CN114669289A - Synthesis method of carbon quantum dot/ZnO composite photocatalyst - Google Patents
Synthesis method of carbon quantum dot/ZnO composite photocatalyst Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 39
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 27
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
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- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Inorganic materials [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 1
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Abstract
A synthetic method of a carbon quantum dot/ZnO composite photocatalyst comprises the following steps: adding the air-dried sugarcane peel into distilled water, and carrying out ultrasonic crushing; transferring all the solution into a reaction container, placing the reaction container into an oven for reaction, transferring the solution in the reaction container into a dialysis bag, and dialyzing to obtain a carbon quantum dot solution; adding 2-methylimidazole into distilled water, magnetically stirring, and adding Zn (NO) dropwise3)2·6H2O water solution, continuing magnetic stirring, ultrasonic treating, centrifuging, and addingWashing with anhydrous methanol for more than 5 times, and drying the solid collected after washing in an oven to obtain ZIF-8; heating ZIF-8, calcining and pyrolyzing to obtain a ZnO nano material; dispersing the ZnO nano material in a carbon quantum dot solution, adding absolute ethyl alcohol and distilled water, carrying out magnetic stirring reaction, centrifuging and washing in sequence, and finally placing in an oven for drying to obtain the carbon quantum dot/ZnO composite photocatalyst. The carbon quantum dots are uniformly distributed on the surfaces of the ZnO nanoparticles, so that the dispersibility of the ZnO nanoparticles is improved, and the increase of the specific surface area of the catalyst is facilitated.
Description
Technical Field
The invention relates to the technical field of preparation of photocatalytic materials, in particular to a synthesis method of a carbon quantum dot/ZnO composite photocatalyst.
Background
In the rapid development of the modern day, environmental pollution, particularly water pollution, is a difficult problem which people must face, and the rapid development of the industries such as chemical industry, textile industry, dye industry, pharmaceutical industry, leather industry and the like causes a large amount of harmful substances in water, thereby seriously damaging the living environment of aquatic organisms in human beings and oceans. How to treat the negative effects brought by the extensive economic development mode and adopt an effective method to treat the water body pollution is a problem which people need to solve urgently.
ZnO is an important semiconductor material, and nano ZnO materials are widely applied in many technical fields. Because ZnO has the advantages of high surface activity, stable chemical property, rich content in nature and the like, the ZnO has potential application value in the field of photocatalysis. However, the rapid recombination of photogenerated electrons and holes reduces the photocatalytic efficiency of ZnO, and the wide band gap property makes it almost non-responsive to visible light, which limits further applications of ZnO. Researchers have widened the photoresponse range of ZnO by modifying ZnO, and inhibited the recombination of photo-generated electrons and holes, thereby being beneficial to improving the photocatalytic performance of ZnO. As Wang J et al consider that oxygen vacancies are a self-doping method without introducing any impurity element, high concentration of oxygen vacancies are successfully introduced into ZnO, the increase of oxygen vacancies leads to the reduction of band gap, the visible light absorption of ZnO is increased, and the photocurrent response of ZnO under the irradiation of visible light is enhanced (Wang J, et al, ACS Applied Materials)&Interfaces,2012,4(8), 4024-. The liquid phase precipitation method is used for synthesizing the rare earth doped nano zinc oxide microspheres of Sin J C and the like, pure ZnO andcommercial TiO2Compared with the prior art, the material has red shift in absorption spectrum, shows better photocatalytic activity, and shows good photocatalytic activity when phenol is degraded under visible light irradiation (Sin J C, et al, Ceramics International,2014,40(4), 5431-5440.). Rajbongshi B M et al synthesized Co-doped ZnO nanorods by hydrothermal method, performed visible light catalytic degradation on methylene blue and phenol, red-shifted the absorption spectrum, and showed high photocatalytic activity (Rajbongshi B M, et al, Materials Science and Engineering: B,2014,182, 21-28.).
