CN111822002B - Preparation of cadmium sulfide@hydrothermal carbon composite photocatalytic material and application of cadmium sulfide@hydrothermal carbon composite photocatalytic material in degradation of methylene blue - Google Patents
Preparation of cadmium sulfide@hydrothermal carbon composite photocatalytic material and application of cadmium sulfide@hydrothermal carbon composite photocatalytic material in degradation of methylene blue Download PDFInfo
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- CN111822002B CN111822002B CN202010819770.4A CN202010819770A CN111822002B CN 111822002 B CN111822002 B CN 111822002B CN 202010819770 A CN202010819770 A CN 202010819770A CN 111822002 B CN111822002 B CN 111822002B
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- 239000000463 material Substances 0.000 title claims abstract description 74
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 66
- 229910052980 cadmium sulfide Inorganic materials 0.000 title claims abstract description 65
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 239000002131 composite material Substances 0.000 title claims abstract description 58
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 48
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 229960000907 methylthioninium chloride Drugs 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 230000015556 catabolic process Effects 0.000 title abstract description 13
- 238000006731 degradation reaction Methods 0.000 title abstract description 13
- 239000000243 solution Substances 0.000 claims abstract description 50
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 39
- LHQLJMJLROMYRN-UHFFFAOYSA-L cadmium acetate Chemical compound [Cd+2].CC([O-])=O.CC([O-])=O LHQLJMJLROMYRN-UHFFFAOYSA-L 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229920001661 Chitosan Polymers 0.000 claims abstract description 15
- FRLJSGOEGLARCA-UHFFFAOYSA-N cadmium sulfide Chemical class [S-2].[Cd+2] FRLJSGOEGLARCA-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229920002125 Sokalan® Polymers 0.000 claims abstract description 10
- 239000012670 alkaline solution Substances 0.000 claims abstract description 10
- 239000004584 polyacrylic acid Substances 0.000 claims abstract description 10
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 239000000047 product Substances 0.000 claims description 13
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 238000005286 illumination Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 2
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 14
- 230000000694 effects Effects 0.000 abstract description 11
- 238000000034 method Methods 0.000 abstract description 7
- 238000007146 photocatalysis Methods 0.000 abstract description 5
- 239000002096 quantum dot Substances 0.000 abstract description 5
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 239000003513 alkali Substances 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 238000010382 chemical cross-linking Methods 0.000 abstract 1
- 230000000593 degrading effect Effects 0.000 description 8
- 238000002835 absorbance Methods 0.000 description 5
- 239000011941 photocatalyst Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 238000001308 synthesis method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 230000005418 spin wave Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000002211 ultraviolet spectrum Methods 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 150000004032 porphyrins Chemical class 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
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Abstract
The invention discloses a preparation method of a cadmium sulfide@hydrothermal carbon composite photocatalytic material and an application of the material in degradation of methylene blue, and belongs to the field of photocatalysis. The preparation method of the composite photocatalytic material comprises the following steps: adding cadmium acetate and thiourea into water, adding polyacrylic acid and ammonia water, uniformly stirring, heating at high temperature for reaction, centrifuging and drying to obtain the cadmium sulfide quantum dot. Adding cadmium sulfide quantum dots into acetic acid solution, adding chitosan, stirring thoroughly, performing ultrasonic defoaming, performing alkali bath treatment by using alkaline solution, and reacting in a high-temperature oven to obtain the cadmium sulfide@hydrothermal carbon composite photocatalytic material. The composite photocatalytic material synthesized by the invention has the advantages of good stability, high catalytic activity, quick response, low energy consumption, repeated use and the like, and the composite material with the three-dimensional structure is obtained by adding cadmium sulfide in the process through chemical crosslinking, and the composite photocatalytic material has the characteristics of quick response, low energy consumption, good degradation effect, easy realization of industrial production and the like in the using process.
Description
Technical Field
The invention relates to a preparation method of a novel and simple cadmium sulfide@hydrothermal carbon composite photocatalytic material and an application of the novel and simple cadmium sulfide@hydrothermal carbon composite photocatalytic material in degradation of methylene blue, and belongs to the field of photocatalysis.
