CN113058655A - Preparation method and application of BiOCl/Fe-MOFs composite catalytic material - Google Patents
Preparation method and application of BiOCl/Fe-MOFs composite catalytic material Download PDFInfo
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- CN113058655A CN113058655A CN202110336642.9A CN202110336642A CN113058655A CN 113058655 A CN113058655 A CN 113058655A CN 202110336642 A CN202110336642 A CN 202110336642A CN 113058655 A CN113058655 A CN 113058655A
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- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 239000002131 composite material Substances 0.000 title claims abstract description 49
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 47
- 239000000463 material Substances 0.000 title claims abstract description 46
- 239000013082 iron-based metal-organic framework Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 239000000243 solution Substances 0.000 claims abstract description 46
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 39
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims abstract description 22
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 claims abstract description 11
- 229960002089 ferrous chloride Drugs 0.000 claims abstract description 11
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims abstract description 11
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 11
- 239000007864 aqueous solution Substances 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000003054 catalyst Substances 0.000 claims description 12
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 239000011541 reaction mixture Substances 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910001451 bismuth ion Inorganic materials 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 229910021645 metal ion Inorganic materials 0.000 claims description 6
- 239000006228 supernatant Substances 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 238000004065 wastewater treatment Methods 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 239000000047 product Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 abstract description 9
- 239000002351 wastewater Substances 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 8
- 230000003647 oxidation Effects 0.000 abstract description 6
- 238000007254 oxidation reaction Methods 0.000 abstract description 6
- 230000000593 degrading effect Effects 0.000 abstract description 3
- 239000003960 organic solvent Substances 0.000 abstract description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- 230000015556 catabolic process Effects 0.000 description 11
- 238000006731 degradation reaction Methods 0.000 description 11
- 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 description 9
- 229940043267 rhodamine b Drugs 0.000 description 9
- 230000001699 photocatalysis Effects 0.000 description 6
- 239000013144 Fe-MIL-100 Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000012621 metal-organic framework Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 230000027756 respiratory electron transport chain Effects 0.000 description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- 229940073609 bismuth oxychloride Drugs 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 238000010525 oxidative degradation reaction Methods 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 1
- 239000013291 MIL-100 Substances 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 238000009303 advanced oxidation process reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- UXGNZZKBCMGWAZ-UHFFFAOYSA-N dimethylformamide dmf Chemical compound CN(C)C=O.CN(C)C=O UXGNZZKBCMGWAZ-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 238000005375 photometry Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/842—Iron
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The invention belongs to the field of advanced oxidation advanced treatment of wastewater, and particularly relates to preparation and application of a BiOCl/Fe-MOFs composite catalytic material, which is suitable for removing organic pollutants in wastewater. The preparation method comprises the step of mixing and reacting ferrous chloride, a bismuth trichloride aqueous solution and a sodium hydroxide solution of trimesic acid to obtain the BiOCl/Fe-MOFs composite catalytic material. The preparation method has the advantages of high preparation speed, adjustable product composition, high purity, simple preparation method, no need of special equipment, no need of DMF (dimethyl formamide), ethylene glycol and other organic solvents, low cost, green and environment-friendly preparation process, and suitability for industrializationProduction, can meet the requirement of practical application, and has good catalysis H under the assistance of visible light2O2Persulfate, O3The isooxygen source has the effect of degrading organic matters.
Description
Technical Field
The invention belongs to the field of advanced oxidation advanced treatment of wastewater, and particularly relates to preparation and application of a BiOCl/Fe-MOFs composite catalytic material, which is suitable for removing organic pollutants in wastewater.
