CN116212833A - Preparation method and application of bimetal MOF-CMC aerogel composite material - Google Patents
Preparation method and application of bimetal MOF-CMC aerogel composite material Download PDFInfo
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- 239000004964 aerogel Substances 0.000 title claims abstract description 81
- 239000002131 composite material Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 67
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 57
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- 239000002184 metal Substances 0.000 claims abstract description 41
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
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- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000004033 plastic Substances 0.000 claims abstract description 17
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 15
- 239000010941 cobalt Substances 0.000 claims abstract description 15
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 15
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
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- 238000000034 method Methods 0.000 claims description 21
- 239000008367 deionised water Substances 0.000 claims description 19
- 229910021641 deionized water Inorganic materials 0.000 claims description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 239000000084 colloidal system Substances 0.000 claims description 14
- 239000002243 precursor Substances 0.000 claims description 14
- -1 polytetrafluoroethylene Polymers 0.000 claims description 11
- 229910001385 heavy metal Inorganic materials 0.000 claims description 10
- 238000004140 cleaning Methods 0.000 claims description 9
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 9
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 9
- 230000032683 aging Effects 0.000 claims description 7
- 238000005520 cutting process Methods 0.000 claims description 7
- 150000002500 ions Chemical class 0.000 claims description 7
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- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- 230000004913 activation Effects 0.000 claims description 2
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- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 1
- 150000001805 chlorine compounds Chemical group 0.000 claims 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims 1
- 239000003463 adsorbent Substances 0.000 abstract description 24
- 238000001179 sorption measurement Methods 0.000 abstract description 24
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- 238000004458 analytical method Methods 0.000 description 2
- 239000013246 bimetallic metal–organic framework Substances 0.000 description 2
- 150000003841 chloride salts Chemical class 0.000 description 2
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- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
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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
- 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
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
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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
- 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]
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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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28047—Gels
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- 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
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- 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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Abstract
The invention discloses a preparation method and application of a bimetal MOF-CMC aerogel composite material, wherein the preparation method comprises the following steps: pyrolyzing PET plastic by a hydrothermal method to obtain terephthalic acid; dissolving cobalt metal salt, nickel metal salt and terephthalic acid in DMF solution to obtain clear solution, wherein the molar ratio of the total amount of the cobalt metal salt and the nickel metal salt to the terephthalic acid is 1: 3-3: 1, a step of; placing CMC aerogel in a stainless steel reaction kettle, adding the obtained clear solution, and reacting for 12-20 h at 80-160 ℃; and after the reaction is finished, washing the obtained initial product for a plurality of times by using DMF, activating the initial product by using alcohol within two days, and then freezing and drying the initial product to obtain the nickel-cobalt bimetallic MOF-CMC aerogel composite material. The composite material prepared by the invention can improve the adsorption capacity of the adsorbent, reduce the cost and solve the problem of plastic pollution.
Description
Technical Field
The invention relates to the technical field of water treatment, in particular to a preparation method and application of a bimetal MOF-CMC aerogel composite material.
Background
With the development of industry, water pollution problems are becoming more serious, wherein heavy metal pollution, particularly Cu 2+ 、Pb 2+ 、Cd 2+ The pollution problems are not ignored. Cu (Cu) 2+ 、Pb 2+ 、Cd 2+ The heavy metal ions are heavy metal ions with larger environmental toxicity and serious pollution, and the heavy metal ions are not biodegradable and can exist in the environment for a long time, so that the heavy metal pollution, particularly Cu, is effectively solved for the life health of human beings 2+ 、Pb 2+ 、Cd 2+ Pollution problems are an important issue today. The adsorption method is simple to operate and low in energy consumption, and is one of the important methods for removing heavy metal ions in the water body. The key to the improvement of pollutant removal capacity by adsorption methods is the development of novel adsorbents. At present, the problems of the traditional heavy metal adsorbent mainly include: (1) Most adsorbents exist in a powder form, so that the regeneration and the reuse are difficult; (2) the adsorbent has limited adsorption capacity for the target contaminant; (3) the adsorbent is expensive.
