CN114672064A - Preparation method and application of MIL-100 (Fe)/cellulose porous composite pellet - Google Patents
Preparation method and application of MIL-100 (Fe)/cellulose porous composite pellet Download PDFInfo
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Abstract
The invention discloses a preparation method of an MIL-100 (Fe)/cellulose porous composite pellet, which specifically comprises the following steps: (1) adding a cellulose binder into water, stirring in a water bath, and performing ultrasonic treatment to obtain a cellulose solution; (2) adding MIL-100(Fe) into a cellulose solution, uniformly stirring, and carrying out water bath ultrasonic treatment to obtain a mixed solution; (3) adding the mixed solution into a metal ion solution for primary soaking, filtering, and adding water for secondary soaking to obtain composite small-ball hydrogel; (4) and drying the composite small ball hydrogel to obtain the hydrogel. The MIL-100 (Fe)/cellulose porous composite pellet has the advantages of good mechanical property, large specific surface area, high porosity, large MIL-100(Fe) load capacity, high adsorption and degradation efficiency, easiness in recycling and the like, can realize high-efficiency adsorption and degradation of dye, and has a wide application prospect.
Description
Technical Field
The invention relates to the technical field of new materials, in particular to a preparation method and application of an MIL-100 (Fe)/cellulose porous composite pellet.
Background
With the acceleration of industrialization process, industrial wastewater and artificially generated harmful wastewater are randomly discharged, a large amount of pollutants are accumulated in natural water resources and are difficult to degrade, and the ecological environment and the living environment of human beings are seriously damaged.
The textile industry, as a dominant industry in China, occupies a leading position in the global textile industry, but the problem of printing and dyeing wastewater discharge of the industry is very severe. Meanwhile, dyes in printing and dyeing wastewater are the most important pollutants. The dye is widely used in the industries of textile, leather, paper making, drawing, plastics and the like. The waste water has complex components and contains various toxic and harmful substances, so that aquatic organisms and the ecological environment are endangered. Some dyes are carcinogenic and can be concentrated in organisms causing acute or chronic diseases. In addition, some dyes absorb or reflect sunlight into the water, thereby inhibiting the proliferation and growth of bacteria and not effectively degrading impurities in the water. Therefore, it is important to develop a technology for removing the dye in the wastewater with high efficiency and safety.
In recent years, the advanced oxidation method has great application value and prospect as a method for removing the dye in water with high efficiency, low cost and no secondary pollution. Metal Organic Frameworks (MOFs) are porous functional materials formed by self-assembly of metal nodes (metal ions or metal clusters) and organic ligands through coordination bonds, and are widely applied to advanced oxidation technologies due to the characteristics of high specific surface area, adjustable pore size, unsaturated metal-containing sites, easy functionalization and surface modification, and the like.
However, the problems of difficult recycling of powdered MOFs, high loss rate, easy secondary pollution and the like seriously hinder the industrial application of powdered MOFs.
Therefore, how to provide a safe and environment-friendly MOFs composite pellet which is formed by machining, has low cost, good removal efficiency and high recycling rate is a problem to be solved by those skilled in the art.
Disclosure of Invention
In view of the above, the present invention aims to provide a preparation method and an application of an MIL-100 (Fe)/cellulose porous composite pellet, so as to solve the defects in the prior art. The MIL-100 (Fe)/cellulose porous composite pellet has the advantages of good mechanical property, large specific surface area, high porosity, high MIL-100(Fe) load capacity, easiness in recycling and the like, can realize efficient adsorption and in-situ catalytic degradation of dye, and has a wide application prospect.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of an MIL-100 (Fe)/cellulose porous composite pellet specifically comprises the following steps:
(1) adding a cellulose binder into water, stirring in a water bath, and performing ultrasonic treatment to obtain a cellulose solution;
(2) adding MIL-100(Fe) into a cellulose solution, uniformly stirring, and carrying out water bath ultrasonic treatment to obtain a mixed solution;
(3) adding the mixed solution into a metal ion solution for primary soaking, filtering, and adding water for secondary soaking to obtain composite small-ball hydrogel;
(4) and drying the composite small ball hydrogel to obtain the MIL-100 (Fe)/cellulose porous composite small ball.