Background
The photocatalysis principle is based on the oxidation-reduction capability of the photocatalyst under the condition of illumination, so that the application purposes of pollutant degradation, organic synthesis, nitrogen fixation, hydrogen production and the like are realized. In general, the photocatalytic degradation reaction uses a semiconductor as a catalyst and light as energy to degrade organic matters into carbon dioxide and water. As a high-efficiency and safe environment-friendly environment purification technology, the photocatalysis technology has been accepted by the international academy for improving the indoor air and sewage quality. The principle of photocatalysis is to excite a semiconductor material by light, and to participate in oxidation-reduction reactions by electrons and holes generated on the surface of the semiconductor material. When light with energy greater than or equal to the energy gap is irradiated onto the semiconductor surface, electrons in the valence band thereof will be excited to transit to the conduction band, leaving relatively stable holes in the valence band, thereby forming electron-hole pairs. Due to the large number of defects in the nanomaterial, these defects can trap electrons or holes and prevent recombination of electrons and holes. These trapped electrons and holes diffuse to the surface of the material, respectively, creating a strong redox potential. The photocatalyst has a great variety of catalytic effects including titanium dioxide, zinc oxide, tin oxide, zirconium dioxide, cadmium sulfide and the like, and also part of silver salt, porphyrin and the like, but basically has a disadvantage that the photocatalyst has a loss, namely the photocatalyst itself is consumed before and after the reaction. Therefore, the development of a high-efficiency stable photocatalyst is of great importance.
Disclosure of Invention
The invention aims to provide a novel and simple preparation method of a cadmium sulfide@hydrothermal carbon composite photocatalytic material and application thereof in degrading methylene blue, aiming at the problems of poor catalytic performance, low stability and the like of a catalytic material in the existing photocatalytic system. The invention uses chitosan as raw material, and utilizes a simple method to prepare the composite photocatalytic material with high catalytic activity and good stability. The chitosan used in the invention has wide sources, low cost and easy obtainment, and has good biocompatibility, safety and biodegradability. The synthesis method of the invention is simple and easy to control, and is green and pollution-free.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a preparation method of a cadmium sulfide@hydrothermal carbon composite photocatalytic material comprises the following steps:
(1) Adding cadmium acetate and thiourea into water, uniformly stirring, slowly adding polyacrylic acid and ammonia water, uniformly stirring, heating and reacting for 5-6 h at the high temperature of 150-200 ℃ after the solution is clarified, centrifuging and drying the reaction product to obtain the cadmium sulfide quantum dot; wherein the ratio of the cadmium acetate, the thiourea, the water, the polyacrylic acid and the ammonia water is 0.5-5 mmol:0.5 to 5mmol: 40-100 mL:50 to 500uL:50 to 500uL;
(2) Dispersing the cadmium sulfide quantum dots obtained in the step (1) in acetic acid solution, slowly adding chitosan, stirring until the chitosan is completely dissolved, and then performing ultrasonic defoaming; the method comprises the steps of carrying out a first treatment on the surface of the Wherein the concentration of the acetic acid solution is 1-10% (v/v); the ratio of the cadmium sulfide quantum dots, the chitosan and the acetic acid solution is 0.001-0.05 g:0.1 to 1.5g:15mL;
(3) Immersing the mixture obtained in the step (2) into an alkaline solution, performing alkaline bath treatment by using the alkaline solution, and standing overnight to obtain a formed gel material; wherein the concentration of the alkaline solution is 0.1-10 mol/L;
(4) And (3) reacting the product obtained in the step (3) for 18 hours at the temperature of 90-220 ℃ to obtain the cadmium sulfide@hydrothermal carbon (CdS@Hy-H) composite photocatalytic material.
According to the above technical solution, in the preferred case, in the step (1), the ratio of cadmium acetate, thiourea, water, polyacrylic acid and ammonia water is 1mmol:3mmol:70mL:300uL:300uL.
