CN113275022A - Water-soluble zinc-cadmium-sulfur quantum dot photocatalyst and room-temperature preparation method - Google Patents
Water-soluble zinc-cadmium-sulfur quantum dot photocatalyst and room-temperature preparation method Download PDFInfo
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- 239000002096 quantum dot Substances 0.000 title claims abstract description 124
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 88
- IGUWUAGBIVHKDA-UHFFFAOYSA-N cadmium;sulfanylidenezinc Chemical compound [Zn].[Cd]=S IGUWUAGBIVHKDA-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052793 cadmium Inorganic materials 0.000 claims abstract description 27
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 27
- 239000011701 zinc Substances 0.000 claims abstract description 27
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims abstract description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 24
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 claims abstract description 24
- 229940012189 methyl orange Drugs 0.000 claims abstract description 24
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229940043267 rhodamine b Drugs 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 150000001768 cations Chemical class 0.000 claims abstract description 19
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 18
- 238000005286 illumination Methods 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 230000001699 photocatalysis Effects 0.000 claims abstract description 10
- -1 sulfhydryl compound Chemical class 0.000 claims abstract description 8
- 239000011859 microparticle Substances 0.000 claims abstract description 6
- 150000001450 anions Chemical class 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims abstract description 5
- 239000004065 semiconductor Substances 0.000 claims abstract description 5
- 229910052979 sodium sulfide Inorganic materials 0.000 claims abstract description 5
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims abstract 3
- 239000002243 precursor Substances 0.000 claims description 42
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 13
- LHQLJMJLROMYRN-UHFFFAOYSA-L cadmium acetate Chemical compound [Cd+2].CC([O-])=O.CC([O-])=O LHQLJMJLROMYRN-UHFFFAOYSA-L 0.000 claims description 13
- 239000004246 zinc acetate Substances 0.000 claims description 13
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 12
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 claims description 12
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- YKYOUMDCQGMQQO-UHFFFAOYSA-L cadmium dichloride Chemical compound Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 6
- ZZTCCAPMZLDHFM-UHFFFAOYSA-N ammonium thioglycolate Chemical compound [NH4+].[O-]C(=O)CS ZZTCCAPMZLDHFM-UHFFFAOYSA-N 0.000 claims description 3
- 229940075861 ammonium thioglycolate Drugs 0.000 claims description 3
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Inorganic materials [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 claims description 3
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical compound OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 20
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 15
- 239000011593 sulfur Substances 0.000 abstract description 15
- 229910052717 sulfur Inorganic materials 0.000 abstract description 15
- 230000015556 catabolic process Effects 0.000 abstract description 12
- 238000006731 degradation reaction Methods 0.000 abstract description 12
- 238000002156 mixing Methods 0.000 abstract description 8
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 description 40
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 238000010586 diagram Methods 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- 229940048181 sodium sulfide nonahydrate Drugs 0.000 description 8
- WMDLZMCDBSJMTM-UHFFFAOYSA-M sodium;sulfanide;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Na+].[SH-] WMDLZMCDBSJMTM-UHFFFAOYSA-M 0.000 description 8
- 230000000593 degrading effect Effects 0.000 description 5
- 239000000975 dye Substances 0.000 description 4
- CEKJAYFBQARQNG-UHFFFAOYSA-N cadmium zinc Chemical compound [Zn].[Cd] CEKJAYFBQARQNG-UHFFFAOYSA-N 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000002957 persistent organic pollutant Substances 0.000 description 3
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229940079101 sodium sulfide Drugs 0.000 description 2
- ZGHLCBJZQLNUAZ-UHFFFAOYSA-N sodium sulfide nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Na+].[Na+].[S-2] ZGHLCBJZQLNUAZ-UHFFFAOYSA-N 0.000 description 2
- 238000003911 water pollution Methods 0.000 description 2
- 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 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 229910001566 austenite Inorganic materials 0.000 description 1
- 231100000693 bioaccumulation Toxicity 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000013590 bulk material Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
