CN114797906B - BiOCl@Bi 2 S 3 In-situ synthesis method and application of composite material - Google Patents
BiOCl@Bi 2 S 3 In-situ synthesis method and application of composite material Download PDFInfo
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- CN114797906B CN114797906B CN202110108476.7A CN202110108476A CN114797906B CN 114797906 B CN114797906 B CN 114797906B CN 202110108476 A CN202110108476 A CN 202110108476A CN 114797906 B CN114797906 B CN 114797906B
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- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 239000002131 composite material Substances 0.000 title claims abstract description 28
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 17
- 238000001308 synthesis method Methods 0.000 title claims abstract description 11
- 239000000243 solution Substances 0.000 claims abstract description 50
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000011259 mixed solution Substances 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000003242 anti bacterial agent Substances 0.000 claims abstract description 11
- 229940088710 antibiotic agent Drugs 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 11
- JZRWCGZRTZMZEH-UHFFFAOYSA-N thiamine Chemical compound CC1=C(CCO)SC=[N+]1CC1=CN=C(C)N=C1N JZRWCGZRTZMZEH-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 9
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 9
- 238000000926 separation method Methods 0.000 claims abstract description 8
- 229930003270 Vitamin B Natural products 0.000 claims abstract description 6
- 235000019156 vitamin B Nutrition 0.000 claims abstract description 6
- 239000011720 vitamin B Substances 0.000 claims abstract description 6
- 238000010335 hydrothermal treatment Methods 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims abstract description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 13
- MYSWGUAQZAJSOK-UHFFFAOYSA-N ciprofloxacin Chemical compound C12=CC(N3CCNCC3)=C(F)C=C2C(=O)C(C(=O)O)=CN1C1CC1 MYSWGUAQZAJSOK-UHFFFAOYSA-N 0.000 claims description 8
- 239000011941 photocatalyst Substances 0.000 claims description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical compound O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FBXVOTBTGXARNA-UHFFFAOYSA-N 0.000 claims description 6
- OGJPXUAPXNRGGI-UHFFFAOYSA-N norfloxacin Chemical compound C1=C2N(CC)C=C(C(O)=O)C(=O)C2=CC(F)=C1N1CCNCC1 OGJPXUAPXNRGGI-UHFFFAOYSA-N 0.000 claims description 6
- 229960001180 norfloxacin Drugs 0.000 claims description 6
- 230000003115 biocidal effect Effects 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000003786 synthesis reaction Methods 0.000 claims description 5
- 229960003405 ciprofloxacin Drugs 0.000 claims description 4
- GSDSWSVVBLHKDQ-UHFFFAOYSA-N 9-fluoro-3-methyl-10-(4-methylpiperazin-1-yl)-7-oxo-2,3-dihydro-7H-[1,4]oxazino[2,3,4-ij]quinoline-6-carboxylic acid Chemical compound FC1=CC(C(C(C(O)=O)=C2)=O)=C3N2C(C)COC3=C1N1CCN(C)CC1 GSDSWSVVBLHKDQ-UHFFFAOYSA-N 0.000 claims description 3
- KIPLYOUQVMMOHB-MXWBXKMOSA-L [Ca++].CN(C)[C@H]1[C@@H]2[C@@H](O)[C@H]3C(=C([O-])[C@]2(O)C(=O)C(C(N)=O)=C1O)C(=O)c1c(O)cccc1[C@@]3(C)O.CN(C)[C@H]1[C@@H]2[C@@H](O)[C@H]3C(=C([O-])[C@]2(O)C(=O)C(C(N)=O)=C1O)C(=O)c1c(O)cccc1[C@@]3(C)O Chemical compound [Ca++].CN(C)[C@H]1[C@@H]2[C@@H](O)[C@H]3C(=C([O-])[C@]2(O)C(=O)C(C(N)=O)=C1O)C(=O)c1c(O)cccc1[C@@]3(C)O.CN(C)[C@H]1[C@@H]2[C@@H](O)[C@H]3C(=C([O-])[C@]2(O)C(=O)C(C(N)=O)=C1O)C(=O)c1c(O)cccc1[C@@]3(C)O KIPLYOUQVMMOHB-MXWBXKMOSA-L 0.000 claims description 3
- 229960001699 ofloxacin Drugs 0.000 claims description 3
- 229940063650 terramycin Drugs 0.000 claims description 3
- KKMOSYLWYLMHAL-UHFFFAOYSA-N 2-bromo-6-nitroaniline Chemical compound NC1=C(Br)C=CC=C1[N+]([O-])=O KKMOSYLWYLMHAL-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 239000004098 Tetracycline Substances 0.000 claims description 2
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 claims description 2
- 230000000593 degrading effect Effects 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- 229960002135 sulfadimidine Drugs 0.000 claims description 2
- ASWVTGNCAZCNNR-UHFFFAOYSA-N sulfamethazine Chemical compound CC1=CC(C)=NC(NS(=O)(=O)C=2C=CC(N)=CC=2)=N1 ASWVTGNCAZCNNR-UHFFFAOYSA-N 0.000 claims description 2
- 229960005404 sulfamethoxazole Drugs 0.000 claims description 2
- JLKIGFTWXXRPMT-UHFFFAOYSA-N sulphamethoxazole Chemical compound O1C(C)=CC(NS(=O)(=O)C=2C=CC(N)=CC=2)=N1 JLKIGFTWXXRPMT-UHFFFAOYSA-N 0.000 claims description 2