According to the above technical scheme, in the step (1), the heating reaction temperature is preferably 180 ℃, and the heating reaction time is preferably 6 hours.
According to the above technical scheme, in the step (1), the reaction product is preferably centrifuged with deionized water and ethanol, respectively.
According to the above technical solution, in the step (1), preferably, the drying conditions are: 50 ℃ for 24-48 h.
According to the technical scheme, in the preferred case, in the step (1), the product after the reaction is centrifuged, dried and ground into powder to obtain the cadmium sulfide quantum dot.
According to the above technical solution, in the preferred case, in the step (3), the ratio of the cadmium sulfide quantum dot, chitosan and acetic acid solution is 0.005g:0.5g:15mL.
According to the above technical solution, in the step (2), the volume concentration of the acetic acid solution is preferably 2%.
According to the above technical scheme, in the step (3), the alkaline solution is preferably KOH solution, naOH solution or Na solution 2 CO 3 A solution.
According to the above technical scheme, in the step (3), the concentration of the alkaline solution is preferably 4mol/L.
According to the above technical solution, in the preferred case, in the step (3), the volume ratio of the acetic acid solution to the alkaline solution is 1:10;
according to the above technical scheme, in the step (4), the reaction temperature is preferably 140 ℃.
According to the technical scheme, in the preferred case, in the step (4), the product obtained in the step (3) is reacted for 18 hours at the temperature of 90-220 ℃, then the obtained material is cleaned, dried, uniformly crushed and then is stored in a sealing manner, and the cadmium sulfide@hydrothermal carbon composite photocatalytic material is obtained.
The cadmium sulfide@hydrothermal carbon composite photocatalytic material prepared by the method is applied to photocatalytic degradation of methylene blue, and the cadmium sulfide@hydrothermal carbon composite photocatalytic material, a methylene blue solution and a KOH solution are uniformly mixed in a dark environment to react under an illumination condition. The absorbance of the sample obtained by ultraviolet spectrum test, and thus the degradation efficiency of the methylene blue (the concentration of the degraded methylene blue can be calculated from the absorbance, and the formula is a=lg (1/T) = Kbc, wherein a is absorbance, T is transmittance, K is molar absorptivity, c is the concentration of the degraded methylene blue, in mol/L, b is the thickness of the absorption layer, and in cm).
According to the above-described technical scheme, preferably, the concentration of the methylene blue solution is 1-7 mg/mL, preferably 5mg/mL.
According to the above-mentioned technical scheme, the concentration of the KOH solution is preferably 0.03-0.12 mol/L, and more preferably 0.1mol/L.
According to the technical scheme, the reaction time is preferably 0-90 min, but not 0; the reaction temperature is room temperature, typically 25 ℃.
According to the technical scheme, in a preferred case, the ratio of the cadmium sulfide@hydrothermal carbon composite photocatalytic material, the methylene blue solution and the KOH solution is 0.05-0.15 g:2.0mL:8mL, preferably 0.05g:2.0mL:8mL.
The composite photocatalytic material synthesized by the invention has the advantages of good stability, high catalytic activity, quick response, low energy consumption, repeated use and the like, and belongs to a green synthesis method which is simple and convenient to operate and environment-friendly. The composite photocatalytic material obtained by the invention has wide application prospect in the aspect of wastewater treatment, and can be used as one of photocatalytic degradation materials with the highest application potential in the 21 st century.
The synthesis method of the invention has the following advantages:
(1) The invention adopts the chitosan which is cheap, nontoxic, renewable, biodegradable and good in biocompatibility as the raw material to prepare the composite photocatalytic material, thereby being beneficial to environmental protection;
(2) The preparation method of the composite photocatalytic material is simple to operate, and the reaction conditions are easy to control;
(3) The composite photocatalytic material prepared by the invention has the advantages of quick response, low energy consumption, good effect, easy realization of industrial production and the like in the use process;
(4) The product of the invention provides an effective solution for the problems of poor catalytic performance, low stability and the like of the catalytic material in the existing photocatalytic system.
