CN109158125B - Graphite carbon nitride quantum dot modified zinc oxide catalytic material and preparation method thereof - Google Patents
Graphite carbon nitride quantum dot modified zinc oxide catalytic material and preparation method thereof Download PDFInfo
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- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 39
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- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical class [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 title claims abstract 10
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- 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
- B01J27/24—Nitrogen compounds
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Abstract
The invention relates to a graphite carbon nitride quantum dot modified zinc oxide catalytic material and a preparation method thereofg‑C3N4A quantum dot dispersion solution; then mixing the zinc oxide raw material with g-C3N4And mixing the quantum dot dispersion solution, ball-milling and drying to obtain the graphite carbon nitride quantum dot modified zinc oxide catalytic material. According to the invention, a special device and a solvent are not needed, the graphite carbon nitride quantum dots are prepared by a mechanical ultrasonic oscillation method, a mechanical ball milling method is directly utilized, the formation of the graphite carbon nitride quantum dot modified zinc oxide powder is promoted by means of mechanochemistry, and then the graphite carbon nitride quantum dot modified zinc oxide visible light catalytic material is prepared by a forced air drying method, so that the preparation process is simplified, the experiment cost is reduced, the preparation process is environment-friendly, the industrial production can be realized, and an effective path is provided for preparing other powder materials on a large scale.
Description
Technical Field
The invention relates to a graphite carbon nitride quantum dot modified zinc oxide catalytic material and a preparation method thereof, belonging to the field of photocatalysis.
Background
The zinc oxide mineral has wide distribution, rich content and low price in nature, and has good application prospect in the fields of photocatalysis, coating fillers, chemical pigments and the like due to the special electronic structure and excellent photoelectric property. Although zinc oxide minerals are excellent in optical performance, low in price and wide in industrial application, zinc oxide is wide in forbidden band width, only can absorb ultraviolet light in sunlight, and photogenerated carriers generated by photoexcitation are easy to recombine, so that the application of zinc oxide in the photocatalysis industry is limited. Therefore, it is necessary to improve the spectral response range and photocatalytic activity of zinc oxide by modification.
Semiconductor compounding is an effective means for widening the spectral response range of zinc oxide catalytic materials and reducing the recombination of photon-generated carriers, and is widely applied to the fields of sewage treatment, environmental protection and the like. Among a plurality of narrow band-based semiconductors, graphite phase carbon nitride (g-C)3N4) The forbidden band width is 2.74 eV, the self can absorb visible light to form a photon-generated carrier, and the good catalytic property is shown; all in oneIn addition, the method has the advantages of good stability, acid and alkali resistance, excellent electrochemical properties and the like, and has a plurality of sources and abundant reserves, thereby being paid more and more attention by researchers. The graphite-phase carbon nitride modification can obviously improve the photocatalytic activity and spectral response range of the zinc oxide, improve the photocatalytic efficiency and promote the application in the fields of environmental protection, sewage treatment, air purification and the like.
At present, a plurality of methods for obtaining the modified zinc oxide photocatalytic material exist, but the preparation process is complex, the industrial scale production is not easy to realize, the production price is high, and the large-scale production and application are not easy, so that the method for obtaining the modified zinc oxide photocatalytic material which is simple and easy to realize the industrial production is very necessary.
Disclosure of Invention
The invention aims to realize graphite carbon nitride quantum dot modified zinc oxide powder by a mechanical ball milling method on the basis of preparing graphite carbon nitride quantum dots by using a mechanical stirring and ultrasonic oscillation method, broaden the spectral response range of zinc oxide and improve the photocatalytic activity, thereby providing a graphite carbon nitride quantum dot modified zinc oxide catalytic material which has simple process and low cost and is easy to industrially prepare and a preparation method thereof.