Further, in the step (1), the cellulose binder is sodium carboxymethyl cellulose; the mass-volume ratio of the sodium carboxymethylcellulose to the water is 1g (50-100) mL.
Further, in the step (1), the temperature of water bath stirring is 30-40 ℃, the rotating speed is 1000-; the ultrasonic treatment time is 5-10 min.
The further technical scheme has the beneficial effect that bubbles in the solution can be removed by ultrasonic.
Further, in the step (2), the mass ratio of MIL-100(Fe) to sodium carboxymethylcellulose is (8-9): 1.
Further, in the step (2), the stirring temperature is 20-30 ℃, the rotation speed is 10000-; the ultrasonic treatment in water bath is carried out for 20-30 min.
Further, in the step (3), the metal ions in the metal ion solution are at least one of copper ions, iron ions and zinc ions, and the concentration is 0.5-2 mol/L.
Further, in the step (3), the temperature for the first soaking is 20-30 ℃, and the time is 20-30 min; the second soaking is carried out at 20-30 deg.C for 2-3 hr.
The technical scheme has the beneficial effects that the MIL-100 (Fe)/cellulose composite pellets are formed in the metal ion solution through first soaking; by the second soaking, the excess metal ions and the corresponding anions can be removed.
Further, in the step (4), the drying temperature is 20-40 ℃ and the drying time is 8-12 h.
The invention also claims an application of the MIL-100 (Fe)/cellulose porous composite bead prepared by the preparation method in adsorption and degradation of dyes, which specifically comprises the following steps: the mass-volume ratio of 1g to 200mL is defined as that the specific surface area is 1200-1300m2Mixing MIL-100 (Fe)/cellulose porous composite pellets per gram with water containing 10-40mg/L of dye and having pH of 3-9, performing shock adsorption, and adding potassium hydrogen persulfate for degradation.
According to the technical scheme, compared with the prior art, the invention has the following beneficial effects:
1. the specific surface area of the MIL-100 (Fe)/cellulose porous composite pellet prepared by the invention is 1200-1300m2(iv)/g, with little loss.
2. The loading capacity of the MIL-100(Fe) in the MIL-100 (Fe)/cellulose porous composite pellet prepared by the method can reach 80-90%, and the high specific surface area and porosity of the MIL-100(Fe) are ensured.
3. The MIL-100 (Fe)/cellulose porous composite pellet is prepared and molded, so that the loss of materials in the using and recycling processes is reduced, and the recycling performance of the materials is improved; the mechanical strength of the spherical MIL-100(Fe) is improved, and the method is very suitable for industrial use; the molded MIL-100(Fe) has better water stability.
4. The cellulose binder disclosed by the invention is rich in reserve, non-toxic and free of secondary pollution.
5. The preparation process of the MIL-100 (Fe)/cellulose porous composite spheres is simple and convenient to synthesize and operate, low in cost, suitable for preparing MOFs with various shapes on a large scale, and significant in development of MOFs material forming processes and further significant in commercial and industrial application of the MOFs materials.
6. The MIL-100(Fe) in the MIL-100 (Fe)/cellulose porous composite pellet can effectively catalyze and activate the oxidant and efficiently degrade dye molecules in water.
7. The method for adsorbing and degrading the dye by the MIL-100 (Fe)/cellulose porous composite spheres has the advantages of simple treatment process and degradation apparatus, low cost, high material degradation efficiency and good recycling performance, is a dye treatment method which can be widely adopted, and has high commercial value and practical application prospect.