Drawings
FIG. 1 is a graph showing the effect of different cadmium sulfide amounts on the photocatalytic degradation of methylene blue by a cadmium sulfide@hydrothermal carbon composite photocatalytic material in example 9.
Fig. 2 is a graph showing the effect of photocatalytic degradation of methylene blue by the cadmium sulfide@hydrothermal carbon composite photocatalytic material prepared in example 11 and example 9 at different treatment (reaction) temperatures.
Detailed Description
The invention will be further illustrated by the following examples for better understanding of technical features of the invention, but the scope of the invention is not limited thereto.
Example 1
A preparation method of a cadmium sulfide@hydrothermal carbon composite photocatalytic material comprises the following steps:
(1) Cadmium acetate (0.5 mmol, 1mmol, 2mmol, 3mmol, 4mmol, 5mmol respectively) and thiourea (3 mmol) with different masses are accurately weighed and added into 70mL of deionized water, and uniformly stirred for 10min;
(2) Slowly adding 300uL of polyacrylic acid and 300uL of ammonia water into the product obtained in the step (1), stirring for 10min, transferring to a 100mL reaction kettle after the solution is clarified, and heating for 6h at 180 ℃;
(3) Collecting the product obtained in the step (2), respectively centrifuging for three times in a centrifuge by using deionized water and ethanol, drying at 50 ℃ under vacuum for 24 hours, and grinding the obtained product into powder to obtain cadmium sulfide quantum dots;
(4) Accurately weighing 0.005g of the product (cadmium sulfide quantum dot) obtained in the step (3), slowly adding the product into 15mL of 2% acetic acid solution, and stirring at room temperature until the cadmium sulfide is completely and uniformly dispersed;
(5) Slowly adding 0.5g of chitosan into the product obtained in the step (4), stirring until the chitosan is completely dissolved, and then performing ultrasonic defoaming;
(6) Adding the mixture obtained in the step (5) into 50mL of 4mol/L KOH solution for alkali bath treatment, and standing overnight;
(7) And (3) reacting the product obtained in the step (6) for 18 hours at the temperature of 150 ℃ in a high-temperature oven, and then cleaning, drying and grinding the product into powder, and then sealing and preserving the powder to obtain the cadmium sulfide@hydrothermal carbon composite photocatalytic material.
Example 2
A preparation method of a cadmium sulfide@hydrothermal carbon composite photocatalytic material comprises the following steps:
in the step (1), the dosage of cadmium acetate is maintained at 1mmol, and the dosage of thiourea is respectively 0.5mmol, 1mmol, 2mmol, 4mmol and 5mmol, and the other steps are the same as in the step (1) of the example 1;
step (2), step (3), step (4), step (5), step (6) and step (7) are the same as step (2), step (3), step (4), step (5), step (6) and step (7) in example 1.
Example 3
A preparation method of a cadmium sulfide@hydrothermal carbon composite photocatalytic material comprises the following steps:
the dosage of cadmium acetate in the step (1) is maintained at 1mmol, and the dosage of water is respectively 40mL, 50mL, 60mL, 80mL, 90mL and 100mL, and the steps are the same as the step (1) of the example 1;
step (2), step (3), step (4), step (5), step (6) and step (7) are the same as step (2), step (3), step (4), step (5), step (6) and step (7) in example 1.
Example 4
A preparation method of a cadmium sulfide@hydrothermal carbon composite photocatalytic material comprises the following steps:
the amount of cadmium acetate used in step (1) was maintained at 1mmol, otherwise the same as in step (1) of example 1;
the amounts of polyacrylic acid used in step (2) were 100uL, 150uL, 200uL, 250uL, 350uL, 400uL, 450uL, 500uL, respectively, and the same as in step (2) of example 1;
step (3), step (4), step (5), step (6) and step (7) are the same as step (3), step (4), step (5), step (6) and step (7) in example 1.
