CN113398955B - Preparation method of Sillen-type bimetal oxyhalide for antibiotic degradation - Google Patents

Preparation method of Sillen-type bimetal oxyhalide for antibiotic degradation Download PDF

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CN113398955B
CN113398955B CN202110602268.2A CN202110602268A CN113398955B CN 113398955 B CN113398955 B CN 113398955B CN 202110602268 A CN202110602268 A CN 202110602268A CN 113398955 B CN113398955 B CN 113398955B
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bromide
source
methylimidazole
cadmium
solution
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CN113398955A (en
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夏杰祥
庞致远
王彬
严兴旺
尹盛
李华明
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Jiangsu University
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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
    • B01J27/06—Halogens; Compounds thereof
    • B01J35/23—
    • B01J35/39—
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/10—Heat treatment in the presence of water, e.g. steam
    • 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
    • C02F2101/308—Dyes; Colorants; Fluorescent agents
    • 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
    • C02F2101/34—Organic compounds containing oxygen
    • 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
    • C02F2101/36—Organic compounds containing halogen
    • 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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/30—Wastewater or sewage treatment systems using renewable energies
    • Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy

Abstract

The invention belongs to the fields of photocatalysis technology and environmental pollution treatment, and discloses a preparation method of a Sillen-type bimetal oxyhalide for antibiotic degradation. The invention takes brominated 1-hexadecyl-3-methylimidazole as a bromine source and cadmium acetate dihydrate as a cadmium source, the synthesis is carried out in a mixed solution of water and mannitol by a solvothermal method, and the product is cooled, filtered and washed and is air-dried to obtain CdBiO 2 An ultrathin Br nanosheet. Compared with CdBiO prepared by using a potassium bromide-position bromine source 2 Br, cdBiO prepared by using cadmium nitrate as cadmium source 2 Br, high catalytic efficiency of degrading organic dye ciprofloxacin by photocatalysis. The photocatalyst adopts a solvent thermal synthesis method, is simple to prepare, is green and environment-friendly, has low cost and is easy to control.

