CN115445631A - Preparation method and test method of carbon-based catalytic material of metal organic framework - Google Patents
Preparation method and test method of carbon-based catalytic material of metal organic framework Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 71
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 40
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 39
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000010998 test method Methods 0.000 title abstract description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000013082 iron-based metal-organic framework Substances 0.000 claims abstract description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 13
- 238000001816 cooling Methods 0.000 claims abstract description 12
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 7
- 239000010453 quartz Substances 0.000 claims abstract description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000008367 deionised water Substances 0.000 claims abstract description 6
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 5
- 238000007789 sealing Methods 0.000 claims abstract description 3
- 238000005406 washing Methods 0.000 claims abstract description 3
- 239000004098 Tetracycline Substances 0.000 claims description 29
- 229960002180 tetracycline Drugs 0.000 claims description 29
- 229930101283 tetracycline Natural products 0.000 claims description 29
- 235000019364 tetracycline Nutrition 0.000 claims description 29
- 150000003522 tetracyclines Chemical class 0.000 claims description 29
- 230000015556 catabolic process Effects 0.000 claims description 18
- 238000006731 degradation reaction Methods 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 239000001301 oxygen Substances 0.000 claims description 13
- 229910052760 oxygen Inorganic materials 0.000 claims description 13
- 239000007800 oxidant agent Substances 0.000 claims description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 238000002474 experimental method Methods 0.000 claims description 10
- 230000001590 oxidative effect Effects 0.000 claims description 9
- 230000001699 photocatalysis Effects 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 claims description 3
- 239000004809 Teflon Substances 0.000 claims 1
- 229920006362 Teflon® Polymers 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- RDQSSKKUSGYZQB-UHFFFAOYSA-N bismuthanylidyneiron Chemical compound [Fe].[Bi] RDQSSKKUSGYZQB-UHFFFAOYSA-N 0.000 abstract description 8
- 239000003344 environmental pollutant Substances 0.000 abstract description 7
- 231100000719 pollutant Toxicity 0.000 abstract description 7
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- 239000010865 sewage Substances 0.000 description 9
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 3
- 239000002957 persistent organic pollutant Substances 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- FHHJDRFHHWUPDG-UHFFFAOYSA-N peroxysulfuric acid Chemical compound OOS(O)(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-N 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- 208000005623 Carcinogenesis Diseases 0.000 description 1
- 208000031320 Teratogenesis Diseases 0.000 description 1
- 230000001154 acute effect Effects 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000036952 cancer formation Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 231100000504 carcinogenesis Toxicity 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
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- 230000007613 environmental effect Effects 0.000 description 1
- 229940011871 estrogen Drugs 0.000 description 1
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- 238000002703 mutagenesis Methods 0.000 description 1
- 231100000350 mutagenesis Toxicity 0.000 description 1
- 238000012803 optimization experiment Methods 0.000 description 1
- KHIWWQKSHDUIBK-UHFFFAOYSA-N periodic acid Chemical compound OI(=O)(=O)=O KHIWWQKSHDUIBK-UHFFFAOYSA-N 0.000 description 1
- FHHJDRFHHWUPDG-UHFFFAOYSA-L peroxysulfate(2-) Chemical compound [O-]OS([O-])(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-L 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 238000001308 synthesis method Methods 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/084—Decomposition of carbon-containing compounds into carbon
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/843—Arsenic, antimony or bismuth
- B01J23/8437—Bismuth
-
- 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
- B01J37/082—Decomposition and pyrolysis
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
-
- 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
- C02F2101/34—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
- C02F2101/38—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
Abstract
The invention belongs to the technical field, and particularly relates to a preparation method and a test method of a carbon-based catalytic material of a metal organic framework. The preparation method of the carbon-based catalytic material comprises the following steps: the molar concentration ratio is Bi (NO) 3 ) 3 ·5H 2 O：Fe(NO 3 ) 3 ·9H 2 O: DTTDC: CTAB = (1 to 4): (1-4): 1: (0-1) the four components are respectively placed in a polytetrafluoroethylene lining and then respectively addedDMF and ethanol are stirred until the DMF and the ethanol are completely dissolved; sealing the high-pressure reaction kettle, placing the high-pressure reaction kettle in a muffle furnace, heating to 100-120 ℃, keeping the temperature for 68-76 h, and cooling to room temperature; washing brown material with methanol, DMF and deionized water respectively; drying in a vacuum box for 20-28 h to obtain Bi/Fe-MOFs; and (3) placing the Bi/Fe-MOFs into a quartz square boat, placing the quartz square boat into a tube furnace, heating to 500 ℃, heating for 68-76 hours, and cooling to room temperature to obtain Bi/Fe-D. The invention provides a method for synthesizing a carbon-based catalytic material based on a metal-organic framework of iron-bismuth bimetal and application of the carbon-based catalytic material to treatment of micro-polluted water containing refractory pollutants.