Example 5
A preparation method of a cadmium sulfide@hydrothermal carbon composite photocatalytic material comprises the following steps:
the amount of cadmium acetate used in step (1) was maintained at 1mmol, otherwise the same as in step (1) of example 1;
the amount of polyacrylic acid used in the step (2) was maintained at 300uL, and the amounts of ammonia water used were 100uL, 150uL, 200uL, 250uL, 350uL, 400uL, 450uL, 500uL, respectively, in the same manner as in the step (2) of example 1;
step (3), step (4), step (5), step (6) and step (7) are the same as step (3), step (4), step (5), step (6) and step (7) in example 1.
Example 6
A preparation method of a cadmium sulfide@hydrothermal carbon composite photocatalytic material comprises the following steps:
the amount of cadmium acetate used in step (1) was maintained at 1mmol, otherwise the same as in step (1) of example 1;
step (2) and step (3) are the same as step (2) and step (3) of example 1;
the dosage of the cadmium sulfide quantum dots in the step (4) is 0.001g, 0.01g, 0.015g, 0.02g, 0.03g, 0.04g and 0.05g respectively, and the other steps are the same as those in the example 1;
step (5), step (6) and step (7) are the same as step (5), step (6) and step (7) of example 1.
Example 7
A preparation method of a cadmium sulfide@hydrothermal carbon composite photocatalytic material comprises the following steps:
the amount of cadmium acetate used in step (1) was maintained at 1mmol, otherwise the same as in step (1) of example 1;
step (2), step (3) and step (4) are the same as step (2), step (3) and step (4) of example 1;
the chitosan dosage in the step (5) is 0.1g, 0.3g, 0.7g, 0.9g, 1.1g, 1.3g and 1.5g respectively, and the other steps are the same as the step (5) in the example 1;
step (6) and step (7) are the same as step (6) and step (7) of example 1.
Example 8
A preparation method of a cadmium sulfide@hydrothermal carbon composite photocatalytic material comprises the following steps:
the amount of cadmium acetate used in step (1) was maintained at 1mmol, otherwise the same as in step (1) of example 1;
step (2), step (3), step (4), step (5) and step (6) are the same as step (2), step (3), step (4), step (5) and step (6) in example 1;
the reaction temperature in the step (7) was 90℃at 100℃at 110℃at 120℃at 130℃at 140℃at 160℃at 170℃at 180℃at 190℃at 200℃at 210℃at 220℃respectively, and the same procedure as in the step (7) of example 1 was repeated.
Example 9
The application of the cadmium sulfide@hydrothermal carbon composite photocatalytic material in degrading methylene blue comprises the following steps:
(1) Taking 0.05g of cadmium sulfide@hydrothermal carbon composite photocatalytic material (cadmium sulfide@hydrothermal carbon composite photocatalytic material is cadmium sulfide quantum dots prepared by 1mmol of cadmium acetate in the example 1 and cadmium sulfide@hydrothermal carbon composite photocatalytic material prepared by 0.005g of cadmium sulfide quantum dots, the cadmium sulfide quantum dots in the example 6 are respectively 0.001g, 0.01g and 0.02g of prepared cadmium sulfide@hydrothermal carbon composite photocatalytic material), and adding 2.0mL of methylene blue solutions with different concentrations (respectively 1mg/mL,2mg/mL,3mg/mL,4mg/mL,5mg/mL,6mg/mL and 7 mg/mL) into a pressure-resistant bottle;
(2) Adding a magnon into the system in the step (1), and uniformly stirring for 30min in a dark environment;
(3) And (3) reacting the system in the step (2) at room temperature under a xenon lamp (300W), taking one sample every 5min, reacting for 90min, standing for a period of time, and measuring the absorbance of the sample, thereby determining the effect of catalyzing and degrading methylene blue.
Example 10
The application of the cadmium sulfide@hydrothermal carbon composite photocatalytic material in degrading methylene blue comprises the following steps:
maintaining the concentration of the methylene blue solution in the step (1) at 5mg/mL, wherein the concentration of the KOH solution is 0.03mol/L, 0.04mol/L, 0.06mol/L, 0.07mol/L, 0.08mol/L, 0.09mol/L, 0.1mol/L, 0.11mol/L and 0.12mol/L, respectively, in the same manner as in the step (1) of example 9;
step (2) and step (3) are the same as step (2) and step (3) in example 9.