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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
- 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
-
- 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
-
- 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
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- 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
- C02F2101/38—Organic compounds containing nitrogen
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- 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 Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
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Abstract
The invention relates to a water-soluble zinc-cadmium-sulfur quantum dot photocatalyst and a preparation method thereof, belonging to the technical field of water-soluble quantum dot photocatalysts. The water-soluble zinc-cadmium-sulfur quantum dot photocatalyst is powdery microparticles, the size of the microparticles is 2-5 nanometers, and the molar ratio of cations (zinc and cadmium) to anions (sulfur) is 1: 1; the material has the characteristics of semiconductor quantum dots, and emits visible light under the irradiation of ultraviolet light; and the rhodamine B and the methyl orange are degraded in a photocatalytic manner under the illumination condition. The preparation method comprises the following steps: mixing a zinc source, a cadmium source, a sulfhydryl compound and water, adding sodium hydroxide or potassium hydroxide until the solution is clear, adding sodium sulfide, adjusting the pH value by using 3-mercaptopropionic acid, and stirring at room temperature to obtain the water-soluble quantum dot photocatalyst. 1 mg of the photocatalyst is used for photocatalytic degradation of 1 mg of rhodamine or methyl orange, and the highest degradation efficiency can reach 99% within 10 minutes. The preparation method can be quickly synthesized at room temperature and is suitable for large-scale production.
Description
Technical Field
The invention belongs to the technical field of water-soluble quantum dot photocatalysts, and particularly relates to a water-soluble zinc-cadmium-sulfur quantum dot photocatalyst and a room-temperature preparation method thereof.
Background
A large amount of sewage is discharged into rivers every year all over the world to cause water pollution, wherein the natural degradation speed of artificial azo organic dyes such as rhodamine B, methyl orange, methylene blue and the like is very slow and has bio-accumulation, the health of human beings and offspring is seriously threatened, and the water pollution control is very urgent. Photocatalytic degradation utilizes sunlight to excite a semiconductor to generate electrons and holes, and organic pollutants are oxidized into H on the surface of the semiconductor2O and CO2And compared with biological and physical removal technologies, the organic dye in the industrial wastewater can be more effectively degraded by inorganic matters. Under the influence of the distance of a transmission path, the activity of the monodisperse quantum dot photocatalyst with the particle size range in the nanometer size is obviously stronger than that of a bulk material, so that the photocatalytic activity can be effectively improved by preparing the quantum dot photocatalyst material. Cadmium sulfide equivalent quantum dots have been reported as photocatalysts, but the narrow band gap makes the generated photogenerated electron-hole pairs very easy to recombine, which is not beneficial to photocatalytic degradation. The zinc-cadmium-sulfur quantum dots are II-VI group transition metal sulfides, have the advantages of both zinc sulfide and cadmium sulfide, have band gaps which can be adjusted randomly between 3.5 eV and 2.4 eV, have strong corrosion resistance and have great application prospects in the field of photodegradation.
At present, most of the preparation processes of zinc-cadmium-sulfur quantum dots are carried out by heating in a reaction kettle, a three-mouth bottle and other containers, and are limited by a plurality of conditions, such as small volume of the reaction container (several milliliters to tens of milliliters), high reaction temperature (generally over 160 ℃), and long reaction time (several hours to tens of hours). Although the photocatalyst is not consumed in the process of degrading the organic dye theoretically, the industrial wastewater treatment capacity is large, the concentration is high, the scale of the existing preparation method is small, the macro preparation cannot be realized, and the practical application of degrading the organic pollutants by the photocatalysis is difficult to realize. In view of this, it is very necessary to develop a water-soluble zinc-cadmium-sulfur quantum dot photocatalyst which can be rapidly and massively prepared at room temperature and has high photocatalytic degradation efficiency.