- 229960002180 tetracycline Drugs 0.000 claims description 2
- 229930101283 tetracycline Natural products 0.000 claims description 2
- 235000019364 tetracycline Nutrition 0.000 claims description 2
- 150000003522 tetracyclines Chemical class 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 239000012855 volatile organic compound Substances 0.000 claims 4
- 230000015556 catabolic process Effects 0.000 abstract description 17
- 238000006731 degradation reaction Methods 0.000 abstract description 17
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 7
- 239000003054 catalyst Substances 0.000 abstract description 7
- 239000011593 sulfur Substances 0.000 abstract description 7
- 229910052717 sulfur Inorganic materials 0.000 abstract description 7
- 239000004094 surface-active agent Substances 0.000 abstract description 5
- 230000006798 recombination Effects 0.000 abstract description 4
- 238000005215 recombination Methods 0.000 abstract description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 229940073609 bismuth oxychloride Drugs 0.000 abstract description 3
- 239000000460 chlorine Substances 0.000 abstract description 3
- 229910052801 chlorine Inorganic materials 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 238000005530 etching Methods 0.000 abstract description 3
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 3
- 239000000463 material Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 10
- 230000001351 cycling effect Effects 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- 230000001699 photocatalysis Effects 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 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
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 1
- 229910001152 Bi alloy Inorganic materials 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- RLUTZWOWBMJUQY-UHFFFAOYSA-K O.O.O.O.O.[Bi](Cl)(Cl)Cl Chemical compound O.O.O.O.O.[Bi](Cl)(Cl)Cl RLUTZWOWBMJUQY-UHFFFAOYSA-K 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- -1 bismuth citrate pentahydrate Chemical compound 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000593 microemulsion method Methods 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- DPJRMOMPQZCRJU-UHFFFAOYSA-M thiamine hydrochloride Chemical compound Cl.[Cl-].CC1=C(CCO)SC=[N+]1CC1=CN=C(C)N=C1N DPJRMOMPQZCRJU-UHFFFAOYSA-M 0.000 description 1
- 238000005303 weighing Methods 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
- B01J27/06—Halogens; Compounds thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8678—Removing components of undefined structure
- B01D53/8687—Organic components
-
- 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
- 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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/343—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the pharmaceutical industry, e.g. containing antibiotics
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Thermal Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Physics & Mathematics (AREA)
- Water Supply & Treatment (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
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Abstract
The invention discloses a BiOCl@Bi 2 S 3 The in-situ synthesis method and application of the composite material comprise the following steps: dissolving bismuth source in alcohol solution to obtain solution A; (2) Vitamin B 1 Dissolving hydrochloride in water to obtain a solution B, and then adding the solution B into the solution A under stirring to obtain a mixed solution C; (3) Carrying out hydrothermal treatment on the mixed solution C, and carrying out solid-liquid separation, washing and drying to obtain the BiOCl@Bi 2 S 3 A composite material. The invention uses vitamin B 1 The hydrochloride is used as a chlorine source and a sulfur source and is used as a surfactant, and is subjected to vitamin B after bismuth oxychloride is generated 1 In-situ etching of a sulfur source decomposed by hydrochloride is beneficial to BiOCl and Bi 2 S 3 The heterojunction is built by recombination, the separation of photo-generated electrons and holes is promoted, the degradation of antibiotics and volatile organic pollutants (VOCs) can be efficiently catalyzed under the condition of visible light, and the activity of the catalyst is almost unchanged after the catalyst is recycled for many times.