In recent years, an emerging metal-organic framework compound (metal organic frameworks) (MOFs for short) is a porous crystalline material with a periodic network structure, which is formed by self-assembly of a multidentate organic ligand and a metal coordination center (metal ion or metal cluster), and has a high specific surface area>500m 2 And/g), large porosity, diversified structures, good thermal stability and the like, and shows excellent performance in the aspect of heavy metal ion adsorption in water bodies. However, most MOFs materials exist in powder form, have poor framework stability and are very prone to collapse after encountering water. In addition, the method has low atomic density and completely open pore space, has huge defects in adsorption capacity and capture capacity on small molecular substances, and severely limits the application of the method in the field of water treatment.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation method and application of a bimetal MOF-CMC aerogel composite material, so as to achieve the purposes of improving the adsorption capacity of an adsorbent, reducing the cost and solving the problem of plastic pollution.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
a preparation method of a bimetallic MOF-CMC aerogel composite material comprises the following steps:
step (1), pyrolyzing PET plastic by a hydrothermal method to obtain terephthalic acid;
step (2), dissolving cobalt metal salt, nickel metal salt and terephthalic acid in DMF solution to obtain clear solution, wherein the molar ratio of the total amount of the cobalt metal salt and the nickel metal salt to the terephthalic acid is 1: 3-3: 1, a step of;
step (3), placing CMC aerogel in a stainless steel reaction kettle, adding the obtained clear solution, and reacting for 12-20 h at 80-160 ℃;
and (4) after the reaction is finished, washing the obtained initial product for a plurality of times by using DMF, activating the initial product by using alcohol within two days, and then freezing and drying the initial product to obtain the nickel-cobalt bimetallic MOF-CMC aerogel composite material.
In the above scheme, the specific method of step (1) is as follows: cutting PET plastic into blocks, cleaning and drying for later use; then placing 2.5g of PET plastic, 5mL of ethylene glycol and 50mL of deionized water into a polytetrafluoroethylene lining high-pressure reaction kettle, reacting for 4-10 hours at 180-230 ℃, centrifuging, separating, cleaning and drying the obtained terephthalic acid after the reaction is finished.
In the above scheme, the preparation method of the CMC aerogel comprises the following steps: adding carboxymethyl cellulose into deionized water, continuously stirring to dissolve the carboxymethyl cellulose, uniformly dispersing the carboxymethyl cellulose by ultrasonic to obtain transparent uniform colloid, removing bubbles, transferring the colloid into a pore plate, and aging to form a CMC aerogel precursor; and freezing and drying the CMC aerogel precursor to obtain the CMC aerogel.
In the above scheme, the cobalt metal salt nitrate or chloride salt and the nickel metal salt are chloride salts.
Preferably, the molar ratio of the total amount of cobalt metal salt and nickel metal salt to terephthalic acid is 1:1.
in a further technical scheme, the molar ratio of the cobalt metal salt to the nickel metal salt is 3: 7-7: 3.
preferably, the molar ratio of cobalt metal salt to nickel metal salt is 5:5.
preferably, in step (3), the reaction temperature is 120℃and the reaction time is 14h.
In the above scheme, in step (4), the alcohol used for activation is methanol or ethanol.
The application of the nickel-cobalt bimetallic MOF-CMC aerogel composite material prepared by the preparation method in the adsorption of heavy metal ions.
Through the technical scheme, the preparation method of the bimetal MOF-CMC aerogel composite material provided by the invention has the following beneficial effects:
(1) According to the invention, the bimetal MOF is introduced into the CMC aerogel by an in-situ growth method, so that the advantages of the bimetal MOF and the CMC aerogel are fully combined. Excellent synergistic effect can be generated between different metal sites in the nickel-cobalt bimetallic MOFs, and Cu is enhanced 2+ 、Pb 2+ 、Cd 2+ And the like. CMC aerogel is a porous material with three-dimensional network, has good stability, hydrogen bonds exist in the structure of the CMC aerogel after crosslinking, has high thermal stability, and is suitable for Cu 2+ 、Pb 2+ 、Cd 2+ And the like. The invention combines the two to obtain the adsorbent for Cu 2+ 、Pb 2+ 、Cd 2+ And the removing capability is strong.
