, wherein Cu₂Fine particles of O and SnCl₂The mass ratio of (A) to (B) is 1-5: 1.

3. a preparation method of a visible light response type nano composite particle catalyst is characterized in that the catalyst is prepared by adding Cu₂Adding distilled water and SnCl into O particles₂Then carrying out ultrasonic treatment, suction filtration, washing and drying to obtain the visible light response type nano composite particle catalyst.

4. The method for preparing a visible-light-responsive nanocomposite particulate catalyst according to claim 3, wherein Cu is added₂Fine particles of O and SnCl₂The mass ratio of (A) to (B) is 1-5: 1.

5. the method for preparing a visible-light-responsive nanocomposite particulate catalyst according to claim 3, wherein the ultrasonic treatment time is 4 to 8 min.

6. The method for preparing a visible-light-responsive nanocomposite particulate catalyst according to claim 3 or 4, wherein Cu is added₂The preparation method of the O particles comprises the following steps: mixing Cu (CH)₃COO)₂Solution, NaOH solution and C₆H₁₂O₆Uniformly mixing the solution, pouring the solution into a reaction kettle, reacting in a forced air drying oven, cooling, filtering, washing and drying to obtain Cu₂And (4) fine O particles.

7. The method for preparing a visible-light-responsive nanocomposite particulate catalyst according to claim 6, wherein Cu (CH)₃COO)₂Solution, NaOH solution and C₆H₁₂O₆The molar ratio of the solution is 4: 16: 1.

8. the method for preparing a visible-light-responsive nanocomposite particulate catalyst according to claim 7, wherein Cu (CH)₃COO)₂The concentration of the solution is 0.1-0.3 mol/L, the concentration of NaOH solution is 1.0-1.4 mol/L, C₆H₁₂O₆The concentration of the solution is 0.1-0.3 mol/L.

9. The method for preparing a visible-light-responsive nanocomposite particulate catalyst according to claim 6, wherein the temperature of the reaction in the forced air drying oven is 120 ℃ to 150 ℃ and the reaction time is 6h to 10 h.

Technical Field

The invention belongs to the field of environmental pollution treatment technology and nano material preparation, and particularly relates to a visible light response type nano composite particle catalyst and a preparation method thereof.

Background

With the development of society, more and more environmental problems emerge, wherein water pollution becomes a primary problem due to scarcity of water resources. However, the conventional water treatment method has certain limitations, and the photocatalytic oxidation technology can overcome the defects of high energy consumption, secondary pollution and the like, so that the method is widely researched. The wide bandgap semiconductor photocatalyst has strong dependence on ultraviolet light and low absorption and utilization efficiency on visible light. Therefore, cuprous oxide has been studied intensively as the most advantageous photocatalyst at the present stage because it can use a large amount of visible light, is inexpensive, and is easy to prepare.

Disclosure of Invention

The invention aims to provide a visible light response type nano composite particle catalyst which can better utilize sunlight and has good stability.

The invention also aims to provide a preparation method of the visible light response type nano composite particle catalyst.

The first technical proposal disclosed by the invention is that a visible light response type nano composite particle catalyst is prepared by adding Cu₂Adding distilled water and SnCl into O particles₂Then carrying out ultrasonic treatment, carrying out suction filtration and drying to obtain the product.

The technical scheme of the invention also has the following technical characteristics:

further, Cu₂Fine particles of O and SnCl₂The mass ratio of (A) to (B) is 1-5: 1.

the second technical proposal disclosed by the invention is a preparation method of a visible light response type nano composite particle catalyst, which is to add Cu₂Adding distilled water and SnCl into O particles₂Then carrying out ultrasonic treatment, suction filtration, washing and drying to obtain the visible light response type nano composite particle catalyst.

The technical scheme of the invention also has the following technical characteristics:

further, Cu₂Fine particles of O and SnCl₂The mass ratio of (A) to (B) is 1-5: 1.

furthermore, the ultrasonic time is 4-8 min.

Further, Cu₂The preparation method of the O particles comprises the following steps: mixing Cu (CH)₃COO)₂Solution, NaOH solution and C₆H₁₂O₆Uniformly mixing the solution, pouring the solution into a reaction kettle, reacting in a forced air drying oven, cooling, filtering, washing and drying to obtain Cu₂And (4) fine O particles.

Further, Cu (CH)₃COO)₂Solution, NaOH solution and C₆H₁₂O₆The molar ratio of the solution is 4: 16: 1.

further, Cu (CH)₃COO)₂The concentration of the solution is 0.1-0.3 mol/L, the concentration of NaOH solution is 1.0-1.4 mol/L, C₆H₁₂O₆The concentration of the solution is 0.1-0.3 mol/L.

Furthermore, the reaction temperature of the forced air drying oven is 120-150 ℃, and the reaction time is 6-10 h.

Compared with the prior art, the invention can obtain the following technical effects:

the visible light response type nano composite particle catalyst has the advantages of simple preparation method, low cost, better utilization of sunlight, better stability, low probability of photo-induced electron-hole recombination and high photocatalytic activity.