Disclosure of Invention
The invention provides a water-soluble zinc-cadmium-sulfur quantum dot photocatalyst and a preparation method thereof, aiming at solving the problems of small capacity of a reaction vessel, high reaction temperature and longer reaction time in the preparation process of the existing zinc-cadmium-sulfur quantum dot photocatalyst.
A water-soluble zinc cadmium sulfur quantum dot photocatalyst is disclosed, wherein the molar ratio of cations to anions in the water-soluble zinc cadmium sulfur quantum dot photocatalyst is 1: 1; the cations are zinc ions and cadmium ions, and the molar ratio of the zinc ions to the cadmium ions is 1: 16-16: 1; the anion is a sulfide ion;
the water-soluble zinc-cadmium-sulfur quantum dot photocatalyst is dissolved in water and is powdery microparticles, and the size of the microparticles is 2-5 nanometers; the material has the characteristics of semiconductor quantum dots, and emits visible light under the irradiation of ultraviolet light; and the rhodamine B and the methyl orange are degraded in a photocatalytic manner under the illumination condition.
The preparation operation steps of the water-soluble zinc-cadmium-sulfur quantum dot photocatalyst are as follows:
(1) preparation of precursor solution
The molar ratio of the raw materials is 1: 16-16:1, adding a zinc source and a cadmium source into water, and adding a sulfhydryl compound, wherein the addition amount of the sulfhydryl compound is four times of the total molar amount of the zinc source and the cadmium source; adding sodium hydroxide or potassium hydroxide until the solution is clear to form a precursor solution;
(2) preparation of water-soluble zinc-cadmium-sulfur quantum dot photocatalyst
Adding sodium sulfide into the precursor solution, wherein the addition amount of the sodium sulfide is 1-10 times of the total molar amount of the zinc source and the cadmium source; and (3) adjusting the pH value of the solution to 3-10 by using 3-mercaptopropionic acid, and stirring at room temperature for 15-30 minutes to obtain the water-soluble zinc-cadmium-sulfur quantum dot photocatalyst.
The specific technical scheme is as follows:
in the step (1), the zinc source is one of zinc chloride, zinc acetate or zinc nitrate.
In the step (1), the cadmium source is one of cadmium chloride, cadmium acetate or cadmium nitrate.
In the step (1), the mercapto compound is one or more of 3-mercaptopropionic acid, thioglycolic acid and ammonium thioglycolate.
The beneficial technical effects of the invention are embodied in the following aspects:
1. the preparation process of the water-soluble zinc-cadmium-sulfur quantum dot photocatalyst does not need reaction vessels such as a reaction kettle, a three-neck flask and the like, and is not limited by an experimental site and an experimental vessel; the method can be quickly synthesized in the air atmosphere at room temperature, does not generate the agglomeration phenomenon caused by austenite curing, has high experimental reproducibility, is suitable for large-scale production, and greatly reduces the preparation cost.
2. The zinc-cadmium-sulfur quantum dot photocatalyst selected by the invention can directly absorb visible light, and the energy utilization rate is high; the photocatalyst can be directly degraded without being loaded on other materials, and the preparation process is simple.
3. The water-soluble quantum dot photocatalyst prepared by the invention has no long-chain organic ligand, can be directly used for photocatalytic hydrogen production and organic dye degradation without complex ligand exchange, is simple to operate and is easy to realize industrialization.
4. According to the water-soluble zinc-cadmium-sulfur quantum dot photocatalyst prepared by the invention, the amount of organic pollutants degraded by the catalyst per unit mass is far higher than that of most of the existing photocatalysts, 1 mg of the photocatalyst is used for photocatalytic degradation of 1 mg of rhodamine or methyl orange, and the highest degradation efficiency can reach 99% within 10 minutes.
Drawings
FIG. 1 is a degradation diagram of rhodamine B degraded by the water-soluble quantum dot photocatalyst prepared in example 1 when the ratio of cations to sulfur sources is 1:1.2, 1:2, 1:4, 1:5, 1:6, and 1:8, respectively.
