CN114367271B - Load type MnO X Preparation method of @ NiCo-MOF composite material - Google Patents
Load type MnO X Preparation method of @ NiCo-MOF composite material Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 32
- 239000012924 metal-organic framework composite Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 45
- 239000002904 solvent Substances 0.000 claims abstract description 25
- 150000002500 ions Chemical class 0.000 claims abstract description 15
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 50
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 20
- 239000000843 powder Substances 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 12
- 229910001385 heavy metal Inorganic materials 0.000 claims description 11
- 239000011572 manganese Substances 0.000 claims description 11
- 238000001354 calcination Methods 0.000 claims description 10
- 229910017052 cobalt Inorganic materials 0.000 claims description 10
- 239000010941 cobalt Substances 0.000 claims description 10
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000003760 magnetic stirring Methods 0.000 claims description 9
- 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 description 8
- 239000013067 intermediate product Substances 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 6
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 6
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 5
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical group O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims description 3
- 230000000630 rising effect Effects 0.000 claims description 3
- 238000001179 sorption measurement Methods 0.000 abstract description 25
- 239000003463 adsorbent Substances 0.000 abstract description 10
- 239000011148 porous material Substances 0.000 abstract description 8
- 239000002131 composite material Substances 0.000 abstract description 6
- 238000000926 separation method Methods 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 3
- 239000002243 precursor Substances 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 abstract description 2
- 238000005470 impregnation Methods 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 229910052760 oxygen Inorganic materials 0.000 abstract description 2
- 239000001301 oxygen Substances 0.000 abstract description 2
- 125000000524 functional group Chemical group 0.000 abstract 1
- 239000013335 mesoporous material Substances 0.000 abstract 1
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- FLDSMVTWEZKONL-AWEZNQCLSA-N 5,5-dimethyl-N-[(3S)-5-methyl-4-oxo-2,3-dihydro-1,5-benzoxazepin-3-yl]-1,4,7,8-tetrahydrooxepino[4,5-c]pyrazole-3-carboxamide Chemical compound CC1(CC2=C(NN=C2C(=O)N[C@@H]2C(N(C3=C(OC2)C=CC=C3)C)=O)CCO1)C FLDSMVTWEZKONL-AWEZNQCLSA-N 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 230000002085 persistent effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0225—Compounds of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
-
- 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
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a load type MnO X The preparation method of the @ NiCo-MOF composite material comprises the steps of firstly preparing a bimetal NiCo-MOF with a spherical structure, taking the bimetal NiCo-MOF as a precursor, adopting a mild double-solvent impregnation method, utilizing the pore space of the MOF material to highly disperse Mn ions with a certain concentration on the surface of the precursor mesoporous material NiCo-MOF, generating a process of 'partially removing functional groups' with different degrees by changing the heat treatment conditions, and finally obtaining the supported MnO X @NiCo-MOF composite material. The heat-treated material effectively maintains the structure and pore canal of the MOF material, and simultaneously further exposes the metal sites with different original saturation degrees to form a metal-oxygen bond which is easier to access and is similar to MnO X The occurring ortho-synergistic effect improves the adsorption capacity of the composite material and greatly improves the adsorption reaction space. The material of the invention can realize Pb 2+ The rapid adsorption and the high-efficiency separation of the adsorbent have good stability, and Pb after being recycled for 5 times 2+ The removal efficiency of the catalyst can still reach more than 85 percent.
Description
Technical Field
The invention belongs to the field of heavy metal ion adsorption materials, and particularly relates to a supported MnO X Preparation method of @ NiCo-MOF composite material.
Background
The effective separation and enrichment of heavy metal ions is a very challenging project in the treatment of persistent pollution.
