CN112403440A - Magnetic recyclable CoNi-MOFs @ GR adsorbent, preparation method and application to adsorption of organic dye - Google Patents
Magnetic recyclable CoNi-MOFs @ GR adsorbent, preparation method and application to adsorption of organic dye Download PDFInfo
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Abstract
The invention belongs to the technical field of dye adsorption material preparation, and provides a magnetic recyclable CoNi-MOFs @ GR adsorbent, a preparation method and an adsorption application to organic dyes. The CoNi-MOFs @ GR adsorbent is a bimetallic organic framework compound CoNi-MOFs loaded on graphene GR. CoNi-MOFs have large specific surface area, active sites and pores. The GR has high thermal stability, can be used as an adsorbent carrier and has an adsorption effect, and has larger specific surface area and active sites. The adsorbent formed by GR and CoNi-MOFs has the advantages of increased specific surface area, increased active sites, enhanced chemical stability and the like, enhances the adsorptive capacity, can realize efficient adsorption and separation of methylene blue MB, Congo red CR and neutral red NR, is convenient to separate from a solution, and can be recycled.
Description
Technical Field
The invention belongs to the technical field of dye adsorption material preparation, and particularly relates to a magnetic recyclable CoNi-MOFs @ GR adsorbent, a preparation method and an application to adsorption of organic dyes, especially to adsorption of three organic dyes.
Background
With the rapid development of science and technology and the steady promotion of industrial technology, dyes have been widely applied to various fields such as printing, textile, plastics, leather, coating, food industry and the like, and make extremely important contributions to economic development and people's life. However, dye contamination, which inevitably results from discharge into the water body during production, transportation and employment, may pose adverse and serious threats to the ecological environment and human health. Most dyes in wastewater are generally highly toxic and difficult to degrade due to their complex structure and poor biodegradability, and thus there is an urgent need to explore an eco-friendly, convenient and economical means for treating dyes.
Metal organic framework compounds (MOFs) are novel porous coordination compounds with highly regular network structures formed by metal ions or metal clusters and organic ligands through coordination bonds and other weak action modes, and have various characteristics of large specific surface area, small density, designable diversified framework structures, adjustable potential pore sizes and the like compared with traditional porous materials (such as zeolite, molecular sieve and the like). Meanwhile, the bimetallic MOFs has the functional characteristics of both metal and organic ligands, has wide application in the fields of gas storage, separation and purification, catalysis and the like, and is a hotspot of research in recent years.
Graphene (GR) not only has good physical and mechanical properties, but also has a large specific surface area, resulting in many surface active sites, and is considered to be one of the most promising commercial materials for the development of suitable industries today. The unique adsorption property of the graphene promotes the graphene to be used as an adsorbent carrier or form a compound to improve the adsorption activity, and the graphene is the adsorbent carrier and has the adsorption effect. The organic dye in the sewage is removed by forming a compound with a metal organic framework compound, has an important function and is a research hotspot in novel carbon materials.
Disclosure of Invention
The invention provides a magnetic recyclable CoNi-MOFs @ GR adsorbent, a preparation method and an adsorption application to organic dyes, aiming at solving the problems of high cost and low efficiency of the existing wastewater treatment. The adsorbent is prepared by loading a bimetallic MOFs material (CoNi-MOFs) on Graphene (GR), so that Methylene Blue (MB), Congo Red (CR) and Neutral Red (NR) can be quickly and efficiently adsorbed. The obtained adsorbent is simple in preparation process, low in cost, magnetic, recyclable, high in adsorption quantity to methylene blue, Congo red and neutral red, high in adsorption speed and good in industrial application prospect.
The invention is realized by the following technical scheme: the magnetic recyclable CoNi-MOFs @ GR adsorbent is a bimetallic CoNi organic framework compound CoNi-MOFs loaded on graphene GR.