FIG. 2 is the UV-VIS absorption spectrum of the quantum dot photocatalyst degrading methyl orange in example 2.
FIG. 3 is a degradation diagram of quantum dot photocatalytic rhodamine B prepared by reaction precursor solutions with different pH values in example 3.
FIG. 4 is a degradation diagram of quantum dot photocatalytic rhodamine B prepared according to different zinc-cadmium ratios in the example.
The specific implementation mode is as follows:
for a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
Example 1
The preparation operation steps of the water-soluble zinc-cadmium-sulfur quantum dot photocatalyst are as follows:
(1) taking six beakers, respectively adding 15 ml of deionized water, 17 mg of 3-mercaptopropionic acid, 3.6 mg of zinc acetate and 4.6 mg of cadmium acetate into each beaker according to a formula, uniformly mixing, adding sodium hydroxide until the solution is clear, and obtaining six identical quantum dot reaction precursor solutions, wherein the molar ratio of zinc ions to cadmium ions in the quantum dot reaction precursor solutions is 1:1.
(2) 11.5 mg, 19.2 mg, 38.4 mg, 48 mg, 57.6 mg and 76.8 mg of sodium sulfide nonahydrate are added into six parts of quantum dot reaction precursor solution respectively, then the pH value of five parts of reaction precursor solution is adjusted to 4.0 by using 3-mercaptopropionic acid, and the reaction is carried out for 20 minutes under the stirring condition, so as to obtain six parts of water-soluble zinc-cadmium-sulfur quantum dot photocatalyst solution. The molar ratio of zinc to cadmium in the six parts of water-soluble zinc-cadmium-sulfur quantum dot photocatalyst is 1:1, and the molar ratio of cations (zinc to cadmium) to sulfur is 1:1. The dried water-soluble zinc cadmium sulfur quantum dot photocatalyst is powdery, the size of the powder particles is 2-5 nanometers, the obtained six parts of water-soluble zinc cadmium sulfur quantum dot photocatalyst can be well dissolved in water, can emit visible light under the irradiation of ultraviolet light, and can be used for photocatalytic degradation of rhodamine B and methyl orange under the illumination condition.
The rhodamine B cannot be degraded in natural environment, and the water-soluble zinc-cadmium-sulfur quantum dot photocatalyst prepared by the method can be rapidly degraded under the illumination condition. Fig. 1 is a degradation diagram of water-soluble zinc cadmium sulfur water-soluble quantum dot photocatalytic degradation rhodamine B prepared by using different cation/sulfur source ratios in this example 1, and 10 ml of rhodamine B with a concentration of 0.1 mg/ml is degraded by using 1 mg of water-soluble zinc cadmium sulfur quantum dot photocatalyst, and it can be seen from the diagram that all the water-soluble zinc cadmium sulfur quantum dot photocatalysts prepared by using different cation/sulfur source ratios can degrade rhodamine B, initially, with the increase of the cation/sulfur source ratio, the photocatalytic degradation rate gradually increases, reaches a maximum when the cation/sulfur source =1/5, and then, the cation/sulfur source ratio continues to increase, and the photocatalytic degradation rate does not increase any more.
Example 2
The preparation operation steps of the water-soluble zinc-cadmium-sulfur quantum dot photocatalyst are as follows:
(1) taking 1 beaker with 5 liters, taking 4 liters of deionized water, 4.57 grams of 3-mercaptopropionic acid, 0.996 grams of zinc acetate and 1.23 grams of cadmium acetate according to the formula, adding the deionized water, the 3-mercaptopropionic acid, the zinc acetate and the cadmium acetate into the beaker, mixing, adding sodium hydroxide until the solution is clear, and obtaining a quantum dot reaction precursor solution, wherein the molar ratio of zinc ions to cadmium ions in the precursor solution is 1:1.