Background
At present, printing and dyeingThe discharged wastewater of the industries such as medicine, chemical industry and the like contains a large amount of organic matters, the wastewater has high concentration, high toxicity and poor biodegradability, and along with the improvement of the current wastewater discharge standard, the ideal removal effect cannot be achieved by simply depending on a physical and biological degradation method, so that the industry has attracted great attention. Advanced oxidation technology has been widely used as an efficient, environmentally friendly technology in the removal of harmful and toxic organic compounds from wastewater. The advanced oxidation technology generally utilizes a catalyst to catalyze active oxygen substances ROS such as hydrogen peroxide, persulfate or ozone to generate hydroxyl radicals, persulfate radicals, superoxide radicals and the like with strong oxidizing property, and the ROS oxidize various toxic and non-degradable organic compounds so as to achieve the purpose of removing pollutants. The MOFs has the advantages of high porosity, large specific surface area and the like, and the Lewis acid Fe in the framework3+The component can be used as an active center of heterogeneous Fenton reaction and can activate H2O2Persulfate, O3Etc. generate ROS to degrade organic pollutants. However, Fe in the advanced oxidation process3+/Fe2+The electron transfer speed in the circulating process directly determines the catalytic oxidation efficiency. Researches show that visible light can effectively promote Fe3+Reduction to Fe2+Thereby accelerating the degradation of the organic pollutants. MIL-100(Fe) has good absorption effect in the visible light range, has certain photocatalytic performance, but is not efficient. Bismuth oxychloride BiOCl is used as a layered indirect transition band gap semiconductor material, has a unique electronic structure and a unique crystal structure, and can efficiently degrade organic pollutants under the drive of visible light. However, the wide energy band of bismuth oxychloride (Eg. about.3.6 eV) limits the utilization of solar energy, particularly the visible light part, and the photocatalytic reaction efficiency is limited because the photoproduction electron hole is easy to recombine. Therefore, by preparing the BiOCl/Fe-MOFs composite material and constructing a heterojunction, on one hand, the photogenerated electron hole recombination is prevented, the photocatalysis efficiency is improved, on the other hand, the electron transfer is accelerated, and the Fe is promoted3+Rapidly reduced to Fe2+Accelerate H2O2Etc., enhance the generation of ROS, thereby promoting the rapid oxidative degradation of organic pollutants.
Currently, a complex of BiOX (X ═ Cl, Br) and a metal organic framework material has been reported, and the decomposition of pollutants can be effectively improved. However, the synthesis methods of these composite materials are complex, generally adopt a hydrothermal method or solvothermal method to synthesize the MOFs first and then compound the BiOX, or synthesize the BiOX first and then compound the MOFs by the hydrothermal method, and organic solvents such as N, N-dimethylformamide DMF, ethylene glycol EG and the like are mostly used in the preparation reaction, and the whole preparation process is not environment-friendly and is not suitable for large-scale production.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a preparation method of a BiOCl/Fe-MOFs composite catalytic material. The composite material prepared by the method has the advantages of good photocatalytic response, simple preparation method, mild conditions, low cost, green and environment-friendly preparation process and capability of large-scale industrial production. Heterojunction is constructed by BiOCl/Fe-MOFs compounding, so that the photo-generated electron hole compounding is reduced, and the photocatalysis efficiency is improved; accelerates electron transfer and promotes Fe3+Rapidly reduced to Fe2+Acceleration H2O2And the like, and the generation of ROS, the rapid oxidative degradation of organic pollutants is enhanced.
The technical scheme adopted by the invention for solving the technical problems is as follows:
the invention aims to provide a preparation method of a BiOCl/Fe-MOFs composite catalytic material, which comprises the step of mixing ferrous chloride, a bismuth trichloride aqueous solution and a sodium hydroxide solution of trimesic acid for reaction to obtain the BiOCl/Fe-MOFs composite catalytic material. The BiOCl/Fe-MOFs composite catalytic material is a nano material formed by MIL-100(Fe) growing and inserting between BiOCl sheets.
Preferably, the preparation method comprises the following steps:
(1) dissolving ferrous chloride tetrahydrate in deionized water, adding bismuth chloride according to a certain molar ratio, and stirring to dissolve to obtain a solution A;
(2) adding trimesic acid into a sodium hydroxide solution, keeping the temperature of the solution at 60-70 ℃, and stirring and dissolving to obtain a solution B;
(3) slowly dripping the solution B in the step (2) into the solution A, continuously stirring at room temperature for reacting for 6 hours after dripping is finished, and carrying out post-treatment on the obtained product to obtain the BiOCl/Fe-MOFs composite catalytic material of light yellow powder solid.
Preferably, in the preparation method, the molar ratio of the metal salt to the trimesic acid, the NaOH and the water is 1.5:1:3: 750-900, the metal salt comprises ferrous chloride and bismuth chloride, and the molar fraction of the bismuth ions in the total metal ions is 0-100%.