Description
Technical Field
The invention belongs to the technical field, and particularly relates to a preparation method and a test method of a carbon-based catalytic material of a metal organic framework.
Background
With the rapid development of the urbanization process, a large amount of domestic and production wastewater containing refractory organic pollutants of high-concentration medicines and personal care products is discharged into a conventional sewage plant through a municipal pipe network, and then is discharged into a water environment after being treated by the sewage plant. However, the conventional sewage treatment process has difficulty in efficiently removing organic pollutants of pharmaceutical and personal care products in sewage, which in turn leads to the gradual increase of the types and concentrations of the residual refractory organic pollutants in the water environment (lake water, river, reservoir water). The residual pollutants in the water environment mainly comprise various antibiotics, environmental estrogens, pesticides and other residual compounds, the half-life period of the pollutants in the water environment is long, the pollutants are slowly biodegraded, and the pollutants have potential hazards of acute carcinogenesis, teratogenesis and mutagenesis at a certain concentration.
The traditional advanced oxidation technology such as potassium permanganate method, fenton method, light Fenton method and the like has high energy consumption and is easy to generate a large amount of secondary pollution. Aiming at removing pollutants of refractory organic matters, a large number of advanced oxidation systems based on the MOFs-derived catalytic material with double metal cores are applied to sewage treatment.
In recent years, MOFs-derived materials based on Bi and Fe elements have been widely used for water treatment. However, the water instability of the MOFs greatly hinders the wide application of the MOFs in the field of water treatment advanced oxidation. The carbon-based material obtained by pyrolyzing the MOFs can not only keep the structure of the MOFs material, but also further improve the water stability of the MOFs material.
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to provide a method for synthesizing a carbon-based catalytic material based on an iron-bismuth bimetal metal-organic framework and application of the carbon-based catalytic material to treatment of micro-polluted water containing difficultly-degradable pollutants.
The technical scheme adopted by the invention is as follows:
a preparation method of a metal organic framework carbon-based catalytic material comprises the following steps:
s1: the molar concentration ratio is Bi (NO) 3 ) 3 ·5H 2 O：Fe(NO 3 ) 3 ·9H 2 O: DTTDC: CTAB = (1 to 4): (1-4): 1: (0-1) respectively placing the four components in a polytetrafluoroethylene lining of a high-pressure reaction kettle, respectively adding DMF (dimethyl formamide) and ethanol, and stirring until the four components are completely dissolved;
s2: sealing the high-pressure reaction kettle, placing the high-pressure reaction kettle in a muffle furnace, heating to 100-120 ℃, keeping the temperature for 68-76 h, and cooling to room temperature;
s3: washing the brown material obtained in the step S2 with methanol, DMF and deionized water respectively;
s4: drying in a vacuum box for 20-28 h to obtain a metal organic framework photocatalytic material Bi/Fe-MOFs;
s5: and (5) placing the Bi/Fe-MOFs prepared in the step (S4) into a quartz square boat, placing the quartz square boat into a tubular furnace, heating to 500 ℃ for 68-76 h, and cooling to room temperature to obtain the Bi/Fe-MOFs derivative material Bi/Fe-D.