(2) adding 12.8 g of sodium sulfide nonahydrate into the quantum dot reaction precursor solution, then adjusting the pH value of the quantum dot reaction precursor solution to 4.0 by using 3-mercaptopropionic acid, and reacting for 20 minutes under the stirring condition to obtain the water-soluble zinc-cadmium-sulfur quantum dot photocatalyst solution. The molar ratio of zinc to cadmium in the water-soluble zinc-cadmium-sulfur quantum dot photocatalyst is 1:1, and the molar ratio of cations (zinc to cadmium) to sulfur is 1:1. The dried water-soluble zinc cadmium sulfur quantum dot photocatalyst is powdery, the size of powder particles is 2-5 nanometers, the water-soluble zinc cadmium sulfur quantum dot photocatalyst can be well dissolved in water, emits visible light under the irradiation of ultraviolet light, and can be used for photocatalytic degradation of rhodamine B and methyl orange under the illumination condition.
Methyl orange can not be degraded in natural environment, and can be rapidly degraded under the illumination condition after the water-soluble zinc-cadmium-sulfur quantum dot photocatalyst prepared by the invention is added. Fig. 2 is an ultraviolet-visible absorption spectrum of the quantum dot photocatalyst for degrading methyl orange in this example, and 1 mg of quantum dot is used for catalyzing 10 ml of methyl orange with a concentration of 0.1 mg/ml, and it can be seen from the figure that the quantum dot photocatalyst degrades methyl orange very fast, and 98% of methyl orange can be degraded in 8 minutes. This shows that no quantum dot has no reduction of catalytic degradation rate due to amplification reaction, and the invention is proved to have the condition of large-scale production and wide market application prospect.
Example 3
The preparation operation steps of the water-soluble zinc-cadmium-sulfur quantum dot photocatalyst are as follows:
(1) taking six beakers, adding 15 ml of deionized water, 17 mg of 3-mercaptopropionic acid, 3.6 mg of zinc acetate and 4.6 mg of cadmium acetate into each beaker according to a formula, uniformly mixing, adding sodium hydroxide until the solution is clear, and obtaining six identical quantum dot reaction precursor solutions, wherein the molar ratio of zinc ions to cadmium ions in the quantum dot precursor solution is 1:1.
(2) adding 48 mg of sodium sulfide nonahydrate into six parts of quantum dot reaction precursor solution respectively, then adjusting the pH values of the six parts of quantum dot reaction precursor solution to 4.0, 5.0, 6.0, 8.0, 10.0 and 12.0 respectively by using 3-mercaptopropionic acid, and reacting for 20 minutes under the stirring condition to obtain six parts of zinc-cadmium-sulfur water-soluble quantum dot photocatalyst solution. The molar ratio of zinc to cadmium in the six zinc-cadmium-sulfur quantum dot photocatalysts is 1:1, and the molar ratio of cations (zinc to cadmium) to sulfur is 1:1. The dried water-soluble zinc-cadmium-sulfur quantum dot photocatalyst is powdery, the size of powder particles is 2-5 nanometers, the obtained six quantum dot photocatalysts can be well dissolved in water, emit visible light under the irradiation of ultraviolet light, and can be used for photocatalytic degradation of rhodamine B and methyl orange under the illumination condition.
Methyl orange can not be degraded in natural environment, and can be rapidly degraded under the illumination condition after the water-soluble zinc-cadmium-sulfur quantum dot photocatalyst prepared by the invention is added. Fig. 3 is a degradation diagram of the water-soluble zinc-cadmium-sulfur quantum dot photocatalytic degradation methyl orange prepared by adjusting different pH values of the precursor solution in this embodiment, and it can be seen from the diagram that the water-soluble zinc-cadmium-sulfur quantum dot photocatalyst prepared by the precursor solution with different pH values can all photocatalytic degrade the methyl orange. With the continuous reduction of the pH value, the rate of the quantum dot photocatalytic degradation is in an increasing trend, when the pH of the precursor solution is =4, the rate of the catalytic degradation of the water-soluble zinc-cadmium-sulfur quantum dot photocatalyst reaches the maximum, and 98.6% of methyl orange in the solution can be degraded in 8 minutes.