Description

Preparation method of Sillen-type bimetal oxyhalide for antibiotic degradation
Technical Field
The invention belongs to the fields of photocatalysis technology and environmental pollution treatment, and particularly relates to a preparation method of a Sillen-type bimetal oxyhalide for antibiotic degradation.
Background
Antibiotic contamination means that a large amount of antibiotics are discharged into the environment in the original state, metabolites, etc. and cause contamination. This is mainly due to the difficulty of complete absorption of the administered antibiotic by humans or animals. According to the analysis of the Chinese river antibiotic pollution map, the main mountain rivers from north to south of China are in antibiotic pollution, and the average concentration of the antibiotic reaches 303 ng/L. In addition, the antibiotic pollution condition in the global water environment is also very serious, so that the antibiotic is ubiquitous in the global water environment and gradually develops into a water pollution problem to be responded to by all mankind. Therefore, the search for a simple and efficient method for removing antibiotics from water has yet to be further discussed and studied.
The photocatalysis technology is a new technology for degrading environmental pollutants, can effectively utilize inexhaustible solar energy resources, generates holes and free radicals with high reaction activity, and makes the degradation of the environmental pollutants possible. The photocatalysis technology has the advantages of simple operation, mild conditions, high reaction speed and the like, provides an effective way for degrading antibiotic pollution in water environment, and has wide research space and application prospect.
The layered structure material has great application potential in the fields of catalysis, energy storage and conversion, electronics and the like, and the layered bismuth-based semiconductor photocatalytic material has attracted people's extensive interest by its unique layered structure, strong photooxidation capability, excellent photocatalytic performance and the like. Comprising Bi of Aurivillius type 2 MO 6 (M = W, mo, cr), sillen-type BiOX (X = Cl, br, I), mixed cation Sillen-type PbBiO 2 X (X = Cl, br), bi of pyrochlore structure 2 MNbO 7 (M = Al, ga, in, fe), bi associated with the newly developed Sillen structure 2 O 2 (OH)(NO 3 ) And Bi 2 O 2 [BO 2 (OH)]. At present, the modification of the laminated bismuth-based semiconductor photocatalytic material mainly focuses on the aspects of microstructure and morphology control, special crystal face synthesis, heterogeneous/homogeneous junction structure and the like, and the research on the crystal structure design for improving the photocatalytic performance of the laminated bismuth-based semiconductor is less. In particular, the relationship between the crystal structure and the photoactivity is not well known at present. In view of the structural diversity, a mixed cation Sillen-type quaternary bismuth-based material BiMO 2 X (M = Cd, pb, ca, ba, sr and X = Cl, br, I) may be a good exploration system.
On the basis of a typical Silen structure BiOBr, a visible light response Silen type mixed cation layered catalyst CdBiO is developed 2 Br, and for the first time proposes a new design of a layered structure for promoting charge separation and oxygen activation reactionsAnd (4) strategy. Is different from [ Bi ] 2 O 2 ] 2+ Layers and interleaved Br - BiOBr, cdBiO characterised by a double layer tablet 2 The crystal structure of Br includes [ CdBiO ] 2 ] + Layers and interleaved individual Br - The interlayer spacing is narrowed, and the CdBiO is greatly shortened 2 Photo-generated electrons (e) in Br - ) And a cavity (h) + ) Thereby allowing advantageous migration of the support from the body to the catalyst surface. Not only the application of visible light active layered materials in environmental chemistry/biochemistry, but also the great potential of crystal structure manipulation in controlling charge transport behavior and photo (electro) chemical properties are revealed.
CdBiO as a novel layered quaternary oxide semiconductor 2 Br has attracted great attention because of its characteristics of low cost, corrosion resistance, excellent photocatalytic performance, high chemical and optical stability, and the like. However, cdBiO is currently available for the ultrathin nanosheets concerned 2 The preparation method of Br and the regulation strategy of the crystal structure have less literature reports. Therefore, a simple and efficient ultrathin nano-sheet CdBiO is explored 2 Br is significant in improving the efficiency of photocatalytic degradation of organic pollutants.
Disclosure of Invention
The invention aims to provide a preparation method of a Sillen-type bimetal oxyhalide for antibiotic degradation. The photocatalyst CdBiO 2 The specific surface area and the oxygen vacancy are increased by doping the Br nano-sheet, and the oxygen defect concentration is improved, so that the efficiency of degrading organic pollutants in a water body by visible light catalysis is improved. The catalyst is synthesized by a solvothermal method, the reaction condition is mild, and the operation is simple.
The technical scheme of the invention is as follows:
a method for preparing a sillen-type bimetallic oxyhalide for antibiotic degradation, comprising the steps of:
(1) Bismuth nitrate pentahydrate, bismuth acetate or bismuth ammonium citrate are used as bismuth sources; cadmium acetate dihydrate or cadmium nitrate is used as a cadmium source, and then mannitol and deionized water are added to prepare a solution A;
(2) Taking brominated ionic liquid or inorganic bromine salt as a bromine source, and then adding mannitol and deionized water to prepare a solution B;