At present, in the traditional or novel water treatment process represented by chemical precipitation, ion exchange, reverse osmosis, adsorption, membrane separation and the like, the adsorption method has the advantages of wide application range, environmental friendliness, easy operation, high speed, high efficiency and the like, and is widely applied. The manganese oxide is used as an environment-friendly metal oxide, has the characteristics of good porous structure, large specific surface area, high negative charge and the like, has a strong adsorption effect on durable pollutants such as heavy metals, organic matters and the like in water, but has poor mechanical rigidity and a certain agglomeration property, so that the actual application of the manganese oxide in the field of wastewater treatment is limited. Therefore, a new adsorbent which is simple to prepare, has good manganese oxide dispersion performance and is easy to separate and is used for adsorbing Pb in wastewater is needed to be searched 2+ And (3) an isoparaffinic metal ion.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a load type MnO X Preparation method of@NiCo-MOF composite material, mnO is prepared by changing pore space and heat treatment conditions of MOF material X The high-strength composite material is highly dispersed on the surface of the NiCo-MOF, simultaneously effectively retains a spherical structure and mesoporous channels of the carrier, has the advantages of multiple active sites, large adsorption reaction space and the like, is simple in composite material separation, and can greatly reduce the energy consumption in the separation process.
The technical scheme adopted for solving the technical problems is as follows:
negative electrodeSupported MnO X The preparation method of the @ NiCo-MOF composite material comprises the following steps:
(1) Dissolving a nickel source and a cobalt source in a certain proportion in a first solvent, magnetically stirring until the nickel source and the cobalt source are uniformly dispersed to obtain a solution A, dispersing a certain amount of polyvinylpyrrolidone and trimesic acid in a mixed solution of a second solvent and a third solvent, carrying out ultrasonic and magnetic stirring uniformly to obtain a solution B, transferring the solution B into the solution A, and magnetically stirring uniformly to obtain a solution C;
(2) Carrying out hydrothermal reaction on the solution C, centrifuging to separate out solid after the reaction is finished, and washing and drying the solid to obtain light purple NiCo-MOF powder;
(3) Dispersing a certain amount of NiCo-MOF powder in normal hexane, carrying out ultrasonic and magnetic stirring to obtain a solution D, dispersing a certain amount of manganese source solution in the solution D, carrying out magnetic stirring until the powder is completely precipitated to obtain a solution E, and drying the solution E to obtain deep purple powder.
(4) Calcining the dark purple powder prepared in the step (3) under the air condition according to a certain temperature and time to obtain an intermediate product; then the intermediate product is further calcined at a certain temperature and time to obtain MnO X @NiCo-MOF composite material.
In the above scheme, the total volume of the first solvent, the second solvent and the third solvent in the step (1) is 60ml, the volume ratio is 1:1:1, 1:0:0, 0:1:0 and 0:0:1 respectively, the first solvent, the second solvent and the third solvent are deionized water, N-dimethylformamide and absolute ethyl alcohol respectively, and the mass ratio of polyvinylpyrrolidone to the third solvent is 1:3-1:10.
In the above scheme, the nickel source in the step (1) is nickel nitrate hexahydrate, the cobalt source is cobalt nitrate hexahydrate, and the molar ratio of the nickel source to the cobalt source is 0.25:0.75, 0.5:0.5, and 0.75:0.25.
In the scheme, the hydrothermal reaction temperature in the step (2) is 130-180 ℃, the reaction time is 8-14h, the centrifugal revolution is 5000-8000 r/min after the reaction, the washing is carried out by respectively washing with deionized water and absolute ethyl alcohol for 3-4 times, and the washing is dried by a vacuum drying oven at the drying temperature of 60-80 ℃ for 12-24 h.
In the above scheme, the manganese source solution in the step (3) is a 50% manganese nitrate solution. The mass ratio of Mn to NiCo-MOF is 1:1-1:10.
In the scheme, the NiCo-MOF powder in the step (3) is added into n-hexane, and the concentration of the formed solution D is 3-15 mg/ml.
In the scheme, the calcination is carried out in a muffle furnace under the air condition in the step (4), the temperature rising rate of the intermediate product during the calcination is 2-10 ℃/min, the calcination temperature is 180-220 ℃, and the time is 1-5 h.
In the above scheme, the MnO of step (4) X The temperature rising rate of the calcined composite material of the@NiCo-MOF is 2-10 ℃/min, the calcining temperature is 320-380 ℃ and the time is 1-3 h.