Example 4
The preparation operation steps of the water-soluble zinc-cadmium-sulfur quantum dot photocatalyst are as follows:
(1) taking 5 beakers as No. 1-5, respectively adding 15 ml of deionized water, and then respectively adding 17 mg of 3-mercaptopropionic acid, 1.47 mg of zinc acetate and 7.38 mg of cadmium acetate into the No. 1 beaker according to the formula; adding 17 mg of 3-mercaptopropionic acid, 2.39 mg of zinc acetate and 6.22 mg of cadmium acetate into a No. 2 beaker; adding 17 mg of 3-mercaptopropionic acid, 3.67 mg of zinc acetate and 4.61 mg of cadmium acetate into a No. 3 beaker; adding 17 mg of 3-mercaptopropionic acid, 4.95 mg of zinc acetate and 3.0 mg of cadmium acetate into a No. 4 beaker; adding 17 mg of 3-mercaptopropionic acid, 5.87 mg of zinc acetate and 0.008 mmol of cadmium acetate into a No. 5 beaker; and respectively adding sodium hydroxide into the five beakers until the solution is clear to obtain five parts of quantum dot reaction precursor solutions, wherein the molar ratios of zinc ions to cadmium ions in the No. 1-5 quantum dot precursor solutions are respectively 1: 4. 1:2, 1:1, 2:1 and 4: 1.
(2) And respectively adding 0.20 mmol of sodium sulfide nonahydrate into the five parts of quantum dot reaction precursor solution, then adjusting the pH value of the five parts of quantum dot reaction precursor solution to 4.0 by using 3-mercaptopropionic acid, and reacting for 20 minutes under the stirring condition to obtain five parts of water-soluble zinc-cadmium-sulfur quantum dot photocatalyst solution. The molar ratio of zinc to cadmium in the five parts of water-soluble zinc-cadmium-sulfur quantum dot photocatalyst is 1:4, 1:2, 1:1, 2:1 and 4:1 respectively; the molar ratio of cations (zinc to cadmium) to sulfur was 1:1. The dried water-soluble zinc cadmium sulfur quantum dot photocatalyst is in a powder shape, the size of powder particles is 2-5 nanometers, the five parts of water-soluble zinc cadmium sulfur quantum dot photocatalyst can be well dissolved in water, can emit visible light under the irradiation of ultraviolet light, and can be used for degrading rhodamine B and methyl orange under the photocatalysis of light.
The rhodamine B can not be degraded in natural environment, and can be rapidly degraded under the illumination condition after the water-soluble zinc-cadmium-sulfur quantum dot photocatalyst prepared by the invention is added. Fig. 4 is a degradation diagram of the quantum dot photocatalytic degradation rhodamine B prepared according to different zinc-cadmium ratios in the present embodiment, and it can be seen from the diagram that the water-soluble zinc-cadmium-sulfur quantum dot photocatalysts with different zinc-cadmium ratios can all perform photocatalytic degradation on rhodamine B. When the molar ratio of zinc to cadmium is 1/2, the photocatalytic degradation rate reaches the maximum, and 98.2 percent of rhodamine B in the solution can be degraded in 2 minutes.
Example 5
The preparation operation steps of the water-soluble zinc-cadmium-sulfur quantum dot photocatalyst are as follows:
(1) adding 15 ml of deionized water, 17 mg of 3-mercaptopropionic acid, 2.73 mg of zinc chloride and 3.67 mg of cadmium chloride into a 20 ml beaker according to the formula, mixing, adding sodium hydroxide until the solution is clear, and obtaining a quantum dot reaction precursor solution, wherein the molar ratio of zinc ions to cadmium ions in the quantum dot reaction precursor solution is 1:1.
