CN109589939B - Preparation method of sandwich type UiO-66/chitosan @ UiO-66 composite bead with high adsorption performance - Google Patents
Preparation method of sandwich type UiO-66/chitosan @ UiO-66 composite bead with high adsorption performance Download PDFInfo
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- 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
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- 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
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- 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
- B01J20/28016—Particle form
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- 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
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
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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
- C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
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- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
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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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
- B01J2220/4825—Polysaccharides or cellulose materials, e.g. starch, chitin, sawdust, wood, straw, cotton
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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
- C02F2101/30—Organic compounds
- C02F2101/306—Pesticides
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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
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
Abstract
The invention belongs to the technical field of composite materials, and particularly relates to a preparation method of a sandwich type UiO-66/chitosan @ UiO-66(UiO-66/CS @ UiO-66) composite bead. The preparation method comprises two processes: 1. mixing UiO-66 and chitosan uniformly and preparing millimeter beads; 2. UiO-66 was deposited on the bead surface. The prepared UiO-66/CS @ UiO-66 composite material has strong adsorption capacity on 2,4-D, has adsorption capacity higher than that of most nano materials, is easy to separate, can be quickly separated and recycled by adopting a simple filtration method, can be repeatedly used, avoids secondary environmental pollution, and is an environment-friendly adsorbent for adsorbing pesticide wastewater. The preparation method is simple, easy to operate and good in stability, and the prepared adsorbent has the advantages of stable structure, high adsorption quantity, easiness in separation, reusability, environmental friendliness and the like.
Description
Technical Field
The invention belongs to the technical field of composite materials, and particularly relates to a preparation method of a sandwich type UiO-66/chitosan @ UiO-66 composite bead.
Background
China is a big agricultural country, the using amount of pesticides is very large, 2,4-D belongs to one of the types with larger using amount of herbicides, and in recent years, the average annual demand of 2,4-D in China reaches more than 5000 t. A large amount of 2,4-D remains in the soil and permeates into the water body, and 2,4-D has a stable structure and good water fluidity and can exist in the environment for a long time (half-life is as long as 300 days in an anaerobic environment). 2,4-D is a pollutant with moderate toxicity to humans and animals, has been shown to be an endocrine disrupter, and can be a carcinogen and mutagen, as well as irritating to human skin and eyes for a long time. Methods for removing 2,4-D from water are known in the art, such as photocatalytic degradation, biodegradation, ozonation, adsorption, and the like. In contrast, the adsorption method is one of the most competitive removal methods of 2,4-D, because it has the advantages of simple process, easy operation and low cost. The commonly used adsorbents include activated carbon, molecular sieves, graphene and derivatives thereof, and most of them have low adsorption capacity and are difficult to separate and recover. Therefore, it is very important to prepare an adsorbent for treating 2,4-D wastewater which is efficient and easy to separate.
UiO-66 has a cation Zr6O4(OH)4The organic ligand terephthalic acid is used as an octahedral cage structure of a connector, and has high specific surface area, excellent water stability and excellent acid stability. However, the recovery of the post-adsorption UiO-66 is inconvenient and often requires extensive post-treatment to separate the adsorbent from the water, which is a disadvantage that is not negligible in practical applications. Chitosan (CS) is a product synthesized by deacetylation of chitin, and is widely present in nature, such as the shell of crustaceans. Chitosan is considered a potential environmentally friendly adsorbent because it is non-toxic, biocompatible, biodegradable and low in cost. It has excellent adsorption capacity to heavy metal ion and dye. However, the effect of pure chitosan in removing organic matters in water by adsorption is not good, so that the application of chitosan in the adsorption field is limited.