Example 11
The application of the cadmium sulfide@hydrothermal carbon composite photocatalytic material in degrading methylene blue comprises the following steps:
(1) Taking 0.05g of prepared cadmium sulfide@hydrothermal carbon composite photocatalytic material (the reaction temperature is 130 ℃ and the reaction temperature is 140 ℃ in the example 8, respectively), adding 2.0mL of methylene blue solutions with different concentrations (1 mg/mL,2mg/mL,3mg/mL,4mg/mL,5mg/mL,6mg/mL,7 mg/mL) and 8mL of KOH solution with 0.05mol/L into a pressure-resistant bottle;
(2) Adding a magnon into the system in the step (1), and uniformly stirring for 30min in a dark environment;
(3) And (3) reacting the system in the step (2) at room temperature under a xenon lamp (300W), taking one sample every 5min, reacting for 90min, testing the absorbance of the solution at each sampling time point through ultraviolet spectrum, and determining the effect of catalyzing and degrading methylene blue.
Example 12
The application of the cadmium sulfide@hydrothermal carbon composite photocatalytic material in degrading methylene blue comprises the following steps:
maintaining the concentration of the methylene blue solution in the step (1) at 5mg/mL, wherein the concentration of the KOH solution is 0.03mol/L, 0.04mol/L, 0.06mol/L, 0.07mol/L, 0.08mol/L, 0.09mol/L, 0.1mol/L, 0.11mol/L, 0.12mol/L, respectively, in the same manner as in the step (1) of example 11;
step (2) and step (3) are the same as step (2) and step (3) in example 11.
FIG. 1 is a graph showing the effect of the cadmium sulfide@hydrothermal carbon composite photocatalytic material synthesized by different cadmium sulfide dosages in example 9 on the catalytic degradation of methylene blue in various time periods, wherein the cadmium sulfide content of the cadmium sulfide@hydrothermal carbon composite photocatalytic material in example 6 is 0.001g (0.2%), 0.01g (2.0%), 0.02g (4.0%) respectively, the cadmium sulfide dosage of the cadmium sulfide@hydrothermal carbon composite photocatalytic material prepared by 1mmol of cadmium acetate in example 1 is 0.005g (1.0%), the concentration of methylene blue solution is 5mg/mL, and the reaction temperature in the preparation process of the cadmium sulfide@hydrothermal carbon composite photocatalytic material is 150 ℃. The fold lines shown in the figure are respectively catalytic degradation conditions corresponding to 0min, 5min, 15min, 30min, 45min, 60min and 90min of cadmium sulfide@hydrothermal carbon composite photocatalytic material prepared from cadmium sulfide quantum dots with contents of 0.001g, 0.005g, 0.01g and 0.02g from top to bottom. Experimental results show that the dosage of cadmium sulfide has a great influence on the catalytic strength of the material, and when the content of cadmium sulfide is 0.005g and the reaction temperature is 150, the maximum degradation value is reached in 80 minutes. The photocatalytic effect gradually decreases when the cadmium sulfide dosage is gradually increased, which indicates that the material achieves the best photocatalytic effect when the cadmium sulfide dosage is 0.005g.