(2) and respectively adding 48 mg of sodium sulfide nonahydrate into the quantum dot reaction precursor solution, then adjusting the pH value of the quantum dot reaction precursor solution to 4.0 by using 3-mercaptopropionic acid, and reacting for 20 minutes under the stirring condition to obtain the water-soluble zinc-cadmium-sulfur quantum dot photocatalyst solution. The molar ratio of zinc to cadmium in the water-soluble zinc-cadmium-sulfur quantum dot photocatalyst is 1:1, and the molar ratio of cations (zinc to cadmium) to sulfur is 1:1. The dried water-soluble zinc cadmium sulfur quantum dot photocatalyst is powdery, the size of powder particles is 2-5 nanometers, the water-soluble zinc cadmium sulfur quantum dot photocatalyst can be well dissolved in water, emits visible light under the irradiation of ultraviolet light, and can be used for photocatalytic degradation of rhodamine B and methyl orange under the illumination condition.
Example 6
The preparation operation steps of the water-soluble zinc-cadmium-sulfur quantum dot photocatalyst are as follows:
(1) adding 15 ml of deionized water, 17 mg of 3-mercaptopropionic acid, 5.95 mg of zinc nitrate and 6.17 mg of cadmium nitrate into a 20 ml beaker according to the formula, uniformly mixing, adding potassium hydroxide until the solution is clear, and obtaining a quantum dot reaction precursor solution, wherein the molar ratio of zinc ions to cadmium ions in the quantum dot reaction precursor solution is 1:1.
(2) and respectively adding 48 mg of sodium sulfide nonahydrate into the quantum dot reaction precursor solution, then adjusting the pH value of the quantum dot reaction precursor solution to 4.5 by using 3-mercaptopropionic acid, and reacting for 20 minutes under the stirring condition to obtain the water-soluble zinc-cadmium-sulfur quantum dot photocatalyst solution. The molar ratio of zinc to cadmium in the water-soluble zinc-cadmium-sulfur quantum dot photocatalyst is 1:1, and the molar ratio of cations (zinc to cadmium) to sulfur is 1:1. The dried water-soluble zinc cadmium sulfur quantum dot photocatalyst is powdery, the size of powder particles is 2-5 nanometers, the obtained water-soluble zinc cadmium sulfur quantum dot photocatalyst can be well dissolved in water, emits visible light under the irradiation of ultraviolet light, and can be used for photocatalytic degradation of rhodamine B and methyl orange under the illumination condition.
Example 7
The preparation operation steps of the water-soluble zinc-cadmium-sulfur quantum dot photocatalyst are as follows:
(1) adding 15 ml of deionized water, 14.74 mg of thioglycolic acid, 3.6 mg of zinc acetate and 4.6 mg of cadmium acetate into a 20 ml beaker according to the formula, uniformly mixing, adding potassium hydroxide until the solution is clear, and obtaining a quantum dot reaction precursor solution, wherein the molar ratio of zinc ions to cadmium ions in the quantum dot reaction precursor solution is 1:1.
(2) and adding 48 mg of sodium sulfide nonahydrate into the quantum dot reaction precursor solution, then adjusting the pH value of the quantum dot reaction precursor solution to 4.0 by using thioglycolic acid, and reacting for 20 minutes under the stirring condition to obtain the water-soluble zinc-cadmium-sulfur quantum dot photocatalyst solution. The molar ratio of zinc to cadmium in the water-soluble zinc-cadmium-sulfur quantum dot photocatalyst is 1:1, and the molar ratio of cations (zinc to cadmium) to sulfur is 1:1. The dried water-soluble zinc cadmium sulfur quantum dot photocatalyst is powdery, the size of powder particles is 2-5 nanometers, the obtained water-soluble zinc cadmium sulfur quantum dot photocatalyst can be well dissolved in water, emits visible light under the irradiation of ultraviolet light, and can be used for photocatalytic degradation of rhodamine B and methyl orange under the illumination condition.