Adding the four components with specific molar concentration ratio into a polytetrafluoroethylene lining of a high-pressure reaction kettle, reacting at a specific temperature to obtain the metal organic framework photocatalytic material Bi/Fe-MOFs based on the iron-bismuth bimetal, and finally performing pyrolysis treatment to obtain the derivative material Bi/Fe-D of the Bi/Fe-MOFs. The invention is realized by adding Bi (NO) 3 ) 3 ·5H 2 O、Fe(NO 3 ) 3 ·9H 2 And O, DTTDC and CTAB are configured according to a specific molar concentration ratio, and after reaction, the carbon-based catalytic material Bi/Fe-D based on the metal-organic framework of the iron-bismuth bimetal can be obtained. Experiments show that when the concentration of the carbon-based catalytic material Bi/Fe-D is 0.1g/100ml, the degradation rate of tetracycline with the concentration of 0.05mM can reach 60.2-91.3. Thus, by the present inventionThe obtained carbon-based catalytic material Bi/Fe-D can be applied to water treatment, and has high stability and high degradation rate.
As a preferable embodiment of the present invention, in step S1, the molar concentration ratio of the four components is Bi (NO) 3 ) 3 ·5H 2 O：Fe(NO 3 ) 3 ·9H 2 O: DTTDC: CTAB =1:1:1:0.1. when molar concentration ratio of Bi (NO) 3 ) 3 ·5H 2 O：Fe(NO 3 ) 3 ·9H 2 O: DTTDC: CTAB =1:1:1: when the concentration of the Bi/Fe-D of the carbon-based catalytic material is 0.1g/100ml, the degradation rate of tetracycline with the concentration of 0.05mM can reach 91.2, and the best degradation effect is achieved.
As a preferable aspect of the present invention, in step S1, the polytetrafluoroethylene inner liner is heated to 30 ℃ by a water bath.
As a preferable embodiment of the present invention, in step S1, the concentration of DMF is 99.8%, and the volume is 40ml; the concentration of ethanol is 99.5%, and the volume is 40ml; stirring for 30min at a rotor speed of 500r/min.
As a preferable aspect of the present invention, in step S2, a gradient temperature increasing mode is set: keeping the temperature for 72h at the temperature of 2 ℃/min to 120 ℃, and setting a gradient cooling mode: 5 ℃/min to room temperature.
As a preferred embodiment of the invention, in step S3, the brown material obtained in step S2 is washed with 3 times 50ml of methanol, 3 times 50ml of DMF and 3 times 200ml of deionized water in sequence.
As a preferable embodiment of the present invention, in step S4, the drying is carried out for 24 hours in a vacuum oven at a temperature of 70 ℃ and a degree of vacuum of 0.1 Kpa.
As a preferable aspect of the present invention, in step S5, a gradient temperature increasing mode is set: 2 ℃/min to a certain temperature, and keeping for 72 hours; setting a gradient cooling mode: 5 ℃/min to room temperature, and a certain protective gas is kept introduced during the period.
An experimental method of a metal organic framework carbon-based catalytic material comprises the following steps:
y1: placing the reactor in a water constant temperature circulator;
y2: introducing oxygen into the simulated solution to saturation by using the simulated solution containing tetracycline, and introducing nitrogen into the simulated solution to a low-oxygen condition;
y3: adding the prepared carbon-based catalytic material Bi/Fe-D of the metal organic framework into a simulated solution containing tetracycline, wherein the concentration of the Bi/Fe-D is 0.1-0.3 g/100ml, the concentration of an oxidant is 0.05-0.4 mW, the concentration of oxygen introduced in the reaction is 0-20 ml/min, the concentration of nitrogen introduced in the reaction is 0-20 ml/min, and the temperature is 5-45 ℃;
y4: calculating the degradation rate of the tetracycline: r Efficient ＝(C 0 -C t )/C 0 ；
Wherein, C 0 Is the initial tetracycline concentration, C t The tetracycline concentration after the reaction was completed.
By analyzing the application conditions of the Fe-Bi bimetal based metal organic framework carbon-based catalytic material Bi/Fe-D in the experimental environment, the application scene of the photocatalytic material can be deduced, so that the catalytic capability of the photocatalytic material can be fully exerted.
In a preferred embodiment of the present invention, in step S3, the concentration of the carbon-based catalytic material of the metal-organic framework is 0.1g/100ml, the concentration of the oxidant is 0.2mW, the concentration of oxygen introduced during the reaction is 20ml/min, and the temperature is 45 ℃.