FIG. 2 is a graph showing the effect of the catalytic degradation of methylene blue in various time periods of the cadmium sulfide@hydrothermal carbon composite photocatalytic material prepared by different treatment (reaction) temperatures in example 11 and example 9, wherein the treatment (reaction) temperature of the cadmium sulfide@hydrothermal carbon composite photocatalytic material in example 8 is 130 ℃ and 140 ℃, the treatment temperature of the cadmium acetate 1mmol in example 1 is 150 ℃, the concentration of the methylene blue solution is 5mg/mL, and the dosage of the cadmium sulfide quantum dots in the preparation of the cadmium sulfide@hydrothermal carbon composite photocatalytic material is 0.005g. The fold line is shown in the figure, the temperature is 130 ℃, 140 ℃ and 150 ℃ from top to bottom in sequence, and the catalytic degradation conditions of the cadmium sulfide@hydrothermal carbon composite photocatalytic material prepared by treatment are respectively corresponding to 0min, 5min, 15min, 25min, 30min, 35min, 40min, 45min, 50min, 55min, 60min, 75min and 90 min. Experimental results show that the material prepared at different temperatures has different effects on photocatalytic degradation of methylene blue, and when the treatment temperature reaches 140 ℃, the material is basically degraded completely in 90 minutes. When the temperature of the treatment material is continuously increased, the effect of the corresponding material for catalyzing and degrading the methylene blue is gradually reduced, which indicates that the material achieves better catalytic and degradation effect when the temperature of the treatment material is 140 ℃.
The foregoing examples are illustrative of part of the practice of the invention, but the invention is not limited to the embodiments, and any other changes, substitutions, combinations, and simplifications that depart from the spirit and principles of the invention are intended to be equivalent thereto and are within the scope of the invention.
Claims (8)
1. The application of the cadmium sulfide@hydrothermal carbon composite photocatalytic material in photocatalytic degradation of methylene blue is characterized in that the preparation method of the cadmium sulfide@hydrothermal carbon composite photocatalytic material comprises the following steps:
(1) Adding cadmium acetate and thiourea into water, uniformly stirring, adding polyacrylic acid and ammonia water, uniformly stirring, heating at 150-200 ℃ for reaction for 5-6 hours, centrifuging and drying the reaction product to obtain cadmium sulfide quantum dots;
wherein the ratio of the cadmium acetate, the thiourea, the water, the polyacrylic acid and the ammonia water is 0.5-5 mmol: 0.5-5 mmol: 40-100 mL: 50-500 uL: 50-500 uL;
(2) Dispersing the cadmium sulfide quantum dots obtained in the step (1) in acetic acid solution, adding chitosan, stirring until the chitosan is completely dissolved, and then performing ultrasonic defoaming;
wherein the volume concentration of the acetic acid solution is 1-10%; the ratio of the cadmium sulfide quantum dots to the chitosan to the acetic acid solution is 0.001-0.05 g: 0.1-1.5 g:15mL;
(3) Adding the mixture obtained in the step (2) into an alkaline solution for alkaline bath treatment, and standing overnight;
wherein the concentration of the alkaline solution is 0.1-10 mol/L;
(4) And (3) reacting the product obtained in the step (3) at the temperature of 90-220 ℃ for 18h to obtain the cadmium sulfide@hydrothermal carbon composite photocatalytic material.
2. The use according to claim 1, wherein in step (1) the ratio of cadmium acetate, thiourea, water, polyacrylic acid and ammonia is 1mmol:3mmol:70mL:300uL:300uL.
3. The use according to claim 1, wherein in step (1) the heating reaction is carried out at a temperature of 180 ℃ for a time of 6h.
4. The use according to claim 1, wherein in step (1) the reaction products are centrifuged separately with deionized water and ethanol; the drying conditions are as follows: 50. and (3) at the temperature of 24-48 h.
5. The use according to claim 1, wherein in step (2) the ratio of cadmium sulfide quantum dots, chitosan to acetic acid solution is 0.005g:0.5g:15 mL; the volume concentration of the acetic acid solution was 2%.
6. The use according to claim 1, wherein in step (3), the alkaline solution is a KOH solution, naOH solution or Na solution 2 CO 3 A solution.
7. The use according to claim 1, wherein the cadmium sulfide @ hydrothermal carbon composite photocatalytic material is mixed with methylene blue solution and KOH solution uniformly in a dark environment and then reacted under light conditions.
8. The use according to claim 7, wherein the concentration of the methylene blue solution is 1-7 mg/ml; the concentration of the KOH solution is 0.03-0.12 mol/L; the reaction time under illumination is 0-90 min, but not 0.
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