In addition, carbon quantum dots, which are a novel carbon material, have rapidly been studied for their excellent optical properties, good chemical inertness, and the like. The carbon quantum dots have no dependence on light excitation wavelength, have rapid photoproduction electron transfer capability and functionalized surface controllability, and can well improve the photocatalytic performance of the material. How to simply and efficiently prepare a composite having good visible light catalytic performance and formed by combining carbon quantum dots and a nano ZnO material is an important subject of current research.
Disclosure of Invention
In order to solve the technical problems in the prior art, the invention provides a method for synthesizing a carbon quantum dot/ZnO composite photocatalyst, the carbon quantum dots of the carbon quantum dot/ZnO composite photocatalyst synthesized by the method are uniformly distributed on the surface of ZnO nanoparticles, so that the dispersibility of the ZnO nanoparticles is improved, and the specific surface area of the catalyst is increased; more active sites are provided, and the photocatalytic effect of the carbon quantum dot/ZnO composite photocatalyst is obviously higher than that of a single ZnO catalyst material.
In order to achieve the purpose, the invention provides a synthesis method of a carbon quantum dot/ZnO composite photocatalyst, which comprises the following steps:
(1) adding the air-dried sugarcane peels into distilled water, and carrying out ultrasonic crushing to obtain a suspension;
(2) transferring all the suspension in the step (1) into a reaction container, placing the reaction container in an oven to react for 4-8h at the temperature of 180-220 ℃, naturally cooling the reaction container to room temperature after the reaction is finished, and transferring the solution in the reaction container into a dialysis bag for dialysis for 24-48h to obtain a carbon quantum dot solution;
(3) adding 2-methylimidazole into distilled water, magnetically stirring, and adding Zn (NO) dropwise3)2·6H2Performing magnetic stirring on the O aqueous solution for 5-10min, performing ultrasonic treatment for 0.5-1h, centrifuging the ultrasonic treated solution, washing with anhydrous methanol for more than 5 times, and drying the washed solid in an oven at 60-75 ℃ for 6-8h to obtain ZIF-8;
(4) heating the ZIF-8 obtained in the step (3) to 500-600 ℃ at the heating rate of 4-6 ℃/min, calcining for 3-5h, and pyrolyzing to obtain a white solid product which is a ZnO nano material;
(5) dispersing the ZnO nano material obtained in the step (4) in the carbon quantum dot solution obtained in the step (2), adding absolute ethyl alcohol and distilled water, and magnetically stirring for 3-5 hours;
(6) and (3) reacting the solution obtained in the step (5) after magnetic stirring at the temperature of 120-160 ℃ for 2-8h, cooling to normal temperature after the reaction is finished, centrifuging and washing the cooled product in sequence, and finally drying in an oven at the temperature of 50-80 ℃ for 6-8h to obtain the carbon quantum dot/ZnO composite photocatalyst.
As a further preferable technical scheme of the invention, in the step (1), the amount of the corresponding distilled water is 40mL per 25-200mg of the air-dried sugarcane peel, and the time for ultrasonic crushing is 30-90 min.
As a further preferred embodiment of the present invention, in the step (3), the amount of distilled water used is 90mL based on the amount of 2.000g of 2-methylimidazole, and the concentration is 50 to 200 mg. multidot.mL-1Zn (NO) of3)2·6H2The amount of the O aqueous solution was 10 mL.
In a further preferred embodiment of the present invention, in step (5), based on the amount of the ZnO nanomaterial of 0.075g, the amount of the corresponding carbon quantum dot solution is 5 to 20mL, the amount of the anhydrous ethanol is 6mL, and the amount of the distilled water is 10 mL.
As a further preferable embodiment of the present invention, the reaction vessel in the step (1) is a stainless autoclave lined with polytetrafluoroethylene.
As a further preferable technical scheme of the invention, in the step (4), the temperature of ZIF-8 is raised to 500-600 ℃ at the temperature raising speed of 4-6 ℃/min through a muffle furnace, and then the calcination is carried out for 3-5 h.
As a further preferable technical scheme of the invention, in the step (6), the solution obtained after magnetic stirring is reacted for 2-8h at the temperature of 120-160 ℃ by a high-pressure reaction kettle.