In order to solve the technical problems, the technical scheme of the invention is as follows:
a preparation method of a graphite carbon nitride quantum dot modified zinc oxide catalytic material comprises the following steps:
s1, mixing g-C3N4Adding the powder into the mixed solution of deionized water and alcohol, ultrasonic dispersing for 20-40min (usually 25-35 min), stirring for 20-40min (usually 25-35 min) to obtain g-C3N4A dispersion liquid;
wherein the volume ratio of the deionized water to the alcohol is 96: 4-98: 2, and 0.3-2g g-C is added into each 100mL of mixed solution3N4Powder, preferably per 100mLAdding 0.6-1.7g g-C into the mixed solution3N4Powder;
aligning the g-C with a mechanical shear under ultrasonic oscillation3N4Shearing the dispersion liquid for 5-6 h to obtain g-C with uniformly dispersed solution3N4A solution; then, the g-C was centrifuged3N4The solution is centrifuged to obtain g-C3N4A quantum dot dispersion solution;
s2, mixing the zinc oxide raw material with g-C obtained in S13N4And mixing the quantum dot dispersion solution, ball-milling and drying to obtain the graphite carbon nitride quantum dot modified zinc oxide catalytic material.
In S1, g-C3N4The preparation method of the powder comprises the following steps: putting the nitrogen-containing compound into a muffle furnace, heating to 500-600 ℃, preferably at a heating rate of 3-5 ℃/min, keeping the temperature for 1.5-7h, generally for 2-6h, preferably for 2.5-5h, cooling to obtain g-C3N4And (3) powder.
The nitrogen-containing compound is at least one of melamine, urea and thiourea.
In S1, the alcohol is at least one of methanol, ethanol, and propanol.
In S1, in the shearing process, the rotating speed of the mechanical shearing machine is 2000-6000 r/min, generally 3000-5000 r/min, and preferably 3500-4500 r/min; in the centrifugal separation process, the rotating speed of the centrifugal machine is 10000-12000 r/min, generally 11000-12000 r/min.
In S2, 1-10mL of C was mixed in per 1g of zinc oxide raw material3N4The quantum dot dispersion solution is preferably prepared by mixing 2-8mL of C per 1g of zinc oxide raw material3N4And (3) a quantum dot dispersion solution.
In S2, the zinc oxide raw material is zinc oxide powder having a particle size of 0.5 to 3 μm. Furthermore, the zinc oxide raw material can also adopt zinc oxide mineral powder, and can also prepare a target product, and the cost of the raw material can be reduced.
The graphite carbon nitride quantum dots not only have the performance of bulk graphite carbon nitride, but also have special quantum size effect, show more excellent performance, have better enhancement effect than carbon nitride laminar materials, and show good industrial application prospect. The zinc oxide mineral catalytic material with wide spectral response range and high catalytic efficiency is obtained by using zinc oxide mineral powder as a raw material, water as a solvent and graphite-phase carbon nitride quantum dots as a reinforcing material, and has the advantages of simple preparation process, environmental protection, low preparation cost, producibility and good industrial application prospect.
In S2, in the ball milling process, the selected grinding beads include large grinding beads and small grinding beads, the number ratio of the large grinding beads to the small grinding beads is 1:3-5, preferably, the diameter ratio of the large grinding beads to the small grinding beads is 2:1, and the grinding beads are preferably zirconia grinding beads. The grading of the large grinding beads and the small grinding beads improves the ball milling effect.
In S2, the ball milling is carried out in a bidirectional operation mode, namely, the ball milling is carried out for 30-40 min in a forward direction and is stopped for 3-5 min, then the ball milling is carried out for 30-40 min in a reverse direction and is stopped for 3-5 min, and the operation is repeated in this way, wherein the total operation time is 3-5 h. Preferably, the ball milling speed is 300-500 r/min.
Further, in S2, ball milling was performed using a horizontal ball mill.
Further, in S2, after the ball milling is completed, drying is performed by air blow drying.
Based on the same inventive concept, the invention also provides a graphite carbon nitride quantum dot modified zinc oxide catalytic material prepared by the preparation method.