Example 8
The preparation operation steps of the water-soluble zinc-cadmium-sulfur quantum dot photocatalyst are as follows:
(1) adding 15 ml of deionized water, 17.5 mg of ammonium thioglycolate, 3.6 mg of zinc acetate and 4.6 mg of cadmium acetate into a 20 ml beaker according to the formula, uniformly mixing, adding potassium hydroxide until the solution is clear, and obtaining a quantum dot reaction precursor solution, wherein the molar ratio of zinc ions to cadmium ions in the quantum dot reaction precursor solution is 1:1.
(2) and adding 48 mg of sodium sulfide nonahydrate into the quantum dot reaction precursor solution, then adjusting the pH value of the reaction quantum dot reaction precursor solution to 4.0 by using 3-mercaptopropionic acid, and reacting for 30 minutes under the stirring condition to obtain the water-soluble zinc-cadmium-sulfur quantum dot photocatalyst solution. The molar ratio of zinc to cadmium in the water-soluble zinc-cadmium-sulfur quantum dot photocatalyst is 1:1, and the molar ratio of cations (zinc to cadmium) to sulfur is 1:1. The dried water-soluble zinc cadmium sulfur quantum dot photocatalyst is powdery, the size of powder particles is 2-5 nanometers, the obtained water-soluble zinc cadmium sulfur quantum dot photocatalyst can be well dissolved in water, emits visible light under the irradiation of ultraviolet light, and can be used for photocatalytic degradation of rhodamine B and methyl orange under the illumination condition.
The above description of the embodiments is only intended to facilitate the understanding of the method and the core idea of the present invention. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (5)
1. A water-soluble zinc-cadmium-sulfur quantum dot photocatalyst is characterized in that: the molar ratio of cations to anions in the water-soluble zinc-cadmium-sulfur quantum dot photocatalyst is 1: 1; the cations are zinc ions and cadmium ions, and the molar ratio of the zinc ions to the cadmium ions is 1: 16-16: 1; the anion is a sulfide ion;
the water-soluble zinc-cadmium-sulfur quantum dot photocatalyst is dissolved in water and is powdery microparticles, and the size of the microparticles is 2-5 nanometers; the material has the characteristics of semiconductor quantum dots, and emits visible light under the irradiation of ultraviolet light; and the rhodamine B and the methyl orange are degraded in a photocatalytic manner under the illumination condition.
2. The preparation method of the water-soluble zinc-cadmium-sulfur quantum dot photocatalyst according to claim 1, which is characterized by comprising the following operation steps:
(1) preparation of precursor solution
The molar ratio of the raw materials is 1: 16-16:1, adding a zinc source and a cadmium source into water, and adding a sulfhydryl compound, wherein the addition amount of the sulfhydryl compound is four times of the total molar amount of the zinc source and the cadmium source; adding sodium hydroxide or potassium hydroxide until the solution is clear to form a precursor solution;
(2) preparation of water-soluble zinc-cadmium-sulfur quantum dot photocatalyst
Adding sodium sulfide into the precursor solution, wherein the addition amount of the sodium sulfide is 1-10 times of the total molar amount of the zinc source and the cadmium source; and (3) adjusting the pH value of the solution to 3-10 by using 3-mercaptopropionic acid, and stirring at room temperature for 15-30 minutes to obtain the water-soluble zinc-cadmium-sulfur quantum dot photocatalyst.
3. The method of claim 2, wherein: in the step (1), the zinc source is one of zinc chloride, zinc acetate or zinc nitrate.
4. The method of claim 2, wherein: in the step (1), the cadmium source is one of cadmium chloride, cadmium acetate or cadmium nitrate.
5. The method of claim 2, wherein: in the step (1), the mercapto compound is one or more of 3-mercaptopropionic acid, thioglycolic acid and ammonium thioglycolate.
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