The method for preparing the magnetic recyclable CoNi-MOFs @ GR adsorbent comprises the following steps:
(1) preparation of CoNi-MOFs: adding 0.275-0.475 mmol of Co (NO)3)20.275-0.475 mmol of Ni (NO)3)2And 0.65 mmol-0.85 mmol of 2-amino terephthalic acid are added into 36 mL of solvent for 40KHz ultrasonic treatment for 30 min; placing the obtained product in a sealed reaction kettle, and heating for 24 hours at 160-220 ℃; then naturally cooling to room temperature, collecting the solid and washing for a plurality of times by secondary water; finally, the obtained solid is dried at 60 ℃ overnight to obtain magnetic CoNi-MOFs powder; wherein the solvent is a mixed solution of 32 mL of N.N-dimethylformamide, 2mL of ethanol and 2mL of secondary water;
(2) preparation of CoNi-MOFs @ GR: adding graphene and the CoNi-MOFs prepared in the step (1) into water, and controlling the concentration of the graphene in the system to be 3.0-7.0 mg/mL and the concentration of the CoNi-MOFs to be 5-10 mg/mL; performing 40KHz ultrasonic treatment for 30 min to obtain uniform dispersion; and (3) drying in vacuum at 60 ℃ to obtain the CoNi-MOFs @ GR adsorbent composite material.
Co (NO) in step (1)3)2The concentration of (2) is 0.375 mmol; ni (NO)3)2The concentration of (2) is 0.375 mmol; the concentration of the 2-amino terephthalic acid is 0.75 mmol; in the step (2), the concentration of the graphene is 5.0 mg/mL, and the concentration of the CoNi-MOFs is 8.0 mg/mL.
The reaction temperature in step (1) was 200 ℃.
Adsorbing organic dyes by using the magnetic recyclable CoNi-MOFs @ GR adsorbent, wherein the organic dyes are methylene blue MB, Congo red CR and neutral red NR; the specific method comprises the following steps: adding CoNi-MOFs @ GR adsorbent into an aqueous solution containing methylene blue MB, Congo red CR and neutral red NR, oscillating and adsorbing for 60-120 min in a constant-temperature oscillator, and then recovering the adsorbent by using a magnet. Preferably, the adsorption is carried out for 120 min under shaking in a constant temperature oscillator.
The dosage of the CoNi-MOFs @ GR adsorbent is 5mg, the adsorption capacity of methylene blue MB is 10.0-90.24 mg/g, the adsorption capacity of Congo red CR is 50.0-284.66mg/g, and the adsorption capacity of neutral red NR is 20.0-108.54 mg/g.
The adsorption of Methylene Blue (MB), Congo Red (CR) and Neutral Red (NR) is realized mainly through the pore structure of the adsorbent, amino groups carried on the surface, large specific surface area and electrostatic interaction.
The CoNi-MOFs @ GR adsorbent can realize efficient adsorption separation of Methylene Blue (MB), Congo Red (CR) and Neutral Red (NR), is convenient to separate from a solution, and can be recycled. The adsorbent is immersed in a water environment containing Methylene Blue (MB), Congo Red (CR) and Neutral Red (NR) for sufficient adsorption, the CoNi-MOFs @ GR adsorbent is separated by a magnet, and then the adsorbent is immersed in ethanol so that the Methylene Blue (MB), the Congo Red (CR) and the Neutral Red (NR) can be resolved, and the adsorbent is recycled.
Compared with the prior art, the invention has the advantages that: bimetallic MOFs materials (CoNi-MOFs) have large specific surface area, active sites and pores. Graphene (GR) has high thermal stability, can be used as an adsorbent carrier, has an adsorption effect, and has a large specific surface area and an active site. Therefore, the novel adsorbent formed by GR and CoNi-MOFs has the advantages of increased specific surface area, increased active sites, enhanced chemical stability and the like, the adsorption capability of the adsorbent is enhanced, and the adsorption effect on Methylene Blue (MB), Congo Red (CR) and Neutral Red (NR) in water is obviously enhanced.