Preferably, the concentration of the sodium hydroxide solution in the step (2) is 1 mol/L.
Preferably, the solution B in the step (3) is added into the solution A at a rate of 0.3-0.6 mL/min.
Preferably, the stirring reaction rate in the step (3) is 300-500 r/min.
Preferably, the reaction temperature in the step (3) is room temperature, the room temperature is 15-35 ℃, and more preferably, the reaction temperature is 20-30 ℃.
Preferably, the post-treatment in the step (3) is that after the reaction is finished, the reaction mixture is kept stand, supernatant liquid is poured out, and the reaction mixture is soaked, centrifuged and washed with water and absolute ethyl alcohol at 50-70 ℃ for 3-5 times respectively, and then dried in vacuum at 60 ℃ to obtain final powder solid.
The invention also aims to provide the application of the BiOCl/Fe-MOFs composite catalytic material obtained by the preparation method of the BiOCl/Fe-MOFs composite catalytic material in wastewater treatment.
Preferably, the application conditions of the BiOCl/Fe-MOFs composite catalytic material in wastewater treatment are that the BiOCl/Fe-MOFs composite catalytic material is used as a catalyst, hydrogen peroxide or persulfate or O is used at 15-50 DEG C3The catalyst is an oxygen source, under the assistance of visible light, the pH value is 4-7, organic pollutants in water can be rapidly degraded, the TOC removal rate can reach more than 80%, and the catalytic performance is basically unchanged after the catalyst is repeatedly used for 5 times.
According to the invention, the BiOCl/Fe-MOFs composite catalyst is prepared by combining two photocatalytic materials of BiOCl and MIL-100(Fe) through a one-pot coprecipitation method and constructing a heterojunction, and the defects of complexity, high cost, difficulty in controlling product components and the like of the existing composite catalytic material preparation method are overcome. The BiOCl/Fe-MOFs composite catalyst prepared by the invention has the characteristics of large specific surface area, high porosity, wide light absorption range, low photo-generated electron hole recombination rate and the like, and can obviously accelerate the decomposition and oxidation of organic pollutants in water by hydrogen peroxide, persulfate or ozone under the assistance of visible light. The composite catalytic material prepared by the preparation method has low preparation cost, high catalytic activity and strong applicability, and has important practical significance for development of novel and efficient heterogeneous Fenton catalysts, depth of wastewater and solution of promoting environment.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention provides a one-step coprecipitation method for preparing BiOCl/Fe-MOFs composite catalytic material, which has the advantages of simple preparation method, no need of special equipment, no need of organic solvents such as DMF (dimethyl formamide) and ethylene glycol, low cost, green and environment-friendly preparation process, suitability for industrial production and capability of meeting the actual application requirement;
(2) the preparation method provided by the invention has the advantages that the preparation speed is high, the composition of BiOCl and MIL-100(Fe) in the composite material is adjustable, and the purity is high;
(3) the composite catalytic material prepared by the invention has good catalytic activity on H under the assistance of visible light2O2Persulfate, O3The isooxygen source has the effect of degrading organic matters.
Drawings
FIG. 1 is an SEM image of a BiOCl/Fe-MOFs composite catalytic material;
FIG. 2 is an XRD spectrum of the composite catalytic material with different BiOCl/Fe-MOFs ratios;
FIG. 3 shows the degradation effect of rhodamine B under different catalytic conditions;
FIG. 4 is a relation between the repeated degradation times and the degradation rate of the BiOCl/Fe-MOFs composite catalytic material.
Detailed Description
The technical solution of the present invention is further specifically described below by way of specific examples in conjunction with the accompanying drawings.
Example 1
1.926g (9.69mmol) of ferrous chloride tetrahydrate is weighed out and dissolved in 97.2g of deionized water, and then 0.539g (1.71mmol) of bismuth trichloride is added and dissolved in the solution to obtain a mixed solution A, wherein the molar fraction of bismuth ions in the metal ions is 15%. Adding 1.676g (7.6mmol) of trimesic acid into 23.72g of 1mol/L NaOH (22.8mmol), heating to 60-70 ℃, and stirring for dissolving to obtain a clear solution B. Then, solution B was slowly added dropwise to solution A at a rate of 0.5mL/min, and the reaction was continued at 30 ℃ with stirring at a rate of 400r/min for 6 h. Standing the obtained reaction mixture, pouring out supernatant, soaking with hot water and absolute ethyl alcohol, washing, centrifuging for multiple times, and drying in a vacuum drying oven at 60 ℃ to obtain the final BiOCl/Fe-MOFs composite catalytic material, wherein FIG. 1 is an SEM (scanning electron microscope) diagram of the BiOCl/Fe-MOFs composite catalytic material.