(2) The nickel-cobalt bi-metal MOF-CMC aerogel composite material prepared by the invention has a three-dimensional macroscopic structure, has stable structure, is not easy to decompose, can be reused, and reduces the production cost. In the preparation process of the material, the CMC aerogel can provide a large number of binding sites for the growth of MOFs, and can enhance the mechanical strength of the MOFs and improve the regeneration and reuse performance of the MOFs.
(3) The nickel-cobalt bimetallic MOF-CMC aerogel composite material prepared by the invention takes PET plastic as a source of organic ligand in the MOF preparation process, so as to synthesize the adsorbent for Cu in wastewater 2+ 、Pb 2+ 、Cd 2+ And the adsorption of the waste, namely 'treating the waste with the waste', can relieve the harm of plastic pollution to the environment, and can reduce the cost of the prepared adsorbent. Meanwhile, the cellulose with the advantages of wide sources, large reserves, environmental protection, biodegradability, processability and the like is used as one of the main raw materials for the synthesis of the adsorbent, so that the method is environment-friendly, and meanwhile, the cost of the adsorbent can be reduced.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below.
FIG. 1 is a photograph showing the appearance of a composite material prepared in example 1 of the present invention;
FIG. 2 is a FT-IR contrast chart of terephthalic acid, CMC aerogel, and Ni/Co-MOF-CMC prepared in example 1;
FIG. 3 is a graph showing the Ni/Co-MOF-CMC prepared in example 1 and its adsorbed Cu 2+ A subsequent SEM image; (a) Ni/Co-MOF-CMC, (b) Ni/Co-MOF-CMC-Cu 2+ The method comprises the steps of carrying out a first treatment on the surface of the (c) is a partial enlarged view of (b);
FIG. 4 shows CMC aerogel prepared in example 1, ni/Co-MOF-CMC, and Ni/Co-MOF-CMC-Cu 2+ XPS comparison graph of (b);
FIG. 5 is a Ni/Co-MOF-CMC adsorbed Cu prepared in example 1 2+ Adsorption equilibrium curve of (2).
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention.
The invention provides a preparation method of a nickel-cobalt bimetallic MOF-CMC aerogel composite material (Ni/Co-MOF-CMC), which comprises the following specific embodiments:
example 1
1. A preparation method of a nickel-cobalt bi-metal MOF-CMC aerogel composite material (Ni/Co-MOF-CMC) comprises the following steps:
(1) Removing labels and bottle caps from PET plastic bottles, cutting into small sheets, cleaning, and drying at 60 ℃ for later use; then, the above-mentioned flake (2.5 g), ethylene glycol (5 mL) and deionized water (50 mL) were placed in a polytetrafluoroethylene-lined autoclave, and kept at 180℃for 10 hours, and subjected to centrifugal separation, washing and drying at 60℃to obtain terephthalic acid.
(2) Adding 1g of carboxymethyl cellulose (CMC) into 15mL of deionized water, and continuously stirring to dissolve the carboxymethyl cellulose; adding 15mL of deionized water into the mixed solution, and uniformly dispersing by ultrasonic to obtain transparent uniform colloid; after removing the bubbles, transferring the obtained colloid into a 96-well plate, and aging for 1h to form CMC aerogel precursor; and freezing and drying the CMC aerogel precursor for 12 hours to obtain the CMC aerogel.
(3) 0.29g Co (NO) 3 ) 2 ·6H 2 O、0.24g NiCl 2 ·6H 2 O and 0.99g H 2 BDC (terephthalic acid) was dissolved in 51.2mL DMF to give a clear solution, designated solution A.
(4) Placing the CMC aerogel cylinder prepared in the step (2) into a 100mL polytetrafluoroethylene-lined stainless steel reaction kettle, adding the solution A prepared in the step (3), and heating for 14h at 120 ℃ to obtain a Ni/Co-MOF-CMC three-dimensional composite material primary product.