Drawings
FIG. 1 is an optical photograph of MIL-100 (Fe)/cellulose composite pellets obtained in example 1;
FIG. 2 is an SEM image of the MIL-100 (Fe)/cellulose composite pellet of example 1, wherein the left side of FIG. 2 is 4 μm, and the right side of FIG. 2 is 2 μm;
FIG. 3 is a PXRD pattern for MIL-100 (Fe)/cellulose composite beads and MIL-100(Fe) made in example 1;
FIG. 4 is a thermogravimetric plot of MIL-100 (Fe)/cellulose composite pellets, sodium carboxymethylcellulose, and MIL-100(Fe) made in example 1;
FIG. 5 is the N at 77K for MIL-100(Fe) and MIL-100 (Fe)/cellulose composite pellets from example 12Adsorption isotherms;
FIG. 6 shows the degradation efficiency of dye methylene blue in water body removed by using MIL-100 (Fe)/cellulose porous composite beads;
FIG. 7(a) is the efficiency of cyclic degradation of MB by MIL-100 (Fe)/cellulose composite beads; FIG. 7(b) PXRD pattern of MIL-100 (Fe)/cellulose composite beads before and after 5 cycles of degradation, and FIGS. 7(c) and 7(d) are SEM patterns of MIL-100 (Fe)/cellulose composite beads after 5 cycles of degradation, wherein FIG. 7(c) is 4 μm and FIG. 7(d) is 2 μm.
Wherein CMC is the abbreviation of sodium carboxymethylcellulose, PMS is the abbreviation of potassium hydrogen persulfate, MIL-100 is the abbreviation of MIL-100(Fe), MIL-100/CMC-HD is the abbreviation of MIL-100 (Fe)/cellulose composite pellet, and MIL-100/CMC-HD-5C is the abbreviation of MIL-100 (Fe)/cellulose composite pellet after 5 times of cyclic degradation.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
Example 1
The preparation method of the MIL-100 (Fe)/cellulose porous composite pellet specifically comprises the following steps:
(1) adding 2g of sodium carboxymethylcellulose into 98mL of deionized water, stirring for 3h in a water bath at 40 ℃ at the rotating speed of 1000r/min, and performing ultrasonic treatment for 50min to obtain a sodium carboxymethylcellulose solution;
(2) adding 3.6g of MIL-100(Fe) powder into 20g of sodium carboxymethylcellulose solution, stirring at a rotation speed of 10000r/min for 1h at a temperature of 20 ℃ by using a homogenizing shearing machine, and carrying out ultrasonic treatment in a water bath at the temperature of 20 ℃ for 20min until the mixture is converted into a uniform thick fluid mixture to obtain a mixed solution;
(3) dripping the mixed solution into a copper chloride solution with the temperature of 20 ℃ and the concentration of 0.5mol/L by using an injector, soaking for 30min, filtering and collecting spherical MOFs, and adding the spherical MOFs into deionized water with the temperature of 20 ℃ for soaking for 3h to obtain composite small ball hydrogel;
(4) and (3) drying the composite pellet hydrogel in a vacuum oven at the temperature of 20 ℃ for 12 hours to obtain the MIL-100 (Fe)/cellulose porous composite pellet.
Example 2
The preparation method of the MIL-100 (Fe)/cellulose porous composite pellet specifically comprises the following steps:
(1) adding 2.5g of sodium carboxymethylcellulose into 97.5mL of deionized water, stirring for 2.5h in a water bath at the temperature of 30 ℃ at the rotating speed of 1200r/min, and performing ultrasonic treatment for 8min to obtain a sodium carboxymethylcellulose solution;
(2) adding 4.2g of MIL-100(Fe) powder into 25g of sodium carboxymethylcellulose solution, stirring at the temperature of 25 ℃ for 1h at the rotating speed of 15000r/min by using a homogenizing shearing machine, and carrying out ultrasonic treatment for 25min in a water bath at the temperature of 25 ℃ until the mixture is converted into a uniform thick fluid mixture to obtain a mixed solution;
(3) dripping the mixed solution into a copper chloride solution with the temperature of 25 ℃ and the concentration of 1mol/L by using an injector, soaking for 20min, filtering and collecting spherical MOFs, and adding into deionized water with the temperature of 25 ℃ to soak for 2h to obtain composite small-ball hydrogel;
(4) and (3) drying the composite pellet hydrogel in a vacuum oven at 25 ℃ for 10h to obtain the MIL-100 (Fe)/cellulose porous composite pellet.