Drawings

The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention and not to limit the invention. In the drawings:

FIG. 1 is an XRD pattern of catalysts prepared in examples 1-4 of the present invention;

FIG. 2 is an EDS analysis chart of the catalyst prepared in example 4 of the present invention;

FIG. 3 is a graph showing the degradation rate of norfloxacin in the catalysts prepared in examples 1 to 4 of the present invention;

FIG. 4 is a graph showing the degradation rate of levofloxacin by the catalysts prepared in examples 1 to 4 of the present invention.

Detailed Description

The following embodiments are described in detail with reference to the accompanying drawings, so that how to implement the technical features of the present invention to solve the technical problems and achieve the technical effects can be fully understood and implemented.

The invention discloses a visible light response type nano composite particle catalyst, which is Cu₂Adding distilled water and SnCl into O particles₂Then carrying out ultrasonic treatment, carrying out suction filtration and drying to obtain the product. Wherein Cu₂Fine particles of O and SnCl₂The mass ratio of (A) to (B) is 1-5: 1.

the preparation method comprises the following steps:

step 1, adding Cu (CH)₃COO)₂Solution, NaOH solution and C₆H₁₂O₆Uniformly mixing the solution, pouring the mixture into a reaction kettle, reacting in a forced air drying oven at the temperature of 120-150 ℃ for 6-10 h, cooling, filtering, washing and drying to obtain Cu₂Fine particles of O;

wherein Cu (CH)₃COO)₂Solution, NaOH solution and C₆H₁₂O₆The molar ratio of the solution is 4: 16: 1;

wherein Cu (CH)₃COO)₂The concentration of the solution is 0.1-0.3 mol/L, the concentration of NaOH solution is 1.0-1.4 mol/L, C₆H₁₂O₆The concentration of the solution is 0.1-0.3 mol/L;

step 2, adding Cu₂Adding distilled water and SnCl into O particles₂Rear ultrasoundAnd (4) sounding for 4-8 min, performing suction filtration, washing and drying to obtain the visible light response type nano composite particle catalyst. Wherein Cu₂Fine particles of O and SnCl₂The mass ratio of (A) to (B) is 1-5: 1.

the visible light response type nano composite particle catalyst has simple preparation method and low cost; the absorption boundary of the sample is increased from 580nm to 600nm through a UV-Vis test, and the red shift of the absorption boundary enables the sample to utilize more visible light, so that sunlight is better utilized; the prepared sample has better stability, and the photocurrent test shows that the photocurrent response intensity of the composite particles is improved by 1.2 times, which shows that the probability of photoproduction electron-hole recombination is reduced, and the prepared sample has higher photocatalytic activity.

Example 1

Separately, 0.3mol/L Cu (CH) was prepared₃COO)₂Solution, 0.2mol/L C₆H₁₂O₆The solution and 1.0mol/L NaOH solution were sequentially sampled, and 11mL of Cu (CH)₃COO)₂、4mL C₆H₁₂O₆Adding 13mL of NaOH solution into a beaker, uniformly stirring, pouring into a reaction kettle, placing in a forced air drying oven, reacting for 8 hours at 150 ℃, cooling, performing suction filtration, washing and drying to obtain Cu₂Fine particles of O;

then 100mg of Cu prepared as described above was taken₂Adding distilled water and 20mg SnCl into the fine O particles₂Performing ultrasonic treatment for 5min, performing suction filtration and drying to obtain Sn-Cu₂O composite particles, namely a visible light response type nanometer composite particle catalyst. The sample obtained is denoted a.

Referring to FIG. 1, Sn-Cu was prepared₂The OXRD pattern shows that the sample is pure and has no other impurity peaks, which indicates that Sn-Cu₂The preparation of the O sample was successful.

Example 2

To the beaker was added 24mL of 0.2mol/L Cu (CH) in sequence₃COO)₂Solution, 16mL of 1.2mol/L NaOH solution and 4mL of 0.3mol/L C₆H₁₂O₆The solution is evenly stirred and poured into a reaction kettle, and is placed into a forced air drying oven to react for 8 hours at the temperature of 150 ℃, and then the solution is cooled, filtered, washed and dried to obtain Cu₂Fine particles of O;

then 100mg of Cu prepared as described above was taken₂Adding distilled water and 30mg SnCl into the fine O particles₂Performing ultrasonic treatment for 5min, performing suction filtration and drying to obtain Sn-Cu₂O composite particles, namely a visible light response type nanometer composite particle catalyst. The resulting sample was designated B.

Referring to FIG. 1, Sn-Cu was prepared₂The XRD pattern of the O composite particles shows that the sample is pure and has no other impurity peaks, which indicates that Sn-Cu₂The preparation of the O sample was successful.

Example 3

16mL of 0.1mol/L Cu (CH) was added to the beaker₃COO)₂Solution, 5mL of 1.2mol/L NaOH solution and 4mL of 0.1mol/L C₆H₁₂O₆The solution is evenly stirred and poured into a reaction kettle, and is placed into a forced air drying oven to react for 8 hours at the temperature of 150 ℃, and then the solution is cooled, filtered, washed and dried to obtain Cu₂And (4) fine O particles.