The supported MnO prepared by the scheme X The template sphere phase of the product is NiCo-MOF, and highly dispersed MnO is loaded outside the NiCo-MOF X 。
Firstly, nickel nitrate hexahydrate, cobalt nitrate hexahydrate, trimesic acid and polyvinylpyrrolidone are used as solutes, deionized water, N-dimethylformamide and absolute ethyl alcohol are used as solvents, and spherical bimetallic NiCo-MOF is prepared by a solvothermal method. Then taking the mixture as a precursor, adopting a double-solvent method and utilizing the change of the pore space and the heat treatment condition of the MOF material to obtain MnO X Highly dispersed on the surface of NiCo-MOF, and effectively retains the spherical structure and mesoporous pore canal of the carrier, and finally obtains the loaded MnO X @NiCo-MOF composite material.
On the one hand, such supported transition metal oxide MnO X The surface of the MOF spherical structure is highly dispersed, so that the adsorption reaction space is greatly improved, and more active sites are exposed; on the other hand, the composite adsorption material has simple and convenient separation operation and great application potential in the field of removing heavy metal ions in wastewater.
The invention has the advantages and positive effects that:
1. the double-solvent method adopted by the invention uses water as a hydrophilic solvent, so that metal ions are better absorbed by hydrophilic pores; with n-hexane as the hydrophobic materialThe solvent, which acts as a suspending agent, facilitates the impregnation process. Thereby utilizing the pore space of the MOF material to better disperse Mn ions, thereby improving MnO X The dispersibility of the polymer on the surface of the MOF material can enhance the adsorption capacity.
2. The optimal dosage of Mn ions is examined according to different adding amounts of Mn ions, and the Mn ions exist along with the increasing of the adding amount to cause the process from unsaturated, saturated to supersaturated of active sites on the surface of the spherical NiCo-MOF, thereby greatly improving MnO X The removal efficiency of heavy metal ions.
3. The 'partial functionalization' process with different degrees is generated by changing the heat treatment conditions, and the heat treated material effectively maintains the structure and pore canal of the MOF material, and simultaneously further exposes the metal sites with different original saturation degrees to form more easily accessible metal-oxygen bond which is similar to MnO X The generated ortho-synergistic effect improves the adsorption capacity of the composite material, greatly improves the adsorption reaction space, and overcomes the defect of MnO under different heat treatment conditions X The technical difficulty of the reduction degree.
4. Prepared supported MnO X The @ NiCo-MOF composite material has excellent heavy metal ions and Pb 2+ Is used for the adsorption performance of the catalyst.
Drawings
FIG. 1 shows MnO obtained in example 1 of the present invention X Schematic preparation flow chart of @ NiCo-MOF;
FIG. 2 shows MnO obtained in example 1 of the present invention X SEM image of @ NiCo-MOF;
FIG. 3 shows MnO obtained in example 1 of the present invention X XRD pattern of @ NiCo-MOF, niCo-MOF as a comparison;
FIG. 4 shows MnO obtained in example 1 of the present invention X FT-IR plot @ NiCo-MOF; niCo-MOF as a comparison;
FIG. 5 shows MnO obtained in example 1 of the present invention X XPS plot of @ NiCo-MOF, where a is Mn 2p and b is O1s.
FIG. 6 shows MnO made in example 1 of the present invention X Adsorption capacity plot at different pH for @ NiCo-MOF;
FIG. 7 shows MnO obtained in example 1 of the present invention X Five cycles of removal at NiCo-MOF.
Detailed Description
The invention is further illustrated by the following examples, which are intended to be illustrative only and not limiting in any way.
In the examples below, the reagents used, unless specifically indicated, were all commercially available chemical reagents analytically pure.