Example 3
The preparation method of the MIL-100 (Fe)/cellulose porous composite pellet specifically comprises the following steps:
(1) adding 3g of sodium carboxymethylcellulose into 97mL of deionized water, stirring for 3h in a water bath at 40 ℃ at the rotating speed of 1000r/min, and performing ultrasonic treatment for 10min to obtain a sodium carboxymethylcellulose solution;
(2) adding 5.1g MIL-100(Fe) powder into 27.5g sodium carboxymethylcellulose solution, stirring at 30 deg.C for 0.5h at 20000r/min with a homogenizing shear, and performing ultrasonic treatment in 30 deg.C water bath for 30min until it is converted into uniform thick fluid mixture to obtain mixed solution;
(3) dripping the mixed solution into a copper chloride solution with the temperature of 30 ℃ and the concentration of 1.5mol/L by using an injector, soaking for 25min, filtering and collecting spherical MOFs, and adding the spherical MOFs into deionized water with the temperature of 30 ℃ to soak for 2.5h to obtain composite small ball hydrogel;
(4) and (3) drying the composite pellet hydrogel in a vacuum oven at 30 ℃ for 12h to obtain the MIL-100 (Fe)/cellulose porous composite pellet.
Performance testing
1. The MIL-100 (Fe)/cellulose porous composite pellets obtained in examples 1 to 3 were each measured for appearance, surface area, MIL-100(Fe) mass ratio, and remaining material.
The results are shown in Table 1.
TABLE 1 appearance, surface area, mass fraction of MIL-100(Fe), and remaining material of the products of examples 1-3
2. An optical photograph of the MIL-100 (Fe)/cellulose composite pellet prepared in example 1 was taken and SEM-characterized. The results are shown in fig. 1 and fig. 2, respectively.
As can be seen from fig. 1 and 2, the MIL-100 (Fe)/cellulose composite pellets have smooth surfaces under the macroscopic view, and the size of the pellets is uniform, indicating that the pellets can be mass-produced; under the microscopic level, the MIL-100 (Fe)/cellulose composite spheres present a network-linked porous structure and MIL-100(Fe) is uniformly distributed, and the highly porous structure is beneficial to the adsorption of pollutants and the transmission of oxides.
3. PXRD characterization was performed for MIL-100 (Fe)/cellulose composite beads and MIL-100(Fe) prepared in example 1. The results are shown in FIG. 3.
As can be seen from FIG. 3, the MIL-100 (Fe)/cellulose composite pellets and MIL-100(Fe) have the same crystal structure. The method proves that the crystal structure of the MOFs material is not changed by the molding method, and the new chemical change is not generated after the MOFs and cellulose are compounded.
4. Thermogravimetric analysis tests were performed on the MIL-100 (Fe)/cellulose composite pellet, sodium carboxymethylcellulose (CMC), and MIL-100(Fe) prepared in example 1, respectively. The results are shown in FIG. 4.
As can be seen from FIG. 4, the loading of MIL-100(Fe) in the MIL-100 (Fe)/cellulose composite pellet was quantitatively calculated from the thermogravimetric curve. When the temperature reaches 750 ℃, the weight loss of the MIL-100(Fe), the CMC and the MIL-100 (Fe)/cellulose composite pellet reaches balance.
The ash content of MIL-100(Fe), CMC and MIL-100 (Fe)/cellulose composite pellets were recorded separately and the results are shown in table 2.