Then 100mg of Cu prepared as described above was taken₂Adding distilled water and SnCl 40mg into fine O particles₂Performing ultrasonic treatment for 5min, performing suction filtration and drying to obtain Sn-Cu₂O composite particles, namely a visible light response type nanometer composite particle catalyst. The resulting sample was designated C.

Referring to FIG. 1, Sn-Cu was prepared₂The XRD pattern of the O composite particles shows that the sample is pure and has no other impurity peaks, which indicates that Sn-Cu₂The preparation of the O sample was successful.

Example 4

To the beaker was added 12mL of 0.2mol/L Cu (CH)₃COO)₂Solution, 4mL of 1.0mol/L NaOH solution and 4mL of 0.2mol/L C₆H₁₂O₆The solution is evenly stirred and poured into a reaction kettle, and is placed into a forced air drying oven to react for 8 hours at the temperature of 150 ℃, and then the solution is cooled, filtered, washed and dried to obtain Cu₂Fine particles of O;

then 100mg of Cu prepared as described above was taken₂Adding distilled water and SnCl 35mg into fine O particles₂Performing ultrasonic treatment for 5min, performing suction filtration and drying to obtain Sn-Cu₂O composite particles, namely a visible light response type nanometer composite particle catalyst. The resulting sample was designated G.

Referring to FIG. 2, Sn-Cu was prepared₂O compositeThe EDS chart of the particles shows that Sn is actually present in the prepared sample, and the method of the invention can lead Cu₂O modification to successfully prepare Sn-Cu₂And (3) O composite particles.

To test Sn-Cu prepared in accordance with examples of the invention₂The O composite photocatalyst is used for treating antibiotic wastewater, and Norfloxacin (NOR) and Levofloxacin (LEV) are respectively used as simulated pollutants, and the photocatalytic effect is tested.

The results are shown in FIGS. 3 and 4. In FIG. 3, the degradation rate of samples A, B, C and G on NOR can reach 65% -80%; in fig. 4, the sample has a LEV degradation rate of 60% to 70%. The catalyst of the invention has higher photocatalytic activity.

Example 5

Separately, 0.3mol/L Cu (CH) was prepared₃COO)₂Solution, 0.2mol/L C₆H₁₂O₆The solution and 1.0mol/L NaOH solution were sequentially sampled, and 11mL of Cu (CH)₃COO)₂、4mL C₆H₁₂O₆Adding 13mL of NaOH solution into a beaker, uniformly stirring, pouring into a reaction kettle, placing in a forced air drying oven, reacting for 10 hours at 120 ℃, cooling, performing suction filtration, washing and drying to obtain Cu₂Fine particles of O;

then 100mg of Cu prepared as described above was taken₂Adding distilled water and 100mg SnCl into fine O particles₂Performing ultrasonic treatment for 8min, performing suction filtration and drying to obtain Sn-Cu₂O composite particles, namely a visible light response type nanometer composite particle catalyst.

Example 6

To the beaker was added 24mL of 0.2mol/L Cu (CH) in sequence₃COO)₂Solution, 16mL of 1.2mol/L NaOH solution and 4mL of 0.3mol/L C₆H₁₂O₆The solution is evenly stirred and poured into a reaction kettle, and is placed into a forced air drying oven to react for 7 hours at the temperature of 130 ℃, and then the solution is cooled, filtered, washed and dried to obtain Cu₂Fine particles of O;

then 100mg of Cu prepared as described above was taken₂Adding distilled water and SnCl 50mg into fine O particles₂Performing ultrasonic treatment for 4min, filtering, and drying to obtain Sn-Cu₂O composite particles, i.e. visible light responsive nanocomposite particlesA particulate catalyst.

Example 7

16mL of 0.1mol/L Cu (CH) was added to the beaker₃COO)₂Solution, 5mL of 1.2mol/L NaOH solution and 4mL of 0.1mol/L C₆H₁₂O₆The solution is evenly stirred and poured into a reaction kettle, and is placed in a forced air drying oven to react for 6 hours at the temperature of 140 ℃, and then the solution is cooled, filtered, washed and dried to obtain Cu₂And (4) fine O particles.

Then 100mg of Cu prepared as described above was taken₂Adding distilled water and SnCl 25mg into fine O particles₂Performing ultrasonic treatment for 6min, performing suction filtration and drying to obtain Sn-Cu₂O composite particles, namely a visible light response type nanometer composite particle catalyst.

While the foregoing description shows and describes several preferred embodiments of the invention, it is to be understood, as noted above, that the invention is not limited to the forms disclosed herein, but is not to be construed as excluding other embodiments and is capable of use in various other combinations, modifications, and environments and is capable of changes within the scope of the inventive concept as expressed herein, commensurate with the above teachings, or the skill or knowledge of the relevant art. And that modifications and variations may be effected by those skilled in the art without departing from the spirit and scope of the invention as defined by the appended claims.