The synthesis method of the carbon quantum dot/ZnO composite photocatalyst can achieve the following beneficial effects by adopting the technical scheme:
1) according to the method, the air-dried sugarcane peel is used as the precursor to prepare the carbon quantum dots, so that the resource utilization of biomass is well realized, and the production cost of the material is reduced;
2) the synthetic method is simple and easy to operate, and has good repeatability;
3) according to the carbon quantum dot/ZnO composite photocatalyst synthesized by the method, the carbon quantum dots are uniformly distributed on the surfaces of the ZnO nanoparticles, so that the dispersibility of the ZnO nanoparticles is improved, and the specific surface area of the catalyst is increased; more active sites are provided, and the photocatalytic effect of the carbon quantum dot/ZnO composite photocatalyst is obviously higher than that of a single ZnO catalyst material;
4) according to the carbon quantum dot/ZnO composite photocatalyst synthesized by the invention, the addition of the carbon quantum dot can inhibit the recombination of ZnO photo-generated electrons and holes, and the up-conversion effect of the carbon quantum dot is utilized to widen the photoresponse range, so that the performance of the carbon quantum dot/ZnO composite photocatalyst is greatly improved.
Drawings
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
FIG. 1 is a High Resolution Transmission Electron Microscope (HRTEM) photograph of the product of example 1;
FIG. 2 is an X-ray diffraction pattern (XRD) of the product of example 1;
FIG. 3 is an infrared spectrum of a carbon quantum dot/ZnO composite;
FIG. 4 is a comparison graph of the photocatalytic performance of the carbon quantum dot/ZnO composite on rhodamine B.
The objects, features and advantages of the present invention will be further explained with reference to the accompanying drawings.
Detailed Description
The invention will be further described with reference to the drawings and the detailed description. In the preferred embodiments, the terms "upper", "lower", "left", "right", "middle" and "a" are used for descriptive purposes only and are not intended to limit the scope of the present invention, and the relative relationships thereof may be changed or modified without substantial change in technical content.
Example 1
Weighing 25mg of air-dried sugarcane peel in 40mL of distilled water, and carrying out ultrasonic crushing for 60min to obtain a clear solution;
transferring all the clear solution into a stainless steel high-pressure autoclave with a polytetrafluoroethylene lining (the volume filling rate is 80%), placing the high-pressure autoclave in an oven for reacting for 4 hours at 200 ℃, naturally cooling to room temperature, transferring the filtered solution into a dialysis bag for dialysis for 48 hours to obtain a carbon quantum dot solution;
accurately weighing 2.000g of 2-methylimidazole in 90mL of distilled water, magnetically stirring to obtain a uniform solution, and dropwise adding 10mL of 75 mg/mL-1Zn(NO3)2·6H2Magnetically stirring an O aqueous solution for 10min, then performing ultrasonic treatment for 1h, centrifuging the ultrasonic solution, washing the solution for more than 5 times by using anhydrous methanol, and drying the collected solid in a drying oven at 70 ℃ for 8h to obtain ZIF-8;
putting ZIF-8 into a muffle furnace, heating to 550 ℃ at a speed of 5 ℃/min, calcining for 4h, and pyrolyzing to obtain a white solid product ZnO nano material;
accurately weighing 0.075g of the prepared ZnO nano material, dispersing the ZnO nano material in 12.5mL of carbon quantum dot solution, sequentially adding 6mL of absolute ethyl alcohol and 10mL of distilled water, magnetically stirring for 4 hours, transferring the solution into a high-pressure reaction kettle after the magnetic stirring is finished, reacting for 4 hours at 140 ℃, sequentially centrifuging and washing the cooled product, and finally drying in a 70 ℃ drying oven for 8 hours to finally prepare the carbon quantum dot/ZnO composite photocatalyst.
The product prepared in this example was examined by scanning with an electron microscope, X-ray diffraction and infrared spectroscopy, as shown in FIGS. 1-3.