(3) Dropwise adding the solution B obtained in the step (2) into the solution A obtained in the step (1), quickly stirring, adjusting the pH to 8-12 with ammonia water after dropwise adding, continuously stirring for 20-60 minutes, pouring the solution into a high-pressure reaction kettle with a polytetrafluoroethylene lining, reacting for 12-24 hours at 150-200 ℃, centrifuging the obtained product, respectively cleaning with deionized water and absolute ethyl alcohol for several times, and drying to obtain BiCdO 2 Br ultrathin nanoplatelet photocatalyst.
In the step (1), mixing a bismuth source in the solution A: a cadmium source: mannitol: the dosage ratio of the deionized water is as follows: 0.5mmol.
In the step (2), mixing the brominated ionic liquid or inorganic bromine salt in the solution B: mannitol: the dosage ratio of the deionized water is as follows: 0.5mmol. In the step (2), the brominated ionic liquid is 1-hexadecyl-3-methylimidazole bromide, 1-dodecyl-3-methylimidazole bromide, 1-tetradecyl-3-methylimidazole bromide, 1-hexyl-2, 3-methylimidazole bromide, 1-hexyl-3-methylimidazole bromide, 1-allyl-3-butylimidazole bromide, 1-allyl-3-ethylimidazole bromide, 1-allyl-3-methylimidazole bromide, 1-decyl-3-methylimidazole bromide, 1-carboxyethyl-3-methylimidazole bromide, 1-carboxymethyl-3-methylimidazole bromide, 1-aminopropyl-3-methylimidazole bromide, 1-aminoethyl-3-methylimidazole bromide or 1-benzyl-3-methylimidazole bromide; the inorganic bromine salt is potassium bromide or sodium bromide.
The ratio of the amount of the brominated ionic liquid in the step (2) to the amount of the bismuth source substance in the step (1) is 1.
In the step (3), a bismuth source: a cadmium source: the mass ratio of the bromine source is 1; the drying temperature is 50-80 ℃, and the reaction time is 12-24 hours.
The invention relates to a CdBiO 2 The Br ultrathin nanosheet photocatalyst is used for photocatalytic degradation of organic dye ciprofloxacin.
The beneficial effects of the invention are as follows:
the invention prepares CdBiO controllably by mild solvothermal method for the first time 2 An ultrathin Br nanosheet.
Compared with BiOBr ultrathin nanosheets, cadmium-doped CdBiO 2 The Br ultrathin nanosheet exhibits excellent visible light photocatalytic ciprofloxacin degradation activity.
Drawings
FIG. 1 shows CdBiO 2 XRD pattern of Br nanosheet;
FIG. 2 shows CdBiO 2 TEM images of Br nanoplates;
FIG. 3 shows CdBiO under visible light irradiation 2 Degradation curve of Br versus ciprofloxacin.
Detailed Description
The invention will be further described with reference to the following figures and specific examples, without limiting the scope of the invention thereto.
Example 1:
CdBiO is prepared by using brominated 1-hexadecyl-3-methylimidazole as a bromine source and cadmium acetate dihydrate as a cadmium source 2 Br nanosheet step:
0.5mmol of bismuth nitrate pentahydrate and 0.5mmol of cadmium acetate dihydrate are taken, 1.8mmol of mannitol and 18mL of deionized water are added to prepare a solution A, 0.5mmol of 1-hexadecyl-3-methylimidazole bromide is taken, and 1.8mmol of mannitol and 18mL of deionized water are added to prepare a solution B. And dropwise adding the solution B into the solution A, quickly stirring, adjusting the pH value to 8 by using ammonia water after dropwise adding, continuously stirring for 20-60 minutes, pouring the solution into a high-pressure reaction kettle with a polytetrafluoroethylene lining, reacting for 24 hours at 150 ℃, centrifuging the obtained product, respectively washing with deionized water and absolute ethyl alcohol for three times, and finally drying at 50-80 ℃.
Example 2:
CdBiO is prepared by using brominated 1-hexadecyl-3-methylimidazole as a bromine source and cadmium nitrate as a cadmium source 2 Br nanosheet step:
0.5mmol of bismuth nitrate pentahydrate and 0.5mmol of cadmium nitrate are taken, 1.8mmol of mannitol and 18mL of deionized water are added to prepare a solution A, 0.5mmol of 1-hexadecyl-3-methylimidazole bromide is taken, and 1.8mmol of mannitol and 18mL of deionized water are added to prepare a solution B. And dropwise adding the solution B into the solution A, quickly stirring, adjusting the pH value to 10 by using ammonia water after dropwise adding, continuously stirring for 20-60 minutes, pouring the solution into a high-pressure reaction kettle with a polytetrafluoroethylene lining, reacting for 20 hours at 180 ℃, centrifuging the obtained product, respectively washing with deionized water and absolute ethyl alcohol for three times, and finally drying at 50-80 ℃.
Example 3:
CdBiO preparation with potassium bromide as bromine source and cadmium acetate dihydrate as cadmium source 2 Br nanosheet step:
0.5mmol of bismuth nitrate pentahydrate and 0.5mmol of cadmium acetate dihydrate are taken, 1.8mmol of mannitol and 18mL of deionized water are added to prepare a solution A, 0.5mmol of potassium bromide is taken, and 1.8mmol of mannitol and 18mL of deionized water are added to prepare a solution B. Dropwise adding the solution B into the solution A, quickly stirring, adjusting the pH to 12 by using ammonia water after dropwise adding, continuously stirring for 20-60 minutes, pouring the solution into a high-pressure reaction kettle with a polytetrafluoroethylene lining, reacting for 12 hours at 200 ℃, centrifuging the obtained product, respectively washing with deionized water and absolute ethyl alcohol for three times, and finally drying at 50-80 ℃.
FIG. 1 shows CdBiO prepared in examples 1 to 3 of the present invention 2 XRD pattern of Br. It can be seen that the catalyst prepared is pure CdBiO 2 A Br material.
FIG. 2 is CdBiO 2 TEM image of Br ultrathin nanosheets.
FIG. 3 is the CdBiO prepared 2 And degrading the ciprofloxacin activity diagram of the Br ultrathin nanosheet under the irradiation of visible light. After 210 minutes of visible light irradiation, cdBiO 2 The Br ultrathin nanosheet material can realize 79.44% degradation of target pollutants. Undoped BiOBr ultrathin nanoplates achieved only 9.82% degradation of the target contaminant (ciprofloxacin).