Example 2
1.473g (7.41mmol) of ferrous chloride tetrahydrate is weighed and dissolved in 97.2g of deionized water, and then 1.528g (3.991mmol) of bismuth trichloride is added and dissolved in the solution to obtain a mixed solution A, wherein the molar fraction of bismuth ions in the metal ions is 35%. 1.676g (7.6mmol) of trimesic acid was added to 23.72g of a 1mol/L NaOH (22.8mmol) solution and heated to 60-70 ℃ to obtain a clear solution B. Solution B was then slowly added dropwise to solution A at a rate of 0.3mL/min, and stirring was continued at 35 ℃ at a rate of 300r/min for 6 h. And standing the obtained reaction mixture, pouring out supernatant, soaking in hot water and absolute ethyl alcohol, washing, centrifuging for multiple times, and drying in a vacuum drying oven at 60 ℃ to obtain the final BiOCl/Fe-MOFs composite catalytic material.
Example 3
1.133g (5.70mmol) of ferrous chloride tetrahydrate is weighed and dissolved in 97.2g of deionized water, and 1.797g (5.70mmol) of bismuth trichloride is added and dissolved in the solution to obtain a mixed solution A, wherein the molar fraction of bismuth ions in the metal ions is 50%. 1.676g (7.6mmol) of trimesic acid was added to 23.72g of a 1mol/L NaOH (22.8mmol) solution and heated to 60-70 ℃ to obtain a clear solution B. Solution B was then slowly added dropwise to solution A at a rate of 0.6mL/min, and stirring was continued at 20 ℃ at a rate of 500r/min for 6 h. And standing the obtained reaction mixture, pouring out supernatant, soaking in hot water and absolute ethyl alcohol, washing, centrifuging for multiple times, and drying in a vacuum drying oven at 60 ℃ to obtain the final BiOCl/Fe-MOFs composite catalytic material.
Example 4
0.688g (3.42mmol) of ferrous chloride tetrahydrate is weighed out and dissolved in 97.2g of deionized water, and then 2.516g (7.98mmol) of bismuth trichloride is added and dissolved in the solution to obtain a mixed solution A, wherein the mole fraction of bismuth ions in the metal ions is 70%. 1.676g (7.6mmol) of trimesic acid was added to 23.72g of a 1mol/L NaOH (22.8mmol) solution and heated to 60-70 ℃ to obtain a clear solution B. Solution B was then slowly added dropwise to solution A at a rate of 0.5mL/min, and stirring was continued at room temperature at 400r/min for 6 h. And standing the obtained reaction mixture, pouring out supernatant, soaking in hot water and absolute ethyl alcohol, washing, centrifuging for multiple times, and drying in a vacuum drying oven at 60 ℃ to obtain the final BiOCl/Fe-MOFs composite catalytic material.
Test example 1
H is catalytically activated by the BiOCl/Fe-MOFs composite catalyst prepared by research with rhodamine B as a model pollutant under the assistance of visible light2O2Persulfate and O3 are used for degrading organic pollutants. Under normal temperature and pressure, a 300W xenon lamp is used as a radiation light source, the reaction solution is 40ml, 40mg/L rhodamine B solution (pH is not adjusted), the adding amount of the catalyst is 8mg, after dark adsorption is carried out for 60min, 60mM H is added2O2The stirring was continued under light irradiation, and a small amount of the reaction solution was withdrawn every 20min and the absorbance of the solution was measured at 554 nm. And measuring the degradation efficiency of the rhodamine B according to an ultraviolet visible light photometry. And the results are shown in figure 3 for the control without visible light assisted degradation. The BiOCl/Fe-MOFs composite catalytic material has the effect of remarkably enhancing the degradation of organic matters, and under the assistance of visible light, the composite catalytic material takes BFM-50 as an example, the degradation rate of rhodamine B in 20 minutes is nearly 100%, the TOC removal rate can reach 80%, and the removal rate is obviously higher than the 50% removal rate of rhodamine B and the 18% removal rate of BiOCl of an independent photocatalytic material MIL-100 (Fe); meanwhile, the light condition can also obviously improve the photocatalysisThe removal rate of the BFM-50 rhodamine B under the assistance of visible light can reach 100 percent, and is higher than 85 percent under the assistance of no light. In addition, after the catalyst is repeatedly used for 5 times, as can be seen from fig. 4, the degradation effect is basically unchanged, and the degradation effect is better when the pH is 4-8, the removal rate of rhodamine B can reach more than 98% within 5 minutes when the pH is 4.0, and the removal rate of rhodamine B can reach more than about 90% within 50 minutes when the pH is 8.