Fig. 1 is an HRTEM of a carbon quantum dot/ZnO composite, and it can be seen from the figure that carbon quantum dots with the size of 2-5nm are uniformly distributed on the surface of ZnO nanoparticles, and small-sized carbon quantum dots are effectively loaded on the surface of ZnO nanoparticles, which is helpful for inhibiting the agglomeration of ZnO nanoparticles, increasing the specific surface area of ZnO nanoparticles, providing more active sites, and hopefully obtaining better photocatalytic effect. FIG. 2 is an XRD pattern of a carbon quantum dot/ZnO composite, and diffraction peaks of the composite at 31.73 °, 34.36 °, 36.21 °, 47.47 °, 56.53 °, 62.75 °, 66.29 °, 67.85 ° and 68.99 ° corresponding to crystal planes of ZnO (100), (002), (101), (102), (110), (103), (200), (112) and (201), respectively, are consistent with those of hexagonal wurtzite-type ZnO (JCPDS No.36-1451), indicating that ZnO in the product has a hexagonal wurtzite-type structure. No significant diffraction peak is found in the range of 20-30 degrees, which may cause that the XRD does not detect the diffraction peak of carbon because the quantity of the carbon quantum dots is too small. To confirm the presence of the carbon quantum dots, the FT-IR spectrum of the carbon quantum dot/ZnO composite was studied, as shown in fig. 3. At wave number of 430cm in FT-IR chart-1The diffraction peak corresponds to the characteristic absorption peak of Zn-O, 2850cm-1In the presence of weak-CH2Characteristic absorption peak, 1260cm-1C-O characteristic absorption peaks appear at the positions, the existence of the carbon quantum dots in the composite is proved, and the shift of the characteristic peaks indicates that the ZnO and the carbon quantum dots have interaction.
To examine the adsorbability of the product prepared according to the invention, the following formula was 10 mg.L-1Rhodamine B (RhB, purchased from national drug group chemical agents Co., Ltd.) is used as a photocatalytic degradation target, a 300W xenon lamp is used as a light source (lambda is more than 420nm by matching with a filter), and the catalytic degradation effect of the carbon quantum dot/ZnO composite is explored. FIG. 4 is a comparison graph of the photocatalytic performance of the purchased ZnO powder (denoted as ZnO) and the carbon quantum dot/ZnO composite (denoted as CQDs/ZnO) on rhodamine B, and the graph shows that the degradation of rhodamine B by the two catalysts shows a rapid and gradual change trend; when the lamp is illuminated for 20min, the degradation rate of the purchased ZnO powder to rhodamine B is 42 percent,the degradation rate of the carbon quantum dot/ZnO compound to rhodamine B is over 95 percent; when the light is irradiated for 30min, the degradation rates of the purchased ZnO powder and the carbon quantum dot/ZnO composite to rhodamine B are 43 percent and 99 percent respectively. The results show that the photocatalytic effect of the carbon quantum dot/ZnO composite is obviously higher than that of the purchased ZnO powder.
Examples 2 to 33
The carbon quantum dot/ZnO composite photocatalyst was prepared according to the preparation process described in example 1, using the amount of the carbon quantum dot solution in table 1 and other experimental conditions.
TABLE 1 comparison of the various experimental conditions and the performance of the photocatalytic degradation of RhB in examples 2-33
According to the experimental data in table 1, it can be seen that:
(1) when the amount of the air-dried sugarcane peel is low (such as 25mg), the solvothermal time is short (such as 4h), and the carbon quantum dot solution can be synthesized and has lower concentration Zn (NO)3)2·6H2O solution (50 mg. mL)-1) The degradation rate of the prepared carbon quantum dot/ZnO composite photocatalyst in photocatalysis RhB is not less than 95%.
(2) When the amount of the air-dried sugarcane peel is more (such as 200mg), longer solvothermal time (such as 8h) is needed, and Zn (NO) participating in compounding is added3)2·6H2The concentration of O solution is also high (e.g. 200 mg. mL)-1) The degradation rate of the prepared carbon quantum dot/ZnO composite photocatalyst in photocatalysis RhB is slightly increased to 98%.