Claims (8)

1. A method for preparing Sillen-type bimetal oxyhalide for antibiotic degradation, which is characterized by comprising the following steps:
(1) Bismuth nitrate pentahydrate, bismuth acetate or bismuth ammonium citrate are used as bismuth sources; cadmium acetate dihydrate or cadmium nitrate is used as a cadmium source, and then mannitol and deionized water are added to prepare a solution A;
(2) Taking brominated ionic liquid or inorganic bromine salt as a bromine source, and then adding mannitol and deionized water to prepare a solution B;
(3) And (3) dropwise adding the solution B obtained in the step (2) into the solution A obtained in the step (1), quickly stirring, adjusting the pH to 8-12 by using ammonia water after dropwise adding, continuously stirring for 20-60 minutes, pouring the solution into a high-pressure reaction kettle with a polytetrafluoroethylene lining, reacting for 12-24 hours at 150-200 ℃, centrifuging the obtained product, respectively cleaning with deionized water and absolute ethyl alcohol for several times, and drying to obtain the CdO 2Br ultrathin nanosheet photocatalyst.
2. The production method according to claim 1, wherein in the step (1), the bismuth source in the solution a is mixed: a cadmium source: mannitol: the dosage ratio of the deionized water is as follows: 0.5mmol.
3. The production method according to claim 1, wherein in the step (2), the ionic bromide liquid or inorganic bromide salt in the mixed solution B: mannitol: the dosage ratio of the deionized water is as follows: 0.5mmol.
4. The method according to claim 1, wherein in the step (2), the ionic liquid bromide is 1-hexadecyl-3-methylimidazole bromide, 1-dodecyl-3-methylimidazole bromide, 1-tetradecyl-3-methylimidazole bromide, 1-hexyl-2, 3-methylimidazole bromide, 1-hexyl-3-methylimidazole bromide, 1-allyl-3-butylimidazole bromide, 1-allyl-3-ethylimidazole bromide, 1-allyl-3-methylimidazole bromide, 1-decyl-3-methylimidazole bromide, 1-carboxyethyl-3-methylimidazole bromide, 1-carboxymethyl-3-methylimidazole bromide, 1-aminopropyl-3-methylimidazole bromide, 1-aminoethyl-3-methylimidazole bromide or 1-benzyl-3-methylimidazole bromide; the inorganic bromine salt is potassium bromide or sodium bromide.
5. The preparation method according to claim 1, wherein the ratio of the amount of the ionic liquid bromide in the step (2) to the amount of the bismuth source substance in the step (1) is 1.
6. The production method according to claim 1, wherein in the step (3), the bismuth source: a cadmium source: the mass ratio of the bromine source is 1; the drying temperature is 50-80 ℃, and the reaction time is 12-24 hours.
7. A Sillen-type bimetallic oxyhalide for antibiotic degradation, characterized in that it is obtainable by the process according to any one of claims 1 to 6.
8. Use of the Sillen-type bimetallic oxyhalide for antibiotic degradation according to claim 7 for the photocatalytic degradation of the organic dye ciprofloxacin.
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CN107684918A (en) * 2017-08-11 2018-02-13 江苏大学 A kind of Porous hollow PbBiO2The preparation method and its usage of Cl catalysis materials
CN109794271A (en) * 2019-01-28 2019-05-24 江苏大学 A kind of ultra-thin PbBiO of oxygen-enriched defect2The preparation method and its usage of Br nanometer sheet

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CN107684918A (en) * 2017-08-11 2018-02-13 江苏大学 A kind of Porous hollow PbBiO2The preparation method and its usage of Cl catalysis materials
CN109794271A (en) * 2019-01-28 2019-05-24 江苏大学 A kind of ultra-thin PbBiO of oxygen-enriched defect2The preparation method and its usage of Br nanometer sheet

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