Example 1
Load type MnO X The preparation method of the @ NiCo-MOF composite material comprises the following steps:
1) Taking 655mg (2.25 mmol) of nickel nitrate and 218mg (0.75 mmol) of cobalt nitrate, mixing and dissolving in 20ml of deionized water according to the proportion of 0.75:0.25, magnetically stirring until the solution is uniformly dispersed to obtain a solution A, dispersing 3.0g of polyvinylpyrrolidone and 15mg (1.5 mmol) of trimesic acid in a mixed solution of 20ml of absolute ethyl alcohol and 20ml of N, N-dimethylformamide, carrying out ultrasonic and magnetic stirring until the solution is uniformly dispersed to obtain a solution B, transferring the solution B into the solution A, then obtaining a solution C, and continuously magnetically stirring until the solution C is uniformly dispersed;
2) Transferring the solution C to a stainless steel autoclave with 100mL polytetrafluoroethylene as a lining, sealing the stainless steel autoclave in a blast drying box for hydrothermal reaction at 180 ℃ for 12 hours, naturally cooling the stainless steel autoclave to room temperature, washing the stainless steel autoclave with deionized water and absolute ethyl alcohol for 4 times respectively, drying the stainless steel autoclave for 12 hours in a vacuum drying box at 70 ℃ and obtaining light purple powder NiCo-MOF after the drying is completed.
3) Dispersing 70mg of NiCo-MOF powder in 12ml of normal hexane, carrying out ultrasonic and magnetic stirring until the solution is uniform to obtain a solution D, dispersing 15 mu L of 50% manganese nitrate solution in the solution D, carrying out magnetic stirring until the powder is completely precipitated to obtain a solution E, drying the solution E for 12 hours at a temperature of 70 ℃ in a vacuum drying oven, and obtaining deep purple powder after the drying is complete.
4) Spreading the prepared dark purple powder in a porcelain boat, placing in a muffle furnace, heating at a heating rate of 5 ℃/min, heating from room temperature to 200 ℃ under air condition, and preserving heat for 1h to obtain an intermediate product; further heating the intermediate product to 350 ℃ and preserving heat for 1h, and then naturally coolingThe black powder obtained is calcined under the air condition to obtain the supported MnO X @NiCo-MOF composite material.
Application example 1
MnO prepared in example 1 X The @ NiCo-MOF is used as an adsorbent, and Pb is selected 2+ MnO for model contamination evaluation X Pb adsorption by @ NiCo-MOF 2+ Is a performance of the (c).
Into a 100mL Erlenmeyer flask was added 20mLPb 2+ Solutions (100 ppm concentration) of metal ions, pb was adjusted with 0.1M NaOH or HCl solution 2+ Under different initial pH conditions of the solution, 2g/LMnO was added X The @ NiCo-MOF was used as an adsorbent and was mechanically stirred at room temperature for 30min. Centrifuging at 3000r/min for 5min, taking supernatant, properly diluting, and measuring the concentration of the residual heavy metal ions in the solution by using an atomic absorption spectrophotometer. The results are shown in FIG. 5, and MnO is produced X The @ NiCo-MOF can be effectively adsorbed over a wide pH range.
After the adsorption test was completed, the solid adsorbent was separated, desorbed with a 0.5mol/L HC1 solution for 0.5h, washed with ultrapure water 3 times, and dried sufficiently. The adsorbent was then tested for recycling according to the above-described test method, and the results are shown in fig. 6. Heavy metal ion Pb after 5 times of circulation of adsorbent 2+ The removal rate is still kept above 85%.
Example 2
The preparation is identical to example 1, except that the ratio of nickel to cobalt is 0.25:0.75. The prepared MnO is treated by the adsorption experimental method X @NiCo-MOF vs Pb 2+ The adsorption is effective in a wide pH range, the adsorbent can be recycled for multiple times, and the heavy metal ions Pb after 5 times of recycling of the adsorbent 2+ The removal rate is still higher than 85%.
Example 3
The preparation was the same as in example 1 except that the 50% manganese nitrate solution was added in an amount of 20. Mu.L. The prepared MnO is treated by the adsorption experimental method X @NiCo-MOF vs Pb 2+ The adsorption is effective in a wide pH range, and the heavy metal ion Pb after 5 times of circulation of the adsorbent 2+ The removal rate is still highAt 87%.
Comparative example 1
The preparation is identical to example 1, except that the ratio of nickel to cobalt is 0.5:0.5. The prepared MnO is treated by the adsorption experimental method X At a broad pH range, the @ NiCo-MOF is specific for Pb 2+ The adsorption efficiency of the model pollutants is lower than 40 percent.