TABLE 2 Ash content after pyrolysis of MIL-100(Fe), CMC and MIL-100 (Fe)/cellulose composite pellets
| Substance(s) | Ash (%) |
| MIL-100(Fe) | 27 |
| CMC | 46 |
| MIL-100 (Fe)/cellulose composite pellet | 42 |
And the load amount of MIL-100(Fe) in the MIL-100 (Fe)/cellulose composite pellet was calculated using the following formula.
The formula is as follows: MIL-100(Fe) loading (wt%) (MIL-100 (Fe)/cellulose composite pellet ash-pure cellulose pellet ash) ÷ (pure MIL-100(Fe) ash-pure cellulose pellet ash).
The MIL-100 (Fe)/cellulose composite pellet has a MIL-100(Fe) loading of 79 wt% as calculated by the above formula. The method of the invention can obviously improve the loading capacity of the MOFs material and does not block the pore channels of the MOFs material.
5. The MIL-100(Fe) and MIL-100 (Fe)/cellulose composite pellets prepared in example 1 were subjected to a nitrogen desorption test at 77K. The results are shown in FIG. 5.
As can be seen from FIG. 5, the specific surface area of the MIL-100 (Fe)/cellulose composite pellet was close to that of MIL-100 (Fe). The cellulose serving as a cross-linking agent in the forming process is proved to be not used for blocking the pore channels of the MOFs material.
6. The method for removing the dye Methylene Blue (MB) in the water body by using the MIL-100 (Fe)/cellulose porous composite pellets comprises the following steps: filling the MIL-100 (Fe)/cellulose composite pellets into a needle cylinder, circularly dripping the MB solution into the needle cylinder by using a circulating pump to soak the MIL-100 (Fe)/cellulose composite pellets, and then adding potassium hydrogen persulfate to degrade.
3 parts of the MIL-100 (Fe)/cellulose porous composite pellet prepared in example 1, each 200mg, were added to an MB aqueous solution, wherein the MB aqueous solution had a volume of 40mL and a concentration of 40mg L-1And finishing the catalytic reaction on the MB under the condition that the rotating speed of the peristaltic pump is 1200 r/min. The dye removal was then monitored by recording the remaining MB content every 5min using a liquid uv spectrometer, and the average was taken. The results are shown in FIGS. 6(a) and 6 (b).
As shown in FIG. 6(a), the MIL-100 (Fe)/cellulose composite pellet + oxone have the most excellent MB degradation performance, and the MB degradation efficiency can reach more than 96% within 60 min. As can be seen from the corresponding pseudo-first order kinetic model in FIG. 6(b), the MIL-100 (Fe)/cellulose composite pellet + oxone have the highest degradation rate constant of 0.052min for MB degradation-1. Of these, the curve of the MIL-100 (Fe)/cellulose composite beads alone in the MB solution showed a slight decrease, and at the same time, the porous beads of the MIL-100 (Fe)/cellulose composite beads gradually turned blue, and it is presumed that MIL-100(Fe) having a high specific surface area produced an adsorption effect on MB, but the adsorption efficiency was low. In addition, in the MB solution system only containing potassium hydrogen persulfate, the curve is slowly reduced, because the potassium hydrogen persulfate can hydrolyze, oxidize and decompose part of MB, and the degradation rate constant is 0.011min-1And the degradation efficiency is far less than that of an MIL-100 (Fe)/cellulose composite pellet + potassium hydrogen persulfate system. Therefore, the MIL-100 (Fe)/cellulose composite pellet can effectively activate the oxone, and realize the efficient degradation of the dye pollutant MB.
7. Separating and taking out the degraded MIL-100 (Fe)/cellulose composite pellets, soaking the MIL-100 (Fe)/cellulose composite pellets in 0.1mol/L potassium hydrogen persulfate for 30min, washing the MIL-100 (Fe)/cellulose composite pellets after the original color is recovered, and performing degradation cycles for a plurality of times by using deionized water, thereby obtaining the cyclic degradation performance of the MIL-100 (Fe)/cellulose composite pellets on MB, wherein the result is shown in figure 7 (a). PXRD characterization was performed on the MIL-100 (Fe)/cellulose composite beads before and after 5 cycles of degradation, and the results are shown in FIG. 7 (b). SEM characterization of MIL-100 (Fe)/cellulose composite beads after 5 cycles of degradation is shown in FIGS. 7(c) and 7 (d).