(5) Washing the initial product obtained in the step (5) for multiple times by using DMF, activating for 3 times by using methanol (dehydrogenation) exchange solvent within two days, and then freezing and drying for 12 hours to obtain the Ni/Co-MOF-CMC three-dimensional composite material.
Example 2
1. A preparation method of a cobalt-nickel bi-metal MOF-CMC aerogel three-dimensional composite material (Ni/Co-MOF-CMC) comprises the following steps:
(1) Removing labels and bottle caps from PET plastic bottles, cutting into small sheets, cleaning, and drying at 60 ℃ for later use; then the flake (2.5 g), ethylene glycol (5 mL) and deionized water (50 mL) are placed in a polytetrafluoroethylene lining high-pressure reaction kettle, and kept at 230 ℃ for 4 hours, centrifugally separated, cleaned and dried at 60 ℃ to obtain terephthalic acid.
(2) Adding 1g of carboxymethyl cellulose (CMC) into 15mL of deionized water, and continuously stirring to dissolve the carboxymethyl cellulose; adding 15mL of deionized water into the mixed solution, and uniformly dispersing by ultrasonic to obtain transparent uniform colloid; after removing the bubbles, transferring the obtained colloid into a 96-well plate, and aging for 1h to form CMC aerogel precursor; and freeze-drying the CMC aerogel precursor for 12 hours to obtain the CMC aerogel.
(3) 0.87g Co (NO) 3 ) 2 ·6H 2 O、0.72g NiCl 2 ·6H 2 O and 0.33g H 2 BDC (terephthalic acid) was dissolved in 51.2mL DMF to give a clear solution, designated solution A.
(4) Placing the CMC aerogel cylinder prepared in the step (2) into a 100mL polytetrafluoroethylene lining stainless steel reaction kettle, adding the solution A prepared in the step (3), and heating for 20h at 80 ℃ to obtain a Ni/Co-MOF-CMC aerogel three-dimensional composite material primary product.
(5) Washing the initial product obtained in the step (5) for multiple times by using DMF, activating for 3 times by using ethanol (dehydrogenation) exchange solvent within two days, and then freezing and drying for 12 hours to obtain the Ni/Co-MOF-CMC aerogel three-dimensional composite material.
Example 3
1. A preparation method of a nickel-cobalt bi-metal MOF-CMC aerogel three-dimensional composite material (Ni/Co-MOF-CMC) comprises the following steps:
(1) Removing labels and bottle caps from PET plastic bottles, cutting into small sheets, cleaning, and drying at 60 ℃ for later use; then the slice (2.5 g), ethylene glycol (5 mL) and deionized water (50 mL) are placed in a polytetrafluoroethylene lining high-pressure reaction kettle, and kept at 180 ℃ for 4 hours, centrifugally separated, cleaned and dried at 60 ℃ to obtain terephthalic acid.
(2) Adding 1g of carboxymethyl cellulose (CMC) into 15mL of deionized water, and continuously stirring to dissolve the carboxymethyl cellulose; adding 15mL of deionized water into the mixed solution, and uniformly dispersing by ultrasonic to obtain transparent uniform colloid; after removing the bubbles, transferring the obtained colloid into a 96-well plate, and aging for 1h to form CMC aerogel precursor; and freeze-drying the CMC aerogel precursor for 12 hours to obtain the CMC aerogel.
(3) 0.29g CoCl 2 ·6H 2 O、0.24g NiCl 2 ·6H 2 O and 0.33g H 2 BDC (terephthalic acid) was dissolved in 51.2mL DMF to give a clear solution, designated solution A.
(4) Placing the CMC aerogel cylinder prepared in the step (2) into a 100mL polytetrafluoroethylene-lined stainless steel reaction kettle, adding the solution A prepared in the step (3), and heating at 120 ℃ for 16 hours to obtain a Ni/Co-MOF-CMC aerogel three-dimensional composite material primary product.
(5) Washing the initial product obtained in the step (5) for multiple times by using DMF, activating for 3 times by using methanol (dehydrogenation) exchange solvent within two days, and then freezing and drying for 12 hours to obtain the Ni/Co-MOF-CMC aerogel three-dimensional composite material.