In conclusion, in order to degrade more rhodamine B, the amount of air-dried sugarcane peel needs to be increased, the solvothermal time needs to be increased, and Zn (NO) with higher concentration needs to be added3)2·6H2And (4) O solution.
Although specific embodiments of the present invention have been described above, it will be appreciated by those skilled in the art that these are merely examples and that many variations or modifications may be made to the embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims.
Claims (7)
1. A synthetic method of a carbon quantum dot/ZnO composite photocatalyst is characterized by comprising the following steps:
(1) adding the air-dried sugarcane peels into distilled water, and carrying out ultrasonic crushing to obtain a suspension;
(2) transferring all the suspension in the step (1) into a reaction container, placing the reaction container in an oven to react for 4-8h at the temperature of 180-220 ℃, naturally cooling to room temperature after the reaction is finished, and transferring the solution in the reaction container into a dialysis bag to dialyze for 24-48h to obtain a carbon quantum dot solution;
(3) adding 2-methylimidazole into distilled water, magnetically stirring, and adding Zn (NO) dropwise3)2·6H2Performing magnetic stirring on the O aqueous solution for 5-10min, performing ultrasonic treatment for 0.5-1h, centrifuging the ultrasonic solution, washing with anhydrous methanol for more than 5 times, and drying the washed solid in an oven at 60-75 ℃ for 6-8h to obtain ZIF-8;
(4) heating the ZIF-8 obtained in the step (3) to 500-600 ℃ at the heating rate of 4-6 ℃/min, calcining for 3-5h, and pyrolyzing to obtain a white solid product which is a ZnO nano material;
(5) dispersing the ZnO nano material obtained in the step (4) in the carbon quantum dot solution obtained in the step (2), adding absolute ethyl alcohol and distilled water, and magnetically stirring for 3-5 hours;
(6) and (3) reacting the solution obtained in the step (5) after magnetic stirring at the temperature of 120-160 ℃ for 2-8h, cooling to normal temperature after the reaction is finished, centrifuging and washing the cooled product in sequence, and finally drying in an oven at the temperature of 50-80 ℃ for 6-8h to obtain the carbon quantum dot/ZnO composite photocatalyst.
2. The method for synthesizing the carbon quantum dot/ZnO composite photocatalyst as claimed in claim 1, wherein in the step (1), the amount of distilled water is 40mL for every 25-200mg of air-dried sugarcane peel, and the time for ultrasonic crushing is 30-90 min.
3. The method for synthesizing a carbon quantum dot/ZnO composite photocatalyst as claimed in claim 2, wherein in the step (3), the amount of the corresponding distilled water is 90mL and the concentration is 50-200 mg-mL based on the amount of 2.000g of 2-methylimidazole-1Zn (NO) of3)2·6H2The amount of the O aqueous solution was 10 mL.
4. The method for synthesizing the carbon quantum dot/ZnO composite photocatalyst according to claim 3, wherein in the step (5), based on the amount of the ZnO nanomaterial of 0.075g, the amount of the corresponding carbon quantum dot solution is 5-20mL, the amount of the absolute ethanol is 6mL, and the amount of the distilled water is 10 mL.
5. The method for synthesizing the carbon quantum dot/ZnO composite photocatalyst as claimed in claim 1, wherein the reaction vessel in the step (1) is a stainless steel autoclave lined with polytetrafluoroethylene.
6. The method for synthesizing the carbon quantum dot/ZnO composite photocatalyst as claimed in claim 1, wherein in the step (4), the ZIF-8 is heated to 600 ℃ at a heating rate of 4-6 ℃/min by a muffle furnace, and then calcined for 3-5 h.
7. The method for synthesizing the carbon quantum dot/ZnO composite photocatalyst as claimed in any one of claims 1 to 6, wherein in the step (6), the solution obtained after magnetic stirring is reacted for 2-8h at 160 ℃ of 120 ℃ by a high-pressure reaction kettle.
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| CN116139867B (en) * | 2023-02-20 | 2024-04-05 | 常州大学 | MOFs derived ZnO@CDs@Co 3 O 4 Composite photocatalyst, preparation method and application thereof |
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