CN114672064B - 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 MIL-100 (Fe)/cellulose porous composite pellets, 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 performing water bath ultrasonic treatment to obtain a mixed solution; (3) Adding the mixed solution into a metal ion solution for first soaking, filtering, and then adding into water for second soaking to obtain a composite pellet hydrogel; and (4) drying the composite pellet hydrogel to obtain the product. 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) loading capacity, high adsorption and degradation efficiency, easiness in recycling and the like, can realize efficient adsorption and degradation of dyes, and has a large application prospect.
Description
Technical Field
The invention relates to the technical field of new materials, in particular to a preparation method and application of MIL-100 (Fe)/cellulose porous composite pellets.
Background
Along with the acceleration of industrialization process, industrial wastewater and artificially generated harmful wastewater are discharged wantonly, 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.
Textile industry is taken as a dominant industry in China and takes a leading place in the global textile industry, but the problem of discharge of printing and dyeing wastewater of the industry is very serious. Meanwhile, dyes in printing and dyeing wastewater are the most dominant pollutants. Dyes are widely used in textile, leather, paper, painting and plastics industries. The wastewater has complex components and contains various toxic and harmful substances, which endanger aquatic organisms and ecological environment. Some dyes are carcinogenic and can be enriched in organisms, causing acute or chronic diseases. In addition, some dyes absorb or reflect sunlight entering water, thereby inhibiting the propagation and growth of bacteria, and failing to effectively degrade impurities in water. Therefore, it is important to develop a technique for efficiently and safely removing dye from wastewater.
In recent years, the advanced oxidation method is used as a method for removing the dye in water with high efficiency, low cost and no secondary pollution, and has great application value and prospect. The Metal Organic Frameworks (MOFs) are porous functional materials formed by self-assembling metal nodes (metal ions or metal clusters) and organic ligands through coordination bonds, and are widely applied to advanced oxidation technology due to the characteristics of high specific surface area, adjustable pore diameter, unsaturated metal site containing, easy functionalization, surface modification and the like.
However, the powdery MOFs are difficult to recycle, have high loss rate, are easy to cause secondary pollution and the like, and cause serious obstruction to the industrialized application of the MOFs.
Therefore, how to provide MOFs composite pellets with low processing and forming cost, good removal efficiency, high recycling rate, safety and environmental protection is a problem to be solved by the technicians in the field.
Disclosure of Invention
In view of the above, the present invention aims to provide a preparation method and application of MILs-100 (Fe)/cellulose porous composite pellets, 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, easy 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 above purpose, the present invention adopts the following technical scheme:
the preparation method of the 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 performing water bath ultrasonic treatment to obtain a mixed solution;
(3) Adding the mixed solution into a metal ion solution for first soaking, filtering, and then adding into water for second soaking to obtain a composite pellet hydrogel;
(4) And drying the composite pellet hydrogel to obtain the MIL-100 (Fe)/cellulose porous composite pellets.
Further, in the step (1), the cellulose binder is sodium carboxymethyl cellulose; the mass volume ratio of the sodium carboxymethyl cellulose 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 1000-1200r/min, and the time is 1-3h; the ultrasonic treatment time is 5-10min.
The technical proposal has the beneficial effect that bubbles in the solution can be removed by ultrasonic treatment.
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 rotating speed is 10000-20000r/min, and the time is 0.5-1h; the time of water bath ultrasonic treatment is 20-30min.
Further, in the step (3), the metal ion in the metal ion solution is at least one of copper ion, iron ion and zinc ion, and the concentration is 0.5-2mol/L.
Further, in the step (3), the temperature of the first soaking is 20-30 ℃ and the time is 20-30min; the second soaking temperature is 20-30deg.C, and the time is 2-3h.
The technical proposal has the beneficial effects that MIL-100 (Fe)/cellulose composite pellets are molded in metal ion solution through first soaking; by the second soaking, the superfluous 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 8-12h.
The invention also claims the application of the MIL-100 (Fe)/cellulose porous composite pellet prepared by the preparation method in adsorbing and degrading dye, which comprises the following steps: the specific surface area is 1200-1300m according to the mass-volume ratio of 1g to 200mL 2 Mixing/g MIL-100 (Fe)/cellulose porous composite pellet with water containing 10-40mg/L dye and pH 3-9, shake adsorbing, and adding potassium hydrogen persulfate for degradation.
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 1200-1300m 2 And/g, little loss.
2. The loading capacity of 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 the porosity of MIL-100 (Fe) are ensured.
3. According to the invention, MIL-100 (Fe)/cellulose porous composite pellets are prepared and formed, 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 spherical MIL-100 (Fe) is very suitable for industrialized use; the water stability of the molded MIL-100 (Fe) is good.