Description
Technical Field
The invention belongs to the technical field of material preparation and environmental protection, and in particular relates to a BiOCl@Bi alloy 2 S 3 In-situ synthesis method of composite materialThe method is applied to visible light catalytic antibiotic degradation and VOCs degradation.
Background
The method adopts the visible light catalytic technology, directly utilizes solar energy to realize complete mineralization and degradation of toxic and harmful organic pollutants in the environment through the semiconductor photocatalytic material, is a low-cost green common technology, and has good application prospect in the field of environmental protection. The key of the visible light catalysis technology is the development of efficient and stable semiconductor catalysts. The existing semiconductor photocatalyst mainly has the following problems: (1) Part of semiconductor materials have low light absorption efficiency and can only absorb ultraviolet light (accounting for 4 percent of solar energy); (2) The photo-generated holes and electrons are easy to be combined, and the separation efficiency is low; (3) The preparation process of the photocatalyst is complex, and toxic and harmful solvents or structure directing agents are required to be introduced; (4) it is difficult to realize mass production of the photocatalyst. Therefore, the development of a green, simple and easily-produced photocatalyst synthesis method in large scale has important significance in preparing the efficient and stable visible light catalyst.
BiOCl and Bi 2 S 3 The material has a lamellar structure, and the forbidden band width is respectively 3.0-3.5 eV and 1.3-1.7 eV. The BiOCl has a larger forbidden bandwidth and usually has better photocatalytic activity only in the ultraviolet region. Bi (Bi) 2 S 3 The narrow forbidden band width is a potential photocatalyst responding to visible light, but due to the fact that the valence band and the conduction band are relatively close, the photo-generated electron-hole recombination rate is high, and the photo-generated electron-hole recombination rate is generally required to be compounded with other materials to show good catalytic activity. BiOCl and Bi have been reported in the literature 2 S 3 The heterojunction is built by compounding, so that the visible light absorption is improved, the generation of photo-generated electrons and holes is facilitated, the separation of the photo-generated electrons and the holes is promoted, and the photocatalysis performance is improved.
Currently synthesizing BiOCl and Bi 2 S 3 The composite material is prepared by a hydrolysis method, a water (solvent) thermal method, an alcohol thermal method, a soft template method, a high-temperature solid phase method, a reverse microemulsion method and the like, and is etched by a sulfur source, so that the synthesis process is complex, and acid or alkali and a surfactant are generally required to be added.
Disclosure of Invention
In order to solve the problems existing in the prior art, the invention aims to provide a BiOCl@Bi 2 S 3 In-situ synthesis method of composite material by using vitamin B 1 The hydrochloride is used as a chlorine source and a sulfur source and is used as a surfactant, and is subjected to vitamin B after bismuth oxychloride is generated 1 In-situ etching of a sulfur source decomposed by hydrochloride is beneficial to BiOCl and Bi 2 S 3 The heterojunction is built by recombination, the separation of photo-generated electrons and holes is promoted, the degradation of antibiotics and volatile organic pollutants (VOCs) can be efficiently catalyzed under the condition of visible light, and the activity of the catalyst is almost unchanged after the catalyst is recycled for many times.