As a preferred embodiment of the present invention,
the invention has the beneficial effects that:
the invention is realized by adding Bi (NO) 3 ) 3 ·5H 2 O、Fe(NO 3 ) 3 ·9H 2 And O, DTTDC and CTAB are configured according to a specific molar concentration ratio, and after reaction, the carbon-based catalytic material Bi/Fe-D based on the metal-organic framework of the iron-bismuth bimetal can be obtained. Experiments show that when the concentration of the carbon-based catalytic material Bi/Fe-D is 0.1g/100ml, the degradation rate of tetracycline with the concentration of 0.05mM can reach 60.2-91.3. Therefore, the carbon-based catalytic material Bi/Fe-D prepared by the method can be applied to water treatment, and has high stability and high degradation rate.
Drawings
Fig. 1 is an SEM image of the most preferred material of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all embodiments of the present invention. The components of embodiments of the present invention generally described and illustrated in the figures herein may be arranged and designed in a wide variety of different configurations.
Thus, the following detailed description of the embodiments of the present invention, presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. It should be noted that the embodiments and features of the embodiments of the present invention may be combined with each other without conflict.
The metal organic framework photocatalytic material of the present invention is composed of Bi (NO) 3 ) 3 ·5H 2 O、Fe(NO 3 ) 3 ·9H 2 O, DTTDC and CTAB are prepared and reacted, and the molar concentration ratio of the four components is Bi (NO) 3 ) 3 ·5H 2 O：Fe(NO 3 ) 3 ·9H 2 O：DTTDC：CTAB＝(1～4)：(1～4)：1：(0～1)。
Table 1 shows the ratios of the four components in 9 examples
The serial numbers 1-5 are the proportion of synthetic materials; serial numbers 6-9 are single metal core MOFs derived materials.
The material synthesis method comprises the following steps:
mixing Bi (NO) with different molar concentration ratios 3 ) 3 ·5H 2 O、Fe(NO 3 ) 3 ·9H 2 O, DTTDC and CTAB were placed in a 100ml polytetrafluoroethylene liner (water bath, 30 deg.C), 40ml DMF (99.8%) and 40ml ethanol (99.5%) were added, and stirred until completely dissolved (30 min, rotor speed 500 r/min). After complete dissolution, the autoclave was sealed and placed in a muffle furnace. Setting a gradient heating mode: 2 ℃/min to 120 ℃, and keeping for 72h. Setting a gradient cooling mode: 5 ℃/min to room temperature.
The brown material obtained was washed with methanol (3 times 50 ml), DMF (3 times 50 ml) and deionized water (3 times 200 ml). Finally, drying was carried out for 24h at 70 ℃ in a vacuum box (degree of vacuum 0.1 Kpa). Obtaining the metal organic framework photocatalytic material (Bi/Fe-MOFs) based on the iron-bismuth bimetal.
Adding the four components with specific molar concentration ratio into a polytetrafluoroethylene lining of a high-pressure reaction kettle, and reacting at a specific temperature to finally obtain the metal organic framework photocatalytic material Bi/Fe-MOFs based on the iron-bismuth bimetal.
Then, a certain amount of Bi/Fe-MOFs is placed in a quartz ark, the ark is placed in a tube furnace, and a gradient temperature-rising mode is set: 2 ℃/min to 500 ℃, and keeping for 72h. Setting a gradient cooling mode: 5 ℃/min to room temperature, and a certain protective gas is kept introduced during the period. Obtaining the derivative material (Bi/Fe-D) of the Bi/Fe-MOFs.
Table 2 BET data of the material before and after pyrolysis
| Material | S BET (m 2 /g) | Pore volume (cm) 3 /g) | Pore size (nm) |
| Bi/Fe-MOFs | 598 | 0.48 | 1.76 |
| Bi/Fe-D | 752 | 0.51 | 1.93 |
And then the degradation rate experiment is carried out on the 9 prepared materials.
Experimental methods for the materials of the invention:
the reaction is placed in a water constant temperature circulator, and the rotating speed of a rotor is 1000r/min; the reactor volume was 100ml. In the unvented state, the vent is sealed. The reaction time was 60min.