Example 4
1. A preparation method of a nickel-cobalt bi-metal MOF-CMC aerogel three-dimensional composite material (Ni/Co-MOF-CMC) comprises the following steps:
(1) Removing labels and bottle caps from PET plastic bottles, cutting into small sheets, cleaning, and drying at 60 ℃ for later use; then the flake (2.5 g), ethylene glycol (5 mL) and deionized water (50 mL) are placed in a polytetrafluoroethylene lining high-pressure reaction kettle, and kept at 230 ℃ for 10 hours, centrifugally separated, cleaned and dried at 60 ℃ to obtain terephthalic acid.
(2) Adding 1g of carboxymethyl cellulose (CMC) into 15mL of deionized water, and continuously stirring to dissolve the carboxymethyl cellulose; adding 15mL of deionized water into the mixed solution, and uniformly dispersing by ultrasonic to obtain transparent uniform colloid; after removing the bubbles, transferring the obtained colloid into a 96-well plate, and aging for 1h to form CMC aerogel precursor; and freeze-drying the CMC aerogel precursor for 12 hours to obtain the CMC aerogel.
(3) 0.18g CoCl 2 ·6H 2 O、0.33g NiCl 2 ·6H 2 O and 0.33g H 2 BDC (terephthalic acid) was dissolved in 51.2mL DMF to give a clear solution, designated solution A.
(4) Placing the CMC aerogel cylinder prepared in the step (2) into a 100mL polytetrafluoroethylene lining stainless steel reaction kettle, adding the solution A prepared in the step (3), and heating for 14h at 160 ℃ to obtain a Co/Ni-MOF-CMC aerogel three-dimensional composite material primary product.
(5) Washing the initial product obtained in the step (5) for multiple times by using DMF, activating for 3 times by using ethanol (dehydrogenation) exchange solvent within two days, and then freeze-drying for 12 hours to obtain the Ni/Co-MOF-CMC aerogel three-dimensional composite material.
Example 5
1. A preparation method of a nickel-cobalt bi-metal MOF-CMC aerogel three-dimensional composite material (Ni/Co-MOF-CMC) comprises the following steps:
(1) Removing labels and bottle caps from PET plastic bottles, cutting into small sheets, cleaning, and drying at 60 ℃ for later use; then the flake (2.5 g), ethylene glycol (5 mL) and deionized water (50 mL) are placed in a polytetrafluoroethylene lining high-pressure reaction kettle, and kept at 210 ℃ for 8 hours, centrifugally separated, cleaned and dried at 60 ℃ to obtain terephthalic acid.
(2) Adding 1g of carboxymethyl cellulose (CMC) into 15mL of deionized water, and continuously stirring to dissolve the carboxymethyl cellulose; adding 15mL of deionized water into the mixed solution, and uniformly dispersing by ultrasonic to obtain transparent uniform colloid; after removing the bubbles, transferring the obtained colloid into a 96-well plate, and aging for 1h to form CMC aerogel precursor; and freeze-drying the CMC aerogel precursor for 12 hours to obtain the CMC aerogel.
(3) 0.41g Co (NO) 3 ) 2 ·6H 2 O、0.14g NiCl 2 ·6H 2 O and 0.33g H 2 BDC (terephthalic acid) was dissolved in 51.2mL DMF to give a clear solution, designated solution A.
(4) Placing the CMC aerogel cylinder prepared in the step (2) into a 100mL polytetrafluoroethylene lining stainless steel reaction kettle, adding the solution A prepared in the step (3), and heating for 12h at 120 ℃ to obtain a Co/Ni-MOF-CMC aerogel three-dimensional composite material primary product.
(5) And (3) washing the initial product obtained in the step (5) for multiple times by using DMF, activating for 3 times by using methanol (dehydrogenation) exchange solvent within two days, and then freeze-drying for 12 hours to obtain the Ni/Co-MOF-CMC aerogel three-dimensional composite material.