4. The cellulose binder of the invention has rich reserves, no toxicity and no secondary pollution.
5. The preparation process of MIL-100 (Fe)/cellulose porous composite pellets is simple and convenient to synthesize, low in cost, suitable for large-scale preparation of MOFs with various morphologies, significant in development of MOFs material forming processes, and further significant in commercial and industrialized application of MOFs materials.
6. According to the invention, MIL-100 (Fe) in the MIL-100 (Fe)/cellulose porous composite pellet can effectively catalyze and activate an oxidant, and efficiently degrade dye molecules in water.
7. The MIL-100 (Fe)/cellulose porous composite pellet adsorption and degradation dye method has the advantages of simple treatment process and degradation appliance, low cost, high material degradation efficiency and good recycling performance, is a widely-used dye treatment method, and has high commercial value and practical application prospect.
Drawings
FIG. 1 is an optical photograph of MIL-100 (Fe)/cellulose composite beads prepared in example 1;
FIG. 2 is an SEM image of MIL-100 (Fe)/cellulose composite beads prepared in 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 of MIL-100 (Fe)/cellulose composite beads and MIL-100 (Fe) prepared in example 1;
FIG. 4 is a thermogravimetric plot of MIL-100 (Fe)/cellulose composite beads, sodium carboxymethylcellulose, and MIL-100 (Fe) prepared in example 1;
FIG. 5 is a graph showing the N at 77K of MIL-100 (Fe) and MIL-100 (Fe)/cellulose composite beads prepared in example 1 2 Adsorption isotherms;
FIG. 6 is a graph showing the degradation efficiency of dye methylene blue removal from water using MIL-100 (Fe)/cellulose porous composite beads;
FIG. 7 (a) is the cyclical degradation efficiency of MIL-100 (Fe)/cellulose composite beads on MB; FIG. 7 (b) is a 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 shorthand of sodium carboxymethyl cellulose, PMS is the shorthand of potassium hydrogen persulfate, MIL-100 is the shorthand of MIL-100 (Fe), MIL-100/CMC-HD is the shorthand of MIL-100 (Fe)/cellulose composite pellet, MIL-100/CMC-HD-5C is the shorthand of MIL-100 (Fe)/cellulose composite pellet after 5 times of cyclic degradation.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the 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 at a rotating speed of 1000r/min in a water bath at 40 ℃, and carrying out ultrasonic treatment for 50min to obtain sodium carboxymethylcellulose solution;
(2) Adding 3.6g of MIL-100 (Fe) powder into 20g of sodium carboxymethyl cellulose solution, stirring at 20 ℃ for 1h at 10000r/min by using a homogenizing cutter, and performing ultrasonic treatment in a water bath at 20 ℃ for 20min until the powder is converted into a uniform thick fluid mixture to obtain a mixed solution;
(3) Dripping the mixed solution into copper chloride solution with the temperature of 20 ℃ and the concentration of 0.5mol/L by a syringe, soaking for 30min, filtering, collecting spherical MOFs, adding into deionized water with the temperature of 20 ℃ and soaking for 3h to obtain composite pellet hydrogel;
(4) And (3) putting the composite pellet hydrogel into a vacuum oven at 20 ℃ for drying 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 carboxymethyl cellulose into 97.5mL of deionized water, stirring for 2.5h at a rotating speed of 1200r/min in a water bath at 30 ℃, and carrying out ultrasonic treatment for 8min to obtain sodium carboxymethyl cellulose solution;
(2) Adding 4.2g of MIL-100 (Fe) powder into 25g of sodium carboxymethyl cellulose solution, stirring at a temperature of 25 ℃ for 1h at a rotating speed of 15000r/min by using a homogenizing cutter, and performing ultrasonic treatment in a water bath at 25 ℃ for 25min until the powder 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 a syringe, soaking for 20min, filtering, collecting spherical MOFs, adding into deionized water with the temperature of 25 ℃ and soaking for 2h to obtain the composite pellet hydrogel;
(4) And (3) putting the composite pellet hydrogel into a vacuum oven at 25 ℃ for drying for 10 hours 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 carboxymethyl cellulose into 97mL of deionized water, stirring for 3h at a rotating speed of 1000r/min in a water bath at 40 ℃, and carrying out ultrasonic treatment for 10min to obtain sodium carboxymethyl cellulose solution;
(2) Adding 5.1g of MIL-100 (Fe) powder into 27.5g of sodium carboxymethyl cellulose solution, stirring at a temperature of 30 ℃ for 0.5h at a rotating speed of 20000r/min by using a homogenizing cutter, and performing ultrasonic treatment in a water bath at 30 ℃ for 30min until the powder is converted into a uniform thick fluid mixture to obtain a mixed solution;
(3) Dripping the mixed solution into copper chloride solution with the temperature of 30 ℃ and the concentration of 1.5mol/L by a syringe, soaking for 25min, filtering, collecting spherical MOFs, adding into deionized water with the temperature of 30 ℃ and soaking for 2.5h to obtain the composite pellet hydrogel;
(4) And (3) putting the composite pellet hydrogel into a vacuum oven at 30 ℃ for drying for 12 hours to obtain the MIL-100 (Fe)/cellulose porous composite pellet.