Disclosure of Invention
The invention aims to provide a simple preparation method of millimeter composite bead UiO-66/CS @ UiO-66, which can efficiently adsorb organochlorine pesticides and has a stable structure and easy separation. The chitosan and the UiO-66 are compounded to form the sandwich-type millimeter-scale bead which is used as the adsorbent, so that the recovery problem of the adsorbent can be easily solved, and the UiO-66 deposited on the surface of the bead can effectively enhance the adsorption capacity of the bead. The preparation method comprises the following steps:
(1) the same mass of chitosan and UiO-66 was added to 40ml of 1% by volume aqueous hydrochloric acid and stirred for 6-8 hours until a homogeneous colloidal solution was formed. Through comparison tests, the result shows that the beads prepared by hydrochloric acid have stronger adsorption capacity on 2, 4-D.
(2) And adding the UiO-66 and the sodium tripolyphosphate with the mass ratio of 2:1 into 30ml of deionized water, and carrying out ultrasonic treatment for 5 minutes to uniformly mix the mixture to obtain a UiO-66/sodium tripolyphosphate solution.
(3) Slowly dripping the uniformly mixed sol prepared in the step (1) into the UiO-66/sodium tripolyphosphate solution prepared in the step (2) by using a burette to immediately form 1-2mm precipitated beads;
wherein, when the dropping speed is slower than 3 seconds per drop, beads with smaller particle size can be obtained, and when the dropping speed is too fast, the particle size of the prepared beads is larger, and the adsorption capacity is influenced.
(4) And (4) after the dropwise addition in the step (3) is finished, integrally transferring the mixture into a water bath constant temperature oscillation box, oscillating the mixture at 120rpm for 6 hours, filtering the mixture, taking out the beads, and washing the beads with deionized water for three times.
(5) The wet beads were transferred to a 0.02mol/L glutaraldehyde solution and incubated at 40 ℃ for 12 hours.
(6) The resulting beads were filtered again, washed repeatedly with deionized water until the pH of the beads was neutral, and lyophilized at-50 ℃ for 10 hours to give UiO-66/CS @ UiO-66 mm composite beads.
In the step (2) of the invention, UiO-66 is added into the sodium tripolyphosphate-water mixed solution to obtain a UiO-66/sodium tripolyphosphate solution, and the beads are cultured in the UiO-66/sodium tripolyphosphate solution in combination with the step (3) to achieve the purpose of loading the UiO-66 on the surfaces of the beads, so that the UiO-66 is loaded in the beads and on the surfaces of the beads. The specific process comprises the following steps: adding chitosan and UiO-66 into a hydrochloric acid aqueous solution, stirring to form a uniform colloidal solution, dropwise adding the colloidal solution into sodium tripolyphosphate to immediately form beads, adsorbing the UiO-66 originally dispersed in the sodium tripolyphosphate solution to the surfaces of the beads in an oscillation process, transferring the beads into glutaraldehyde to promote cross-linking between chitosan molecules, and fixing the UiO-66 loaded inside and on the surfaces of the beads to form the sandwich-type UiO-66/chitosan @ UiO-66 composite beads.
Step (4) shaking at 120rpm for 6 hours was performed to make the UiO-66 load on the bead surface more abundant, so that the entire bead surface was covered with UiO-66. The washing by filtration is to wash out UiO-66 with a weak surface load.
Advantageous effects
The UiO-66 has good water stability and stable structure in the adsorption process. More importantly, the adsorbent prepared by the invention is loaded with UiO-66 in the bead and on the surface of the bead, so that the adsorption quantity of the composite bead is effectively improved. The sandwich structure further increases the adsorption capacity of the adsorbent and makes the structure of the beads more stable.
The millimeter composite bead prepared by the invention has the advantages of simple synthesis, convenient separation, strong adsorption capacity and the like, and can be used for adsorbing organochlorine pesticides.
Drawings
Fig. 1 is a picture actually taken of millimeter composite beads prepared in example 1, comparative example 2 and comparative example 3.
Fig. 2 is a Scanning Electron Microscope (SEM) picture of the surface structure of the millimeter composite beads prepared in example 1, comparative example 2, and comparative example 3.
FIG. 3 is a graph of the adsorption capacity of millimeter composite beads prepared in example 1, comparative example 2 and comparative example 3 for 2,4-D as a function of the initial concentration of 2, 4-D.