In order to solve the problems, the invention adopts the following technical scheme:
BiOCl@Bi 2 S 3 The in-situ synthesis method of the composite material comprises the following steps:
(1) Dissolving a bismuth source in an alcohol solution to obtain a solution A;
(2) Vitamin B 1 Dissolving hydrochloride in water to obtain a solution B, and then adding the solution B into the solution A under stirring to obtain a mixed solution C;
(3) Carrying out hydrothermal treatment on the mixed solution C, and carrying out solid-liquid separation, washing and drying to obtain the BiOCl@Bi 2 S 3 A composite material.
Preferably, in the step (1), the bismuth source is selected from one or more of bismuth nitrate pentahydrate, bismuth chloride and bismuth citrate.
Preferably, in the step (1), the alcohol is one or more selected from methanol, ethanol, isopropanol, ethylene glycol and glycerol.
Preferably, in the step (1), the concentration of the bismuth source in the solution A is 0.05-0.2 mol/L.
Preferably, in step (2), vitamin B is present in the solution B 1 The concentration of the hydrochloride is 0.1 to 0.5mol/L.
Preferably, in step (2), the bismuth source and vitamin B 1 The molar ratio of the hydrochloride is 1-5: 1.
preferably, in the step (3), the temperature of the hydrothermal treatment is 80-160 ℃ and the time is 6-24 hours.
The invention also provides the synthesized BiOCl@Bi 2 S 3 The application of the composite material takes the composite material as a photocatalyst for degrading antibiotics or VOCs under visible light;
the method comprises the following specific steps: at room temperature, biOCl@Bi 2 S 3 The composite material is added into water with the concentration of 15-150 mg/L of antibiotics or gas with the concentration of 0.2-2 mg/L of VOCs, and the reaction is carried out for 0.1-12 h.
Preferably, the antibiotic is selected from one or more of ciprofloxacin, norfloxacin, ofloxacin, tetracycline, sulfamethoxazole, sulfadimidine and terramycin, and the BiOCl@Bi 2 S 3 The mass ratio of the composite material to the antibiotics is 1:0.01 to 0.1.
Preferably, the VOCs are selected from one or more of formaldehyde, toluene, benzene and xylene, and the BiOCl@Bi 2 S 3 The mass ratio of the composite material to the VOCs is 1: 0.005-0.05.
Compared with the prior art, the invention has the technical effects that:
1. vitamin B in the invention 1 The hydrochloride is used as a chlorine source and a sulfur source and is also used as a surfactant, so that a uniform structure is formed, and acid, alkali and the surfactant are avoided.
2. The invention adopts an in-situ synthesis method, and is covered with vitamin B after bismuth oxychloride is generated 1 And the in-situ etching of the sulfur source decomposed by the hydrochloride is beneficial to constructing a heterojunction and promoting the separation of photo-generated electrons and holes.
3. BiOCl@Bi in the invention 2 S 3 The composite material can efficiently catalyze degradation of antibiotics and VOCs under visible light, and the catalytic material can be recycled.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to specific embodiments. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Example 1
At room temperature, 5mmol of bismuth nitrate pentahydrate is weighed and dissolved in 100mL of glycol solution to obtain solution A; 5mmol vitamin B 1 Dissolving hydrochloride in 10mL of water to obtain a solution B; then slowly dripping the solution B into the solution A under stirring to obtain a mixed solution C; sealing the mixed solution C in a crystallization kettle, treating at 160 ℃ for 6 hours, cooling, washing and drying to obtain a material which is BiOCl@Bi 2 S 3 -1 a composite material.
Example 2
At room temperature, 5mmol of bismuth citrate pentahydrate is weighed and dissolved in 50mL of isopropanol solution to obtain solution A; 1mmol vitamin B 1 Dissolving hydrochloride in 10mL of water to obtain a solution B; then slowly dripping the solution B into the solution A under stirring to obtain a mixed solution C; sealing the mixed solution C in a crystallization kettle, treating for 12 hours at 105 ℃, cooling, washing and drying to obtain a material which is BiOCl@Bi 2 S 3 -2 a composite material.