Comparative example 1
The difference from example 1 is that in step (3), 0.58g Co (NO 3 ) 2 ·6H 2 O and 0.99g H 2 BDC (terephthalic acid) was dissolved in 51.2mL DMF to give a clear solution, designated solution A. The rest of the procedure is the same as in example 1.
Comparative example 2
The difference from example 1 is that in step (3), 0.58g of NiCl is added 2 ·6H 2 O and 0.99g H 2 BDC (terephthalic acid) was dissolved in 51.2mL DMF to give a clear solution, designated solution A. The rest of the procedure is the same as in example 1.
Application of
The materials obtained in examples 1-5 and comparative examples 1-2 were used for Cu 2+ 、Pb 2+ 、Cd 2+ Adsorption conditions of (2): cu (Cu) 2 + 、Pb 2+ 、Cd 2+ The initial concentration of the solution is 50mg/L, the adsorbent consumption is 10mg, cu 2+ 、Pb 2+ 、Cd 2+ The volume of the solution was 50mL, the temperature was 25 ℃, ph=5, and the adsorption time was 6h. After the completion of the adsorption, the supernatant was filtered through a 0.45 μm filter membrane, and residual Cu was adsorbed by atoms 2+ 、Pb 2+ 、Cd 2+ Detecting the concentration, and calculating to obtain the Cu of the adsorbent 2+ 、Pb 2+ 、Cd 2+ The adsorption capacity of (2) is shown in Table 1.
TABLE 1 adsorption capacities (mg/g) of adsorbents obtained in examples and comparative examples
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Comparative example 1 | Comparative example 2 | |
| Cu 2+ | 100.2 | 89.4 | 92.5 | 78.7 | 100.3 | 55.5 | 55.9 |
| Pb 2+ | 195.7 | 165.3 | 189.4 | 167.1 | 187.8 | 98.4 | 89.2 |
| Cd 2+ | 94.3 | 76.9 | 86.2 | 73.5 | 90.8 | 48.2 | 47.4 |
As can be seen from the above table, the nickel-cobalt bimetallic MOF-CMC three-dimensional composite material prepared in examples 1-5 of the invention has a specific composition on Cu 2+ 、Pb 2+ 、Cd 2+ All have good adsorption performance, and the adsorption effect is obviously higher than that of the nickel/cobalt single metal MOF-CMC three-dimensional composite material adsorbent.
Characterization of Performance
1. Appearance analysis
The three-dimensional composite material prepared in the embodiment 1 of the invention has the appearance shown in fig. 1 and is of a three-dimensional solid columnar structure, and compared with the traditional powdery adsorbent, the adsorbent disclosed by the invention is favorable for regeneration and reuse.
2. FT-IR analysis
Successful compounding of the nickel-cobalt bimetallic MOF and CMC aerogel is the key for preparing the cobalt-nickel bimetallic MOF-CMC aerogel three-dimensional composite material. The FT-IR contrast plot of terephthalic acid, CMC aerogel, and Ni/Co-MOF-CMC obtained from pyrolysis of PET as shown in FIG. 2 for example 1, was found to be substantially identical to the peak profile of commercial terephthalic acid by FT-IR analysis, indicating that terephthalic acid had been successfully pyrolyzed from PET plastic.
In addition, cobalt nickel metal oxide, carboxymethyl cellulose and terephthalic acid absorption peaks appear in the nickel cobalt bi-metal MOF-CMC aerogel three-dimensional composite material, which indicates that the material has been successfully compounded.
3. SEM image
As shown in (a) of a SEM image of the Ni/Co-MOF-CMC prepared in the embodiment 1, the surface of the Ni/Co-MOF-CMC is loose and porous and is in a three-dimensional space network structure, so that the contact of pollutants and adsorbents is facilitated, and the adsorption of the pollutants is promoted.
Ni/Co-MOF-CMC prepared in example 1 adsorbed Cu 2+ As shown in (b) and (c) of FIG. 3, the SEM images after that adsorb Cu 2 + After that, obvious metal particle deposition appears on the surface of the adsorbent, which indicates Cu 2+ Has been successfully adsorbed onto Ni/Co-MOF-CMC surface area.