Drawings
FIG. 1 is a scanning electron microscope characterization image of CoNi-MOFs prepared by the present invention;
FIG. 2 is a scanning electron microscope characterization image of CoNi-MOFs @ GR prepared by the present invention;
FIG. 3 is a graph showing the adsorption effect of CoNi-MOFs @ GR on Methylene Blue (MB), Congo Red (CR) and Neutral Red (NR) in the present invention;
FIG. 4 is a graph showing the adsorption effect of CoNi-MOFs @ GR on Methylene Blue (MB), Congo Red (CR) and Neutral Red (NR) simultaneously in accordance with the present invention;
FIG. 5 is a graph of the results of adsorption performance measurements of CoNi-MOFs @ GR adsorbent after six regeneration cycles.
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, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments; 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.
The invention is further illustrated by the following examples in conjunction with the accompanying drawings.
Example 1: 0.275 mmol of Co (NO)3)20.275 mmol of Ni (NO)3)2And 0.65 mmol of 2-aminoterephthalic acid were added to 36 mL of a solvent (30 mL of N.N-dimethylformamide, 3mL of ethanol and 3mL of secondary water) to conduct sonication. The product was sealed in a reaction kettle and heated at 160 ℃ for 20 h. The reaction kettle is then cooled to room temperature, the solids are collected and used twiceThe water is washed several times. Finally, the resulting solid was dried at 60 ℃ overnight to give magnetic CoNi-MOFs powder.
Adding 3.0 mg/mL graphene and 5 mg/mL CoNi-MOFs into water, and carrying out ultrasonic treatment on the mixture for 20 min at 40KHz to form a uniform dispersion liquid. And drying at 60 ℃ in vacuum to obtain the CoNi-MOFs @ GR adsorbent.
Example 2: 0.375 mmol of Co (NO)3)20.375 mmol of Ni (NO)3)2And 0.75 mmol of 2-aminoterephthalic acid in 36 mL of solvent (32 mL of N.N-dimethylformamide, 2mL of ethanol and 2mL of secondary water) were sonicated. The product was sealed in a reaction kettle and heated at 200 ℃ for 24 h. The reaction kettle was then cooled to room temperature and the solid was collected and washed several times with secondary water. Finally, the resulting solid was dried at 60 ℃ overnight to give magnetic CoNi-MOFs powder.
Adding 5.0 mg/mL graphene and 8 mg/mL CoNi-MOFs into water, and carrying out ultrasonic treatment on the mixture for 30 min at 40KHz to form a uniform dispersion liquid. And drying at 60 ℃ in vacuum to obtain the CoNi-MOFs @ GR adsorbent.
Example 3: 0.475 mmol of Co (NO)3)20.475 mmol of Ni (NO)3)2And 0.85 mmol of 2-aminoterephthalic acid were added to 36 mL of a solvent (33 mL of N.N-dimethylformamide, 1.5mL of ethanol, and 1.5mL of secondary water) to conduct sonication. The product was sealed in a reaction kettle and heated at 220 ℃ for 28 h. The reaction kettle was then cooled to room temperature and the solid was collected and washed several times with secondary water. Finally, the resulting solid was dried at 60 ℃ overnight to give magnetic CoNi-MOFs powder.
Adding 8.0 mg/mL graphene and 10 mg/mL CoNi-MOFs into water, and carrying out 40KHz ultrasonic treatment for 40 min to form a uniform dispersion liquid. And drying at 60 ℃ in vacuum to obtain the CoNi-MOFs @ GR adsorbent.
Example 4: determination of the amount of adsorption of CoNi-MOFs @ GR adsorbent to Methylene Blue (MB): and (2) respectively putting 5mg of magnetic CoNi-MOFs @ GR adsorbent into 15 conical flasks, measuring 8 mL of magnetic CoNi-MOFs @ GR adsorbent, respectively transferring 200 mg/L of Methylene Blue (MB) aqueous solution into the 15 conical flasks, then putting the conical flasks into a constant-temperature oscillator at the temperature of 25 ℃ for oscillation adsorption, rotating at 180 r/min, respectively sampling every 10 min, and closing the oscillator after sampling for 60-120 min. After the sample was taken out, it was separated, and 2mL of each supernatant sample was taken after separation. And measuring the absorbance value of the Methylene Blue (MB) at the maximum absorption wavelength of 662 nm by using an ultraviolet-visible spectrophotometer, and analyzing and detecting the adsorption effect of the Methylene Blue (MB) aqueous solution. The adsorption capacity of the CoNi-MOFs @ GR adsorbent to Methylene Blue (MB) aqueous solution is obtained by analysis and calculation: 90.24 mg/g.