Representative refractory sewage components: a tetracycline. Representative oxidizing agents: persulfate, peroxymonosulfate, hydrogen peroxide, periodate, permanganate and peroxyacetic acid
Introducing oxygen for reaction: before the reaction, oxygen was introduced into the simulated solution containing tetracycline for 30min in advance until oxygen saturation. Introducing nitrogen for reaction: before reaction, introducing nitrogen into a simulated solution containing tetracycline for 30min in advance until the solution is in a low-oxygen condition;
the tetracycline degradation rate calculation method comprises the following steps: r Efficient ＝(C 0 -C t )/C 0 (ii) a Wherein, C 0 : initial tetracycline concentration, C t : tetracycline concentration after the reaction was complete.
In the experiment, the material concentration is 0.1g/100ml; the concentration of tetracycline is 0.05mM; the oxidant used was sodium persulfate, with an oxidant concentration of 0.1mM.
Table 3 shows the results of the material degradation rate experiments of the present invention
| Material number | Tetracycline degradation rate (%) |
| 1 | 82.5 |
| 2 | 91.3 |
| 3 | 85.5 |
| 4 | 75.3 |
| 5 | 68.5 |
| 6 | 65.2 |
| 7 | 56.5 |
| 8 | 69.9 |
| 9 | 60.2 |
The invention is realized by adding Bi (NO) 3 ) 3 ·5H 2 O、Fe(NO 3 ) 3 ·9H 2 The O, DTTDC and CTAB are configured according to a specific molar concentration ratio, and after reaction, the product can be obtained based onThe carbon-based catalytic material of the metal-organic framework of the iron-bismuth bimetal is Bi/Fe-D. Experiments show that when the concentration of the carbon-based catalytic material Bi/Fe-D is 0.1g/100ml, the degradation rate of tetracycline with the concentration of 0.05mM can reach 60.2-91.3. Therefore, the carbon-based catalytic material Bi/Fe-D prepared by the method can be applied to water treatment, and has high stability and high degradation rate.
When molar concentration ratio of Bi (NO) 3 ) 3 ·5H 2 O：Fe(NO 3 ) 3 ·9H 2 O: DTTDC: CTAB =1:1:1: when the concentration of the Bi/Fe-D of the carbon-based catalytic material is 0.1g/100ml, the degradation rate of tetracycline with the concentration of 0.05mM can reach 91.2, and the best degradation effect is achieved.
Table 4 shows the optimization experimental scheme of the sewage treatment conditions
The experimental results are as follows:
1) Numbers 1-5, the optimum oxidant concentration under the preferred experimental conditions was 0.2mM (number 4).
2) No. 6 to 10, the optimum material concentration was 0.1g/100ml (No. 7) under the preferable test conditions.
3) In Nos. 11 to 15, the tetracycline concentration is preferably 0.05mM (No. 13) under the experimental conditions.
4) In serial numbers 16-20, the tetracycline degradation efficiency is improved along with the increase of the reaction temperature under the temperature-optimized experimental conditions.
5) Serial numbers 21-22, under the optimized experimental conditions of atmosphere, the introduction of oxygen can obviously promote the degradation rate of tetracycline, and the introduction of nitrogen can obviously inhibit the degradation rate of tetracycline.
The optimization experimental scheme aiming at the sewage treatment condition of the oxidant comprises the following steps:
the material concentration is 0.1g/100ml; the concentration of tetracycline is 0.05mM; the oxidant concentration was 0.1mM.
Table 5 shows the results of the optimization experiment of the sewage treatment conditions for the oxidizing agent
According to the data, the persulfate and the peroxymonosulfuric acid can be found to show relatively high tetracycline removal efficiency, and the persulfate and the peroxymonosulfuric acid show good practicability in an advanced oxidation system based on Bi/Fe-MOFs derivative materials.
The invention is not limited to the above alternative embodiments, and any other various forms of products can be obtained by anyone in the light of the present invention, but any changes in shape or structure thereof, which fall within the scope of the present invention as defined in the claims, fall within the scope of the present invention.