The technical conception of the invention is as follows: the special structure and photoelectric property of the graphite carbon nitride quantum dot are utilized to widen the spectral response range of the zinc oxide and improve the photocatalytic activity. In addition, the zinc oxide powder is directly used as a raw material, water is used as a solvent, a simple mechanical ball milling method is adopted to realize uniform mixing of the zinc oxide powder and the graphite carbon nitride quantum dots, and a heterojunction with a 'synergistic effect' is constructed through a mechanochemical action, so that the graphite carbon nitride quantum dot modified zinc oxide catalytic material with excellent photocatalytic performance is prepared.
The invention uses zinc oxide powder and nitrogen-containing compounds as raw materials, uses water as a solvent, uses a simple mechanical oscillation method to prepare the graphite carbon nitride quantum dots, and relies on a mechanical ball milling method to obtain the graphite carbon nitride quantum dot modified zinc oxide visible light catalytic material with wide spectral response range and high catalytic activity.
The principle of the invention is as follows: the graphite carbon nitride quantum dots and the modified zinc oxide visible light catalytic material thereof are obtained by a simple mechanical ball milling method without a special device and an organic solvent. The principle is that the mechanochemical action formed by mechanical ball milling is utilized to form the graphite carbon nitride quantum dot modified zinc oxide catalytic material, on one hand, the mechanical ball milling is utilized to reduce the particle size of a zinc oxide raw material, and simultaneously, the graphite carbon nitride quantum dot and the zinc oxide raw material are uniformly mixed to obtain the composite catalytic material with better performance. On the other hand, the graphite carbon nitride quantum dots are used for modifying the zinc oxide powder raw material, the special structure and the excellent performance of the graphite carbon nitride quantum dots are used for widening the spectral response range of the zinc oxide raw material, increasing the light quantum yield of the zinc oxide catalytic material, and depending on the level of a fault formed between the graphite carbon nitride quantum dots and the zinc oxide, the separation of a photon-generated carrier is accelerated, and the photocatalytic activity of the zinc oxide is improved.
The invention has the following characteristics: the uniformly dispersed graphite carbon nitride quantum dot aqueous solution is prepared by using a mechanical shearing method, and then the graphite carbon nitride quantum dot modified zinc oxide powder raw material is synthesized by using a mechanical ball milling method, so that other additives and solvents are not needed, the preparation process is simple, the cost is low, the preparation process is environment-friendly, and the large-scale production is easy. In addition, the method adopts graphite carbon nitride quantum dots to modify the zinc oxide raw material, so as to obtain the natural sunlight response zinc oxide catalytic material with more excellent performance, and the graphite carbon nitride quantum dots modified zinc oxide catalytic material can be applied to the environmental protection fields of sewage treatment, photodegradation water, air purification and the like.
Compared with the prior art, the invention has the advantages that: according to the invention, a special device and a solvent are not needed, the graphite carbon nitride quantum dots are prepared by a mechanical ultrasonic oscillation method, a mechanical ball milling method is directly utilized, the graphite carbon nitride quantum dots are promoted to modify a zinc oxide raw material by means of mechanochemistry to form a composite system with uniform dispersion and firm combination, and then the graphite carbon nitride quantum dots modified zinc oxide visible light catalytic material is prepared by a forced air drying method, so that the preparation process is simplified, the experiment cost is reduced, the preparation process is environment-friendly, the industrial production can be realized, and an effective path is provided for preparing other powder materials on a large scale.
Drawings
FIG. 1 shows g-C obtained in example 13N4Quantum dot modified ZnO catalytic material (g-C)3N4 QDs/ZnO) and other related materials under ultraviolet light irradiation. C is the concentration of the organic dye in the solution, C0Is the initial concentration of organic dye in solution.
FIG. 2 is g-C obtained in example 23N4XRD (X-ray diffraction) pattern of the quantum dot modified ZnO catalytic material.
FIG. 3 is g-C obtained in example 33N4Quantum dot modified ZnO catalytic material (g-C)3N4 QDs/ZnO) and other related materials under visible light irradiation.