Example 3
Weighing 5mmol of bismuth chloride pentahydrate, and dissolving in 25mL of ethanol solution at room temperature to obtain solution A; 2mmol vitamin B 1 Dissolving hydrochloride in 10mL of water to obtain a solution B; then slowly dripping the solution B into the solution A under stirring to obtain a mixed solution C; sealing the mixed solution C in a crystallization kettle, treating at 80 ℃ for 24 hours, cooling, washing and drying to obtain a material which is BiOCl@Bi 2 S 3 -3 a composite material.
Example 4
At room temperature, 5mmol of bismuth nitrate pentahydrate is weighed and dissolved in 50mL of glycol solution to obtain solution A; 1.67mmol vitamin B 1 Dissolving hydrochloride in 10mL of water to obtain a solution B; then slowly dripping the solution B into the solution A under stirring to obtain a mixed solution C; sealing the mixed solution C in a crystallization kettle, treating at 135 ℃ for 12 hours, cooling, washing and drying to obtain a material which is BiOCl@Bi 2 S 3 -4 a composite material.
Comparative example 1
At room temperature, 5mmol of bismuth nitrate pentahydrate is weighed and dissolved in 50mL of glycol solution to obtain solution A; 2.5mmol vitamin B 1 Hydrochloride saltDissolving in 10mL of water to obtain a solution B; solution B was then slowly added dropwise to solution a with stirring, stirred for 12h, cooled, washed and dried and the resulting material was designated BiOCl.
Comparative example 2
At room temperature, 5mmol of bismuth nitrate pentahydrate is weighed and dissolved in 50mL of glycol solution to obtain solution A; will 10 mmole Na 2 S is dissolved in 30mL of water to obtain solution B; then slowly dropwise adding the solution B into the solution A under stirring, stirring for 12h, cooling, washing and drying to obtain a material which is named Bi 2 S 3 。
Comparative example 3
1.3g of BiOCl (5 mmol) prepared in comparative example 1 was weighed and ultrasonically dispersed in 50mL of ethylene glycol to obtain dispersion A; 1.28g of Bi prepared in comparative example 2 was weighed 2 S 3 (2.5 mmol) was ultrasonically dispersed in 20mL of water to give dispersion B; slowly dripping the dispersion liquid B into the dispersion liquid A, stirring for 12 hours, washing and drying to obtain a material which is BiOCl@Bi 2 S 3 -5。
Antibiotic degradation:
at room temperature, 40mg of the materials prepared in examples 1-4 and comparative examples 1-3 were added into 40mL of an aqueous solution containing antibiotics at a certain concentration, dispersed by light-shielding ultrasonic for 15min, subjected to dark reaction for 30min, turned on a 300W xenon lamp light source, filtered to remove the catalyst after a certain period of reaction, the residual concentration was detected, and the degradation rate was calculated as shown in Table 1:
TABLE 1 antibiotic degradation Rate data sheet
| Example 1 | Example 2 | Example 3 | Example 4 | Comparative example 1 | Comparative example 2 | Comparative example 3 | |
| Antibiotics | Ciprofloxacin | Terramycin | Ofloxacin | Norfloxacin | Norfloxacin | Norfloxacin | Norfloxacin |
| Degradation time (h) | 12 | 7.5 | 4.5 | 1 | 1 | 1 | 1 |
| Initial concentration (mg/L) | 100 | 60 | 45 | 10 | 10 | 10 | 10 |
| Residue ofConcentration (mg/L) | 3.5 | 4.1 | 2.8 | 0.12 | 5.8 | 6.9 | 3.2 |
| Degradation rate (%) | 96.5 | 93.2 | 93.8 | 98.8 | 42 | 31 | 68 |
TABLE 2 BiOCl@Bi of example 1 2 S 3 -1 degradation cycle performance of ciprofloxacin with catalytic initial concentration of 100mg/L
| Circulation for 1 time | Cycling for 2 times | Cycling 3 times | Circulation for 4 times | Cycling 5 times | |
| Degradation rate (%) | 96.5 | 96.3 | 96.0 | 96.0 | 95.8 |
Note that: after single use, the product is filtered, washed and dried for repeated use.