Example 5: determination of Congo Red (CR) adsorption amount by CoNi-MOFs @ GR adsorbent: respectively putting 5mg of magnetic CoNi-MOFs @ GR adsorbent into 15 conical flasks, measuring 8 mL of Congo Red (CR) aqueous solution of 500 mg/L, respectively transferring the Congo Red (CR) aqueous solution into the 15 conical flasks, then putting the Congo Red (CR) aqueous solution into a constant-temperature oscillator at the temperature of 25 ℃ for oscillation adsorption, rotating at 180 r/min, respectively sampling once every 10 min, and closing the oscillator after 60-120 min. After the sample was taken out, it was separated, and 2mL of each supernatant sample was taken after separation. And measuring the absorbance value at the 502nm position of the maximum absorption wavelength of Congo Red (CR) by using an ultraviolet visible light spectrophotometer, and analyzing and detecting the adsorption effect of the Congo Red (CR) aqueous solution. The adsorption capacity of the CoNi-MOFs @ GR adsorbent to Congo Red (CR) aqueous solution is obtained by analysis and calculation: 284.66 mg/g.
Example 6: determination of the amount of adsorption of Neutral Red (NR) by CoNi-MOFs @ GR adsorbent: respectively putting 5mg of magnetic CoNi-MOFs @ GR adsorbent into 15 conical flasks, measuring 8 mL of magnetic CoNi-MOFs @ GR adsorbent, respectively transferring 500 mg/L Neutral Red (NR) aqueous solution into the 15 conical flasks, then putting the conical flasks into a constant-temperature oscillator at the temperature of 25 ℃ for oscillation adsorption, rotating at 180 r/min, respectively sampling every 10 min, and closing the oscillator after sampling for 60-120 min. After the sample was taken out, it was separated, and 2mL of each supernatant sample was taken after separation. And measuring the absorbance value at the 488nm position of the maximum absorption wavelength of Neutral Red (NR) by using an ultraviolet visible light spectrophotometer, and analyzing and detecting the adsorption effect of the Neutral Red (NR) aqueous solution. The adsorption amount of the CoNi-MOFs @ GR adsorbent to a Neutral Red (NR) aqueous solution is obtained by analysis and calculation: 108.54 mg/g.
Example 7: simultaneous adsorption effect of CoNi-MOFs @ GR adsorbent on three dyes, Methylene Blue (MB), Congo Red (CR) and Neutral Red (NR): 5mg of magnetic CoNi-MOFs @ GR is used for placing a mixed solution of Methylene Blue (MB), Congo Red (CR) and Neutral Red (NR) into 1 conical flask, and then the conical flasks are placed into a constant-temperature oscillator at the temperature of 25 ℃ to be oscillated and simultaneously adsorbed, the rotating speed is 180 r/min, and the oscillator is closed when the rotating speed is 120 min. The sample was separated after the sample was removed, and 2mL of the supernatant sample was obtained after the separation. And measuring the absorbance value of the mixed solution by using an ultraviolet-visible spectrophotometer, and analyzing and detecting the adsorption effect of the mixed solution. As shown in fig. 4, the ultraviolet absorbance value of the mixed solution absorbed by the adsorbent was significantly reduced, indicating that the adsorbent has good adsorption capacity.