In FIGS. 1 and 3, the Blank group refers to the natural degradation of the organic dye under light irradiation, the ZnO group refers to the degradation of the organic dye by pure zinc oxide under light irradiation, and g-C3N4 the/ZnO group is g-C3N4g-C in the case of the modified ZnO catalytic material degrading organic dyes under light irradiation3N4The QDs/ZnO group is g-C3N4And (3) degrading the organic dye by the quantum dot modified ZnO catalytic material under the irradiation of light.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
In this example, g-C3N4The preparation method of the quantum dot modified ZnO catalytic material comprises the following steps:
(1) putting urea in a muffle furnace, heating at a heating rate of 4 ℃/min to 500 ℃, then preserving heat for 4 h, naturally cooling, and grinding by a mortar to obtain g-C3N4The powder of (4).
(2) Weighing 5 g of the product prepared in step (1)g-C3N4Adding the powder into 1000 mL of deionized water and methanol mixed solution (volume ratio is 98: 2), ultrasonically dispersing for 20min, and then stirring for 40 min; obtaining g-C3N4A dispersion liquid;
(3) under ultrasonic oscillation, the g-C obtained in the step (2) is sheared by a mechanical shearing machine with the rotating speed of 2000 r/min3N4Shearing the dispersion for 5h to obtain g-C with uniformly dispersed solution3N4A solution;
(4) centrifuging with a high speed centrifuge at 10000 r/min to obtain g-C3N4And (3) a quantum dot dispersion solution.
(5) 25 g of ZnO powder raw material (the particle size is 3 mu m) is put into a ball milling pot, and 50 mLg-C is added3N4And (3) dispersing the solution by the quantum dots, and simultaneously putting the prepared grinding beads into a ball milling tank, wherein the grading of the balls is that the ratio of large balls to small balls is 1:3, the radius of the large balls is 20 mm, and the radius of the small balls is 10 mm.
(6) And (3) placing the ball milling tank on a horizontal ball mill at the rotating speed of 300 r/min, setting the ball milling to rotate forwards for 30 min, then stop for 5min, and then rotate backwards for 40min, and controlling the whole ball milling time to be 3 h. And drying the uniformly mixed powder to obtain the composite photocatalyst. And the photocatalytic performance of the material is tested, as shown in the attached figure 1.
Fig. 1 shows the photocatalytic performance of the related photocatalytic material under ultraviolet light. As can be seen from the figure, g-C3N4The modification of the quantum dots can greatly improve the photocatalytic performance of ZnO powder, and the use time of photocatalytic degradation of the dye with the same concentration is reduced by half. In addition, g-C3N4Ratio g-C of quantum dot modified sample3N4The modified sample showed better photocatalytic performance.
Example 2
In this example, g-C3N4The preparation method of the quantum dot modified ZnO catalytic material comprises the following steps:
(1) putting thiourea in a muffle furnace, heating at the heating rate of 3 ℃/min to 600 ℃, then preserving heat for 5 hours, naturally cooling, and grinding by a mortar to obtain g-C3N4The powder of (4);
(2) weighing 10 g of g-C prepared in the step (1)3N4Adding the powder into 1000 mL of a mixed solution (volume ratio is 96: 4) of deionized water and ethanol, carrying out ultrasonic dispersion for 40min, and then stirring for 40 min; obtaining g-C3N4A dispersion liquid;
(3) under ultrasonic oscillation, the g-C obtained in the step (2) is sheared by a mechanical shearing machine with the rotating speed of 6000 r/min3N4Shearing the dispersion liquid for 6 hours to obtain g-C with uniformly dispersed solution3N4A solution;
(4) centrifuging by a high-speed centrifuge with the rotating speed of 12000 r/min to obtain g-C3N4A quantum dot dispersion solution;
(5) 30 g of ZnO raw material (the particle size is 1 mu m) is put into a ball milling pot, and 200 mLg-C is added3N4And (3) dispersing the solution by the quantum dots, and simultaneously putting the prepared grinding beads into a ball milling tank, wherein the grading of the balls is that the ratio of large balls to small balls is 1:4, the radius of the large balls is 20 mm, and the radius of the small balls is 10 mm.