Claims (10)
1. A preparation method of a carbon-based catalytic material with a metal organic framework is characterized by comprising the following steps: the method comprises the following steps:
s1: the molar concentration ratio is Bi (NO) 3 ) 3 ·5H 2 O：Fe(NO 3 ) 3 ·9H 2 O: DTTDC: CTAB = (1 to 4): (1-4): 1: (0-1) respectively placing the four components in a polytetrafluoroethylene lining of a high-pressure reaction kettle, respectively adding DMF (dimethyl formamide) and ethanol, and stirring until the four components are completely dissolved;
s2: sealing the high-pressure reaction kettle, placing the high-pressure reaction kettle in a muffle furnace, heating to 100-120 ℃, keeping the temperature for 68-76 h, and cooling to room temperature;
s3: washing the brown material obtained in the step S2 with methanol, DMF and deionized water respectively;
s4: drying in a vacuum box for 20-28 h to obtain a metal organic framework photocatalytic material Bi/Fe-MOFs;
s5: and (5) placing the Bi/Fe-MOFs prepared in the step (S4) into a quartz square boat, placing the quartz square boat into a tubular furnace, heating to 500 ℃ for 68-76 h, and cooling to room temperature to obtain the Bi/Fe-MOFs derivative material Bi/Fe-D.
2. The process for the preparation of a metal-organic framework carbon-based catalytic material according to claim 1, characterized in that: in step S1, the molar concentration ratio of the four components is Bi (NO) 3 ) 3 ·5H 2 O：Fe(NO 3 ) 3 ·9H 2 O：DTTDC：CTAB＝1：1：1：0.1。
3. The process for the preparation of a metal-organic framework carbon-based catalytic material according to claim 1, characterized in that: in step S1, the teflon liner is heated to 30 ℃ by a water bath.
4. The process for the preparation of a metal-organic framework carbon-based catalytic material according to claim 1, characterized in that: in step S1, the concentration of DMF is 99.8%, and the volume is 40ml; the concentration of ethanol is 99.5%, and the volume is 40ml; stirring for 30min at a rotor speed of 500r/min.
5. The process for the preparation of a metal-organic framework carbon-based catalytic material according to claim 1, characterized in that: in step S2, a gradient temperature increasing mode is set: keeping for 72h at the temperature of 2 ℃/min to 120 ℃, and setting a gradient cooling mode: 5 ℃/min to room temperature.
6. The process for the preparation of a metal-organic framework carbon-based catalytic material according to claim 1, characterized in that: in step S3, the brown material obtained in step S2 was washed sequentially with 3 times 50ml methanol, 3 times 50ml DMF and 3 times 200ml deionized water.
7. The process for the preparation of a metal-organic framework carbon-based catalytic material according to claim 1, characterized in that: in step S4, the mixture was dried in a vacuum oven at 70 ℃ and a vacuum of 0.1Kpa for 24 hours.
8. The process for the preparation of a metal-organic framework carbon-based catalytic material according to claim 1, characterized in that: in step S5, a gradient temperature increasing mode is set: 2 ℃/min to a certain temperature, and keeping for 72 hours; setting a gradient cooling mode: 5 ℃/min to room temperature, and a certain protective gas is kept introduced during the period.
9. An experimental method of a carbon-based catalytic material with a metal organic framework is characterized by comprising the following steps: the method comprises the following steps:
y1: placing the reactor in a water constant temperature circulator;
y2: introducing oxygen into the simulated solution to saturation by using the simulated solution containing tetracycline, and introducing nitrogen into the simulated solution to a low-oxygen condition;
y3: adding the prepared carbon-based catalytic material Bi/Fe-D of the metal organic framework into a simulated solution containing tetracycline, wherein the concentration of the Bi/Fe-D is 0.1-0.3 g/100ml, the concentration of an oxidant is 0.05-0.4 mW, the concentration of oxygen introduced in the reaction is 0-20 ml/min, the concentration of nitrogen introduced in the reaction is 0-20 ml/min, and the temperature is 5-45 ℃;
y4: calculating the degradation rate of the tetracycline: r Efficient ＝(C 0 -C t )/C 0 ；
Wherein, C 0 As initial tetracycline concentration, C t The tetracycline concentration after the reaction was completed.
10. Experimental method for a metal-organic framework carbon-based catalytic material according to claim 1, characterized in that: in step S3, the concentration of the carbon-based catalytic material of the metal organic framework is selected to be 0.1g/100ml, the concentration of the oxidant is 0.2mW, the concentration of oxygen introduced in the reaction is 20ml/min, and the temperature is 45 ℃.
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