Example 8: reuse efficiency of CoNi-MOFs @ GR adsorbent: in this study, the effect of desorption and adsorbent recycle using ethanol solution to desorb dye from CoNi-MOFs @ GR adsorbent after adsorption is shown in FIG. 5. The results show that the CoNi-MOFs @ GR adsorbent still maintains the better adsorption performance after six regeneration cycles. After six regeneration cycles, the sorbent removal rate for the dye was close to 100%. In addition, the dye desorption rate of the CoNi-MOFs @ GR adsorbent is higher than 90% in each desorption test, which shows that the CoNi-MOFs @ GR adsorbent is high in recoverability and stability and has a wide practical application prospect.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (7)
1. A magnetic recyclable CoNi-MOFs @ GR adsorbent, characterized in that: the magnetic recyclable CoNi-MOFs @ GR adsorbent is formed by loading a bimetallic CoNi organic framework compound CoNi-MOFs on graphene GR.
2. A method of making the magnetically recoverable CoNi-MOFs @ GR adsorbent of claim 1, wherein: the method comprises the following steps:
(1) preparation of CoNi-MOFs: adding 0.275-0.475 mmol of Co (NO)3)20.275-0.475 mmol of Ni (NO)3)2And 0.65 mmol-0.85 mmol of 2-amino terephthalic acid are added into 36 mL of solvent for 40KHz ultrasonic treatment for 30 min; placing the obtained product in a sealed reaction kettle, and heating for 20-28 h at 160-220 ℃; then naturally cooling to room temperature, collecting the solid and washing for a plurality of times by secondary water; finally, the obtained solid is dried at 60 ℃ overnight to obtain magnetic CoNi-MOFs powder; wherein the solvent is a mixed solution of 30-33 mL of N.N-dimethylformamide, 1.5-3mL of ethanol and 1.5-3mL of secondary water;
(2) preparation of CoNi-MOFs @ GR: adding graphene and the CoNi-MOFs prepared in the step (1) into water, and controlling the concentration of the graphene in the system to be 3.0-8.0 mg/mL and the concentration of the CoNi-MOFs to be 5-10 mg/mL; performing 40KHz ultrasonic treatment for 20-40 min to form uniform dispersion; and (3) drying in vacuum at 60 ℃ to obtain the CoNi-MOFs @ GR adsorbent composite material.
3. The method of claim 2, wherein the magnetic recoverable CoNi-MOFs @ GR adsorbent comprises: co (NO) in step (1)3)2The concentration of (2) is 0.375 mmol; ni (NO)3)2The concentration of (2) is 0.375 mmol; the concentration of the 2-amino terephthalic acid is 0.75 mmol; in the step (2), the concentration of the graphene is 5.0 mg/mL, and the concentration of the CoNi-MOFs is 8.0 mg/mL.
4. The method of claim 2, wherein the magnetic recoverable CoNi-MOFs @ GR adsorbent comprises: the reaction temperature in step (1) was 200 ℃.
5. The method of adsorbing an organic dye using the magnetically recoverable CoNi-MOFs @ GR adsorbent of claim 1, wherein: the organic dye is methylene blue MB, Congo red CR and neutral red NR; the specific method comprises the following steps: adding CoNi-MOFs @ GR adsorbent into an aqueous solution containing methylene blue MB, Congo red CR and neutral red NR, oscillating and adsorbing for 60-120 min in a constant-temperature oscillator, and then recovering the adsorbent by using a magnet.
6. The method of claim 5, wherein the adsorption of organic dyes by using a magnetically recoverable CoNi-MOFs @ GR adsorbent is performed by: oscillating and adsorbing in constant temperature oscillator for 120 min.
7. The method of claim 5, wherein the adsorption of organic dyes by using a magnetically recoverable CoNi-MOFs @ GR adsorbent is performed by: the dosage of the CoNi-MOFs @ GR adsorbent is 5mg, the adsorption capacity of methylene blue MB is 10.0-90.24 mg/g, the adsorption capacity of Congo red CR is 50.0-284.66mg/g, and the adsorption capacity of neutral red NR is 20.0-108.54 mg/g.
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| CN117309825A (en) * | 2023-11-30 | 2023-12-29 | 四川蜀道建筑科技有限公司 | Light-transmitting device for detecting methylene blue MB value |
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