(6) And (3) placing the ball milling tank on a horizontal ball mill at the rotating speed of 500 r/min, setting the ball milling to rotate forwards for 40min, then stop for 3 min, and then rotate backwards for 30 min, wherein the whole ball milling time is 5 h. And drying the uniformly mixed powder to obtain the composite photocatalyst. Figure 3 is an XRD of the composite photocatalyst.
FIG. 2 shows g-C3N4XRD pattern of quantum dot modified ZnO catalytic material. As can be seen from the figure, the samples before and after the modification of the graphite carbon nitride quantum dots are represented by zinc oxide with a wurtzite structure, but a new diffraction peak is found at 2 theta =27.4 degrees in the modified samples, which corresponds to g-C3N4(002) crystal plane diffraction peak of (a). This result demonstrates that the obtained sample contains g-C3N4。
Example 3
In this example, g-C3N4The preparation method of the quantum dot modified ZnO catalytic material comprises the following steps:
(1) placing melamine in a muffle furnace, heating at a heating rate of 5 deg.C/min to 550 deg.CThen preserving the heat for 3 hours, naturally cooling, and grinding by a mortar to obtain g-C3N4The powder of (4).
(2) Weighing 8 g of g-C prepared in the step (1)3N4Adding the powder into 800 mL of deionized water and propanol mixed solution (volume ratio is 97: 3), ultrasonically dispersing for 20min, and then stirring for 20 min; obtaining g-C3N4A dispersion liquid;
(3) under ultrasonic oscillation, using a mechanical shearing machine with the rotating speed of 5000 r/min to perform shearing on the g-C obtained in the step (2)3N4Shearing the dispersion liquid for 6 hours to obtain g-C with uniformly dispersed solution3N4A solution;
(4) centrifuging by a high-speed centrifuge with the rotating speed of 11000 r/min to obtain g-C3N4And (3) a quantum dot dispersion solution.
(5) 50 g of ZnO powder raw material (with the particle size of 0.5 mu m) is put into a ball milling pot, and 150 mLg-C is added3N4And (3) dispersing the solution by the quantum dots, and simultaneously putting the prepared grinding beads into a ball milling tank, wherein the grading of the balls is that the ratio of large balls to small balls is 1:5, the radius of the large balls is 20 mm, and the radius of the small balls is 10 mm.
(6) And (3) placing the ball milling tank on a horizontal ball mill at the rotating speed of 400 r/min, setting the ball milling to firstly rotate forwards for 35min, then stop for 4 min, and then rotate backwards for 35min, wherein the whole ball milling time is 4 h. And drying the uniformly mixed powder to obtain the composite photocatalyst. Figure 3 shows the cycle performance of the composite photocatalyst.
Fig. 3 shows the photocatalytic performance of the catalytic material under sunlight. As can be seen from the figure, compared with ZnO powder, the performance of the modified sample under sunlight is greatly improved, the photocatalytic degradation capability of the sample is doubled, wherein g-C3N4The quantum dot modified sample shows better photocatalytic performance, and the photocatalytic activity is improved by about 15%. The result shows that the graphite carbon nitride quantum dots can effectively improve the visible light catalytic activity of the zinc oxide powder and are expected to be applied in the actual industry.
In conclusion, the method uses the zinc oxide powder and the graphite carbon nitride as raw materials and water as a solvent to prepare the graphite carbon nitride quantum dot modified zinc oxide catalytic material with high visible light response and catalytic activity.
The foregoing examples are set forth to illustrate the present invention more clearly and are not to be construed as limiting the scope of the invention, which is defined in the appended claims to which the invention pertains, as modified in all equivalent forms, by those skilled in the art after reading the present invention.