VOCs degradation:
100mg of the materials prepared in examples 1-4 and comparative examples 1-3 were added to 250mL of VOCs gas with a certain concentration at room temperature, a 300W xenon lamp light source was turned on, after a certain period of reaction, a gas sampler was used for sampling and detecting the residual concentration, and the adsorption rate was calculated as shown in Table 3:
TABLE 3 VOCs degradation Rate data sheet
TABLE 4 BiOCl@Bi for example 4 2 S 3 -4 photocatalytic initial concentration of 1mg/L formaldehyde gas degradation cycle usability
| Circulation for 1 time | Cycling for 2 times | Cycling 3 times | Circulation for 4 times | Cycling 5 times | |
| Degradation rate (%) | 99.2 | 99.1 | 99.1 | 99.0 | 98.7 |
Note that: and after the single use is finished, the product is directly reused.
Claims (9)
1. BiOCl@Bi 2 S 3 The in-situ synthesis method of the composite material is characterized by comprising the following steps of:
(1) Dissolving a bismuth source in an alcohol solution to obtain a solution A;
the alcohol is one or more selected from methanol, ethanol, isopropanol, ethylene glycol and glycerol;
(2) Vitamin B 1 Dissolving hydrochloride in water to obtain a solution B, and then adding the solution B into the solution A under stirring to obtain a mixed solution C;
(3) Carrying out hydrothermal treatment on the mixed solution C, and carrying out solid-liquid separation, washing and drying to obtain the BiOCl@Bi 2 S 3 A composite material.
2. The in situ synthesis process according to claim 1, wherein: in the step (1), the bismuth source is selected from one or more of bismuth nitrate pentahydrate, bismuth chloride and bismuth citrate.
3. The in situ synthesis process according to claim 1, wherein: in the step (1), the concentration of the bismuth source in the solution A is 0.05-0.2 mol/L.
4. The in situ synthesis process according to claim 1, wherein: in the step (2), vitamin B in the solution B 1 The concentration of the hydrochloride is 0.1-0.5 mol/L.
5. A BiOCl@Bi according to claim 1 2 S 3 The in-situ synthesis method of the composite material is characterized by comprising the following steps of: in step (2), the bismuth source and vitamin B 1 The molar ratio of the hydrochloride is 1-5: 1.
6. the in situ synthesis process according to claim 1, wherein: in the step (3), the temperature of the hydrothermal treatment is 80-160 DEG C o And C, the time is 6-24 hours.
7. The BiOCl@Bi synthesized by the in-situ synthesis method as claimed in any one of claims 1 to 6 2 S 3 The application of the composite material is characterized in that: the photocatalyst is used as a photocatalyst for degrading antibiotics or VOCs under visible light;
the method comprises the following specific steps: at room temperature, biOCl@Bi 2 S 3 The composite material is added into water with the concentration of 15-150 mg/L of antibiotics or gas with the concentration of 0.2-2 mg/L of VOCs, and the reaction is carried out for 0.1-12 h.
8. The BiOCl@Bi according to claim 7 2 S 3 The application of the composite material is characterized in that: the antibiotic is selected from one or more of ciprofloxacin, norfloxacin, ofloxacin, tetracycline, sulfamethoxazole, sulfamethazine and terramycin, and the BiOCl@Bi 2 S 3 The mass ratio of the composite material to the antibiotics is 1:0.01 to 0.1.
9. The BiOCl@Bi according to claim 7 2 S 3 The application of the composite material is characterized in that: by a means ofThe VOCs are selected from one or more of formaldehyde, toluene, benzene and xylene, and the BiOCl@Bi 2 S 3 The mass ratio of the composite material to the VOCs is 1: 0.005-0.05.
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