Performance testing
1. MIL-100 (Fe)/cellulose porous composite pellets prepared in examples 1 to 3 were each taken and tested for appearance, surface area, mass ratio of MIL-100 (Fe) and remaining materials, respectively.
The results are shown in Table 1.
TABLE 1 appearance, surface area, mass fraction of MIL-100 (Fe) and residual substances of the products of examples 1-3
2. The MIL-100 (Fe)/cellulose composite racquet prepared in example 1 was photographed and SEM characterized. The results are shown in fig. 1 and 2, respectively.
As can be seen from fig. 1 and 2, the MILs-100 (Fe)/cellulose composite pellets show smooth surfaces under macroscopic conditions, and the pellets are uniform in size, indicating that the pellets can be mass-produced; under the microcosmic condition, the MIL-100 (Fe)/cellulose composite pellets show a net-shaped connected porous structure, the 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 on MILs-100 (Fe)/cellulose composite pellets and MILs-100 (Fe), respectively, prepared in example 1. The results are shown in FIG. 3.
As can be seen from FIG. 3, MIL-100 (Fe)/cellulose composite beads and MIL-100 (Fe) have the same crystal structure. The crystal structure of MOFs material is not changed after molding by the method, which indicates that the MOFs is not subjected to new chemical change after compounding with cellulose.
4. Thermogravimetric analysis test was performed on MILs-100 (Fe)/cellulose composite pellets, sodium carboxymethyl cellulose (CMC) and MILs-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 beads was quantitatively calculated from the thermogravimetric curve. When the temperature reaches 750 ℃, the weight loss of MIL-100 (Fe), CMC and MIL-100 (Fe)/cellulose composite pellets are balanced.
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 after pyrolysis of MIL-100 (Fe), CMC and MIL-100 (Fe)/cellulose composite pellets
| Substance (B) | 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 beads was calculated using the following formula.
The formula is: MILs-100 (Fe) loading (wt%) = (MILs-100 (Fe)/cellulose composite pellet ash-pure cellulose pellet ash)/(pure MILs-100 (Fe) ash-pure cellulose pellet ash).
As calculated by the above formula, the loading of MIL-100 (Fe) in the MIL-100 (Fe)/cellulose composite pellet was 79wt%. The method can obviously improve the loading capacity of the MOFs material and does not block the pore canal of the MOFs material.
5. Nitrogen desorption tests were performed on MIL-100 (Fe) and MIL-100 (Fe)/cellulose composite beads prepared in example 1 at 77K. The results are shown in FIG. 5.
As can be seen from FIG. 5, the specific surface area of MIL-100 (Fe)/cellulose composite beads was close to that of MIL-100 (Fe). It was demonstrated that cellulose was used as a cross-linking agent during the formation process to unblock the channels of MOFs material.
6. The method for removing the dye Methylene Blue (MB) in the water body by using MIL-100 (Fe)/cellulose porous composite pellets comprises the following steps: filling MIL-100 (Fe)/cellulose composite pellets into a needle cylinder, using a circulating pump to circularly drop MB solution into the needle cylinder, so that the MB solution infiltrates the MIL-100 (Fe)/cellulose composite pellets, and then adding potassium hydrogen persulfate for degradation.
3 parts of MIL-100 (Fe)/cellulose porous composite beads prepared in example 1, 200mg each, were added to MB aqueous solutions each having a volume of 40mL and a concentration of 40mg L -1 And the catalytic reaction of MB is completed under the condition that the rotating speed of the peristaltic pump is 1200 r/min. The dye removal was then monitored by recording the residual MB content using a liquid uv spectrometer every 5min, taking the average. The results are shown in FIG. 6 (a) and FIG. 6 (b).