4. XPS (XPS) chart
FIG. 4 shows CMC aerogel prepared in example 1, ni/Co-MOF-CMC, and Ni/Co-MOF-CMC-Cu 2+ XPS comparison graph of (c). Use of nickel cobalt bi-metal MOF-CMC aerogel three-dimensional composite material for Cu 2+ After the adsorption reaction is completed, the adsorbent after adsorption contains a certain amount of copper element. As shown in fig. 4, the elemental content analysis by XPS test found that the copper element content in the adsorbent was 4.81%, which indicates that the adsorption reaction was successfully performed.
5. Adsorption equilibrium curve
FIG. 5 is a Ni/Co-MOF-CMC adsorbent prepared in example 1Attached Cu 2+ Adsorption equilibrium curve of (2). As can be seen from FIG. 5, the maximum theoretical adsorption capacity is 233.99mg/g, which is obviously higher than that of the traditional adsorbent by 0-100mg/g.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. The preparation method of the bimetallic MOF-CMC aerogel composite material is characterized by comprising the following steps:
step (1), pyrolyzing PET plastic by a hydrothermal method to obtain terephthalic acid;
step (2), dissolving cobalt metal salt, nickel metal salt and terephthalic acid in DMF solution to obtain clear solution, wherein the molar ratio of the total amount of the cobalt metal salt and the nickel metal salt to the terephthalic acid is 1: 3-3: 1, a step of;
step (3), placing CMC aerogel in a stainless steel reaction kettle, adding the obtained clear solution, and reacting for 12-20 h at 80-160 ℃;
and (4) after the reaction is finished, washing the obtained initial product for a plurality of times by using DMF, activating the initial product by using alcohol within two days, and then freezing and drying the initial product to obtain the nickel-cobalt bimetallic MOF-CMC aerogel composite material.
2. The method for preparing a bimetallic MOF-CMC aerogel composite according to claim 1, wherein the specific method of step (1) is as follows: cutting PET plastic into blocks, cleaning and drying for later use; then placing 2.5g of PET plastic, 5mL of ethylene glycol and 50mL of deionized water into a polytetrafluoroethylene lining high-pressure reaction kettle, reacting for 4-10 hours at 180-230 ℃, centrifuging, separating, cleaning and drying the obtained terephthalic acid after the reaction is finished.
3. The method for preparing a bimetallic MOF-CMC aerogel composite according to claim 1, wherein the method for preparing CMC aerogel is as follows: adding carboxymethyl cellulose into deionized water, continuously stirring to dissolve the carboxymethyl cellulose, uniformly dispersing the carboxymethyl cellulose by ultrasonic to obtain transparent uniform colloid, removing bubbles, transferring the colloid into a pore plate, and aging to form a CMC aerogel precursor; and freezing and drying the CMC aerogel precursor to obtain the CMC aerogel.
4. The method for preparing a bi-metallic MOF-CMC aerogel composite according to claim 1, wherein the cobalt metal salt is nitrate or chloride and the nickel metal salt is chloride.
5. The method for preparing a bimetallic MOF-CMC aerogel composite according to claim 1 or 4, wherein the molar ratio of the total amount of cobalt metal salt and nickel metal salt to terephthalic acid is 1:1.
6. the method for preparing a bi-metallic MOF-CMC aerogel composite according to claim 1 or 4, characterized in that the molar ratio of cobalt metal salt to nickel metal salt is 3: 7-7: 3.
7. the method for preparing a bi-metallic MOF-CMC aerogel composite according to claim 1 or 4, characterized in that the molar ratio of cobalt metal salt to nickel metal salt is 5:5.
8. the method for preparing a bi-metallic MOF-CMC aerogel composite according to claim 1, wherein in the step (3), the reaction temperature is 120 ℃ and the reaction time is 14h.
9. The method of preparing a bimetallic MOF-CMC aerogel composite according to claim 1, wherein in step (4), the alcohol used for activation is methanol or ethanol.
10. The use of the nickel-cobalt bi-metal MOF-CMC aerogel composite material prepared by the preparation method of claim 1 for adsorbing heavy metal ions.
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