FIG. 4 is a plot of the amount of adsorbed 2,4-D versus UiO-66/CS @ UiO-66 versus the pH of the solution for the millimeter composite beads prepared in example 1.
FIG. 5 is a plot of Zeta potential as a function of pH for millimeter composite beads UiO-66/CS @ UiO-66 prepared in example 1.
FIG. 6 is a bar graph of the adsorption of 2,4-D versus the number of cycles for the millimeter composite beads UiO-66/CS @ UiO-66 obtained in example 1.
Detailed Description
The present invention will be described in detail with reference to specific embodiments, which are carried out on the premise of the technical solution of the present invention, but the scope of the present invention is not limited to the following embodiments.
The embodiment of the invention provides a composite millimeter bead UiO-66/CS @ UiO-66 for adsorbing 2, 4-D.
Example 1
Preparation of millimeter composite bead UiO-66/CS @ UiO-66
0.8g of chitosan and 0.8g of UiO-66 were added to 40ml of a 1% hydrochloric acid aqueous solution by volume, and stirred for 6 to 8 hours until a uniform colloidal solution was formed. 0.6g of UiO-66 and 0.3g of sodium tripolyphosphate were added to 30ml of deionized water, and the mixture was sonicated for 5 minutes to mix well. Slowly and dropwise adding the uniformly mixed sol prepared in the step (1) into the prepared UiO-66/sodium tripolyphosphate solution by using a burette to immediately form 1-2mm precipitated beads. After completion of the dropwise addition, the whole was transferred to a water bath constant temperature shaking tank, shaken at 120rpm for 6 hours, filtered to remove beads, and then rinsed three times with deionized water. The wet beads were transferred to a 0.02mol/L glutaraldehyde solution and incubated at 40 ℃ for 12 hours. The resulting beads were filtered again, washed repeatedly with deionized water until the pH of the beads was neutral, and lyophilized at-50 ℃ for 10 hours to give UiO-66/CS @ UiO-66 mm composite beads.
Comparative example 1
0.4g of chitosan and 0.8g of UiO-66 were added to 40ml of a 1% aqueous hydrochloric acid solution by volume and stirred for 6 to 8 hours until a uniform colloidal solution was formed. 0.6g of UiO-66 and 0.3g of sodium tripolyphosphate were added to 30ml of deionized water, and the mixture was sonicated for 5 minutes to mix well. The prepared homogeneous mixed sol was slowly added dropwise to the prepared UiO-66/sodium tripolyphosphate solution using a burette to form 1-2mm precipitated beads immediately. After completion of the dropwise addition, the whole was transferred to a water bath constant temperature shaking tank, shaken at 120rpm for 6 hours, filtered to remove beads, and then rinsed three times with deionized water. The wet beads were transferred to a 0.02mol/L glutaraldehyde solution and incubated at 40 ℃ for 12 hours. The resulting beads were filtered again, washed repeatedly with deionized water until the pH of the beads was neutral, and lyophilized at-50 ℃ for 10 hours to give UiO-66/CS @ UiO-66-1 mm composite beads.
Comparative example 2
Preparation of chitosan composite bead UiO-66/CS with UiO-66 loaded only inside
0.8g of chitosan and 0.8g of UiO-66 were added to 40ml of a 1% hydrochloric acid aqueous solution by volume, and stirred for 6 to 8 hours until a uniform colloidal solution was formed. 0.3g of sodium tripolyphosphate was added to 30ml of deionized water and sonicated for 5 minutes to allow complete dissolution. The colloidal solution was slowly added dropwise to the prepared sodium tripolyphosphate solution using a burette to form 1-2mm precipitated beads immediately. After completion of the dropwise addition, the beads were stored at room temperature for 6 hours, filtered, and then rinsed three times with deionized water. The wet beads were transferred to a 0.02mol/L glutaraldehyde solution and incubated at 40 ℃ for 12 hours. The resulting beads were filtered again, washed repeatedly with deionized water until the pH of the beads was neutral, and lyophilized at-50 ℃ for