The above-described embodiments are merely preferred embodiments of the present invention, which is not intended to be limiting in any way, and other variations and modifications are possible without departing from the scope of the invention as set forth in the appended claims.
Claims (10)
1. A preparation method of a BiOCl/Fe-MOFs composite catalytic material is characterized in that the preparation method comprises the step of mixing ferrous chloride, bismuth trichloride aqueous solution and sodium hydroxide solution of trimesic acid for reaction to obtain the BiOCl/Fe-MOFs composite catalytic material.
2. The preparation method of the BiOCl/Fe-MOFs composite catalytic material according to claim 1, wherein the preparation method comprises the following steps:
(1) dissolving ferrous chloride tetrahydrate in deionized water, adding bismuth chloride according to a certain molar ratio, and stirring to dissolve to obtain a solution A;
(2) adding trimesic acid into a sodium hydroxide solution, keeping the temperature of the solution at 60-70 ℃, and stirring and dissolving to obtain a solution B;
(3) slowly dripping the solution B in the step (2) into the solution A, continuously stirring at room temperature for reacting for 6 hours after dripping is finished, and carrying out post-treatment on the obtained product to obtain the BiOCl/Fe-MOFs composite catalytic material of light yellow powder solid.
3. The preparation method of the BiOCl/Fe-MOFs composite catalytic material according to claim 2, wherein the molar ratio of the metal salt to the trimesic acid, the NaOH and the water is 1.5:1:3: 750-900, and the metal salt comprises ferrous chloride and bismuth chloride.
4. The method for preparing a BiOCl/Fe-MOFs composite catalytic material according to claim 3, wherein the molar fraction of bismuth ions in the total metal ions is 0-100%.
5. The method for preparing the BiOCl/Fe-MOFs composite catalytic material according to claim 2, wherein the concentration of the sodium hydroxide solution in the step (2) is 1 mol/L.
6. The method for preparing a BiOCl/Fe-MOFs composite catalytic material according to claim 2, wherein said solution B is added to said solution A at a rate of 0.3-0.6mL/min in said step (3).
7. The preparation method of the BiOCl/Fe-MOFs composite catalytic material according to claim 2, wherein the stirring reaction rate in the step (3) is 300-500 r/min.
8. The preparation method of the BiOCl/Fe-MOFs composite catalytic material according to claim 2, wherein the post-treatment in the step (3) is that after the reaction is finished, the reaction mixture is kept stand, supernatant liquid is poured out, and the reaction mixture is soaked, centrifuged and washed with water and absolute ethyl alcohol at 50-70 ℃ for 3-5 times respectively, and then vacuum-dried at 60 ℃ to obtain final powder solid.
9. An application of the BiOCl/Fe-MOFs composite catalytic material obtained by the preparation method of the BiOCl/Fe-MOFs composite catalytic material of any one of claims 1 to 8 in wastewater treatment.
10. The application of the BiOCl/Fe-MOFs composite catalytic material in wastewater treatment according to claim 9, wherein the application conditions are that the BiOCl/Fe-MOFs composite catalytic material is used as a catalyst, and hydrogen peroxide, persulfate or O is used as a catalyst at 15-50 ℃3Is an oxygen source, has the pH value of 4-7 under the assistance of visible light, degrades organic pollutants in water, and has the TOC removal rateNot less than 80%.
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| CN115970761A (en) * | 2022-12-14 | 2023-04-18 | 中国五冶集团有限公司 | Synthesis method and test method of catalytic material of alumina reactor |
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