As shown in FIG. 6 (a), MIL-100 (Fe)/cellulose composite pellets and potassium hydrogen persulfate 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 pseudo first order kinetic model corresponding to FIG. 6 (b), MIL-100 (Fe)/cellulose composite pellet+potassium hydrogen persulfate has the highest degradation rate constant of 0.052min for MB degradation -1 . Wherein, the MIL-100 (Fe)/cellulose composite pellet alone shows slight decrease in MB solution, and at the same time, the MIL-100 (Fe)/cellulose composite pellet porous pellet gradually turns blue, and it is presumed that MIL-100 (Fe) with high specific surface area has adsorption effect on MB, but the adsorption efficiency is lower. In addition, in the MB solution system with only potassium hydrogen persulfate, the curve was slowly decreased, since potassium hydrogen persulfate itself could hydrolyze the oxidative decomposition part MB, and the degradation rate constant was 0.011min -1 Far less than the degradation efficiency of MIL-100 (Fe)/cellulose composite pellet and potassium hydrogen persulfate system. From this, can derive, MIL-100 (Fe)/cellulose compound pellet can effectively activate potassium hydrogen persulfate, realize the high-efficient degradation of dye pollutant MB.
7. Separating and taking out the degraded MIL-100 (Fe)/cellulose composite pellets, soaking in 0.1mol/L potassium hydrogen persulfate for 30min, recovering the MIL-100 (Fe)/cellulose composite pellets to the original color, washing with deionized water, and performing the degradation cycle for several times to obtain the cyclic degradation performance of the MIL-100 (Fe)/cellulose composite pellets on MB, wherein the result is shown in figure 7 (a). And PXRD characterization was performed on MILs-100 (Fe)/cellulose composite pellets before and after 5 cycles of degradation, the results are shown in fig. 7 (b). SEM characterization was performed on MIL-100 (Fe)/cellulose composite pellets after 5 cycles of degradation, and the results are shown in FIG. 7 (c) and FIG. 7 (d).
As can be seen from FIG. 7 (a), after 5 degradation cycle experiments, MIL-100 (Fe)/cellulose composite pellets 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 MOFs did not change after recycling. The MIL-100 (Fe)/cellulose composite pellets can ensure the degradation effect, avoid the loss of materials in the recycling process, and strengthen 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 (7)
1. The preparation method of the MIL-100 (Fe)/cellulose porous composite pellet is characterized by comprising the following steps of:
(1) Adding a cellulose binder into water, stirring in a water bath, and performing ultrasonic treatment to obtain a cellulose solution;
the cellulose binder is sodium carboxymethyl cellulose; the mass volume ratio of the sodium carboxymethyl cellulose to the water is 1g (50-100) mL;
(2) Adding MIL-100 (Fe) into a cellulose solution, uniformly stirring, and performing water bath ultrasonic treatment to obtain a mixed solution;
the mass ratio of MIL-100 (Fe) to sodium carboxymethylcellulose is (8-9): 1;
(3) Adding the mixed solution into a metal ion solution for first soaking, filtering, and then adding into water for second soaking to obtain a composite pellet hydrogel;
the metal ions in the metal ion solution are at least one of copper ions, iron ions and zinc ions, and the concentration is 0.5-2mol/L;
(4) And drying the composite pellet hydrogel to obtain the MIL-100 (Fe)/cellulose porous composite pellet.
2. The preparation method of the MIL-100 (Fe)/cellulose porous composite pellets according to claim 1, wherein in the step (1), the temperature of water bath stirring is 30-40 ℃, the rotating speed is 1000-1200r/min, and the time is 1-3h; and the time of the ultrasonic treatment is 5-10min.
3. The preparation method of the MIL-100 (Fe)/cellulose porous composite pellets according to claim 1, wherein in the step (2), the stirring temperature is 20-30 ℃, the rotating speed is 10000-20000r/min, and the time is 0.5-1h; the time of the water bath ultrasonic treatment is 20-30min.
4. The method for preparing MILs-100 (Fe)/cellulose porous composite pellets according to claim 1, wherein in step (3), the first soaking temperature is 20-30 ℃ for 20-30min; the temperature of the second soaking is 20-30 ℃ and the time is 2-3h.
5. The method for preparing MILs-100 (Fe)/cellulose porous composite pellets according to claim 1, wherein in step (4), the drying temperature is 20-40 ℃ and the time is 8-12 hours.
6. Use of MILs-100 (Fe)/cellulose porous composite pellets prepared by the process of any of claims 1-5 for adsorbing and degrading dyes.
7. The use according to claim 6, characterized in that it comprises in particular the following steps: mixing MIL-100 (Fe)/cellulose porous composite pellets with water containing 10-40mg/L dye and having pH of 3-9 according to the mass-volume ratio of 1g to 200mL, vibrating and adsorbing, and adding potassium hydrogen persulfate for degradation.
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