Claims (6)
1. A preparation method of a graphite carbon nitride quantum dot modified zinc oxide catalytic material is characterized by comprising the following steps:
s1, mixing g-C3N4Adding the powder into the mixed solution of deionized water and alcohol, ultrasonically dispersing for 20-40min, and stirring for 20-40min to obtain g-C3N4A dispersion liquid;
wherein the volume ratio of the deionized water to the alcohol is 96: 4-98: 2, and 0.3-2g g-C is added into each 100mL of mixed solution3N4Powder; the alcohol is at least one of methanol, ethanol and propanol;
aligning the g-C with a mechanical shear under ultrasonic oscillation3N4Shearing the dispersion liquid for 5-6 h to obtain g-C with uniformly dispersed solution3N4A solution; then, the g-C was centrifuged3N4The solution is centrifuged to obtain g-C3N4A quantum dot dispersion solution;
s2, mixing the zinc oxide raw material with g-C obtained in S13N4Mixing the quantum dot dispersion solution, ball-milling and drying to obtain a graphite carbon nitride quantum dot modified zinc oxide catalytic material;
wherein the zinc oxide raw material is zinc oxide powder with the particle size of 0.5-3 mu m; 1-10mL of g-C is mixed into 1g of zinc oxide raw material3N4A quantum dot dispersion solution;
in the ball milling process, selected grinding beads comprise large grinding beads and small grinding beads, the number ratio of the large grinding beads to the small grinding beads is 1:3-5, and the diameter ratio of the large grinding beads to the small grinding beads is 2: 1;
the ball milling adopts a bidirectional operation mode, namely the ball milling is carried out for 30-40 min in a forward direction and is stopped for 3-5 min, then the ball milling is carried out for 30-40 min in a reverse direction and is stopped for 3-5 min, and the operation is repeated in such a way, the total operation time is 3-5 h, and the rotating speed is 300-500 r/min.
2. The method for preparing the graphite carbon nitride quantum dot modified zinc oxide catalytic material as claimed in claim 1, wherein in S1, g-C3N4The preparation method of the powder comprises the following steps: placing the nitrogen-containing compound in a muffle furnace, heating to 500-600 ℃, the heating rate is 3-5 ℃/min, keeping the temperature for 1.5-7h, and cooling to obtain g-C3N4And (3) powder.
3. The preparation method of the graphite carbon nitride quantum dot modified zinc oxide catalytic material as claimed in claim 2, wherein the nitrogen-containing compound is at least one of melamine, urea and thiourea.
4. The preparation method of the graphite carbon nitride quantum dot modified zinc oxide catalytic material as claimed in claim 1, wherein in S1, the rotation speed of a mechanical shearing machine is 2000-6000 r/min in the shearing process; in the centrifugal separation process, the rotating speed of the centrifugal machine is 10000-12000 r/min.
5. The method of claim 1, wherein in S2, the grinding beads are zirconia grinding beads.
6. The graphite carbon nitride quantum dot modified zinc oxide catalytic material is characterized by being prepared by the preparation method of any one of claims 1 to 5.
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| CN107649107A (en) * | 2017-09-25 | 2018-02-02 | 兰州大学 | A kind of quantum dot/TiO2The preparation method and applications of composite |
| CN108212191A (en) * | 2018-01-15 | 2018-06-29 | 吉林师范大学 | A kind of preparation method of zinc oxide nitridation carbon quantum dot composite construction visible light catalyst |
| CN108355696A (en) * | 2018-02-05 | 2018-08-03 | 中国科学院深圳先进技术研究院 | Black phosphorus/g-C3N4Composite visible light catalysis material and its preparation method and application |
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| CN107649107A (en) * | 2017-09-25 | 2018-02-02 | 兰州大学 | A kind of quantum dot/TiO2The preparation method and applications of composite |
| CN108212191A (en) * | 2018-01-15 | 2018-06-29 | 吉林师范大学 | A kind of preparation method of zinc oxide nitridation carbon quantum dot composite construction visible light catalyst |
| CN108355696A (en) * | 2018-02-05 | 2018-08-03 | 中国科学院深圳先进技术研究院 | Black phosphorus/g-C3N4Composite visible light catalysis material and its preparation method and application |
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