As can be seen from FIG. 7(a), after 5 degradation cycles, the MIL-100 (Fe)/cellulose composite beads maintain high removal efficiency, and the fifth removal efficiency can reach 93.6%.
As can be seen from fig. 7(b) - (d), the crystal structure and morphology of the MOFs did not change after recycling. The MIL-100 (Fe)/cellulose composite pellets ensure the degradation effect, avoid the loss of materials in the use and recovery process and enhance the recycling performance of the materials.
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. A preparation method of an MIL-100 (Fe)/cellulose porous composite pellet is characterized by comprising the following steps:
(1) adding a cellulose binder into water, stirring in a water bath, and performing ultrasonic treatment to obtain a cellulose solution;
(2) adding MIL-100(Fe) into a cellulose solution, uniformly stirring, and carrying out water bath ultrasonic treatment to obtain a mixed solution;
(3) adding the mixed solution into a metal ion solution for primary soaking, filtering, and adding water for secondary soaking to obtain composite small-ball hydrogel;
(4) and drying the composite small ball hydrogel to obtain the MIL-100 (Fe)/cellulose porous composite small ball.
2. The method for preparing MIL-100 (Fe)/cellulose porous composite beads according to claim 1, wherein in the step (1), the cellulose binder is sodium carboxymethyl cellulose; the mass-volume ratio of the sodium carboxymethylcellulose to the water is 1g (50-100) mL.
3. The method for preparing MIL-100 (Fe)/cellulose porous composite beads as claimed in claim 1, wherein in the step (1), the temperature of the water bath stirring is 30-40 ℃, the rotation speed is 1000-; the ultrasonic treatment time is 5-10 min.
4. The method for preparing MIL-100 (Fe)/cellulose porous composite pellets according to claim 2, wherein in the step (2), the mass ratio of MIL-100(Fe) to sodium carboxymethyl cellulose is (8-9): 1.
5. The method for preparing MIL-100 (Fe)/cellulose porous composite pellet as claimed in claim 1, wherein in the step (2), the stirring temperature is 20-30 ℃, the rotation speed is 10000-; the water bath ultrasound time is 20-30 min.
6. The method for preparing MIL-100 (Fe)/cellulose porous composite beads according to claim 1, wherein in the step (3), the metal ions in the metal ion solution are at least one of copper ions, iron ions and zinc ions, and the concentration is 0.5-2 mol/L.
7. The method for preparing porous MIL-100 (Fe)/cellulose composite pellets according to claim 1, wherein, in the step (3), the first soaking is performed at a temperature of 20-30 ℃ for 20-30 min; the temperature of the second soaking is 20-30 ℃, and the time is 2-3 h.
8. The method for preparing MIL-100 (Fe)/cellulose porous composite pellets according to claim 1, wherein the drying temperature is 20-40 ℃ and the drying time is 8-12h in step (4).
9. Use of the MIL-100 (Fe)/cellulose porous composite beads prepared according to the method of any one of claims 1 to 8 for adsorbing degradation dyes.
10. An application according to claim 9, characterized in that it comprises in particular the following steps: mixing MIL-100 (Fe)/cellulose porous composite pellets with a water body containing 10-40mg/L of dye and having pH of 3-9 according to a mass-volume ratio of 1g to 200mL, performing shock adsorption, and adding potassium hydrogen persulfate for degradation.
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| CN202210404779.8A CN114672064B (en) | 2022-04-18 | 2022-04-18 | Preparation method and application of MIL-100 (Fe)/cellulose porous composite pellet |
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| CN202210404779.8A CN114672064B (en) | 2022-04-18 | 2022-04-18 | Preparation method and application of MIL-100 (Fe)/cellulose porous composite pellet |
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