Comparative example 2
The preparation was the same as in example 1 except that 50% manganese nitrate solution was added in an amount of 10. Mu.L. The prepared MnO is treated by the adsorption experimental method X At a broad pH range, the @ NiCo-MOF is specific for Pb 2+ The adsorption efficiency of the model pollutant is low and the recoverability is poor.
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that it will be apparent to those skilled in the art that variations and modifications can be made without departing from the scope of the invention.
Claims (7)
1. Load type MnO X The preparation method of the @ NiCo-MOF composite material is characterized by comprising the following steps of:
(1) Dissolving a nickel source and a cobalt source in a certain proportion in a first solvent, magnetically stirring until the nickel source and the cobalt source are uniformly dispersed to obtain a solution A, dispersing a certain amount of polyvinylpyrrolidone and trimesic acid in a mixed solution of a second solvent and a third solvent, carrying out ultrasonic and magnetic stirring uniformly to obtain a solution B, transferring the solution B into the solution A, and magnetically stirring uniformly to obtain a solution C;
(2) Carrying out hydrothermal reaction on the solution C, centrifuging to separate out solid after the reaction is finished, and washing and drying the solid to obtain light purple NiCo-MOF powder;
(3) Dispersing a certain amount of NiCo-MOF powder in n-hexane, carrying out ultrasonic and magnetic stirring to obtain a solution D, dispersing a certain amount of manganese source solution in the solution D, carrying out magnetic stirring until the powder is completely precipitated to obtain a solution E, and drying the solution E to obtain dark purple powder;
(4) The dark purple powder prepared in the step (3) is processedCalcining under the air condition according to a certain temperature and time to obtain an intermediate product; then the intermediate product is further calcined at a certain temperature and time to obtain MnO X @NiCo-MOF composite material;
the volume ratio of the first solvent to the second solvent to the third solvent is 1:1:1, the first solvent to the third solvent is deionized water, N-dimethylformamide and absolute ethyl alcohol respectively, and the mass ratio of polyvinylpyrrolidone to the third solvent is 1:3-1:10;
the nickel source in the step (1) is nickel nitrate hexahydrate, the cobalt source is cobalt nitrate hexahydrate, and the molar ratio of the nickel source to the cobalt source is 0.25:0.75 or 0.75:0.25.
2. A supported MnO according to claim 1 X The preparation method of the@NiCo-MOF composite material is characterized by comprising the following steps of (2) carrying out hydrothermal reaction at 130-180 ℃ for 8-14h, wherein the centrifugal revolution after the reaction is 5000-8000 r/min, washing by deionized water and absolute ethyl alcohol for 3-4 times respectively, drying by a vacuum drying box after washing, and drying at 60-80 ℃ for 12-24 h.
3. A supported MnO according to claim 1 X The preparation method of the@NiCo-MOF composite material is characterized in that the manganese source solution in the step (3) is 50% manganese nitrate solution, and the mass ratio of Mn to NiCo-MOF is 1:1-1:10.
4. A supported MnO according to claim 1 X The preparation method of the NiCo-MOF composite material is characterized in that the NiCo-MOF powder in the step (3) is added into n-hexane, and the concentration of the formed solution D is 3-15 mg/ml.
5. A supported MnO according to claim 1 X The preparation method of the @ NiCo-MOF composite material is characterized in that the calcination in the step (4) is carried out in a muffle furnace according to a certain temperature and time under the air condition, and the temperature rising rate during the calcination is that2-10 ℃/min, the calcination temperature is 180-220 ℃ and the time is 1-5 h.
6. A supported MnO according to claim 1 X The preparation method of the @ NiCo-MOF composite material is characterized in that the heating rate of further calcining the intermediate product in the step (4) is 2-10 ℃/min, the calcining temperature is 320-380 ℃ and the time is 1-3 h.
7. A supported MnO prepared by the method of claim 1 X the@NiCo-MOF composite material is used for adsorbing heavy metal ions Pb 2+ Application to the field.
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| CN112023893A (en) * | 2020-09-21 | 2020-12-04 | 桂林理工大学 | MOF material capable of adsorbing heavy metal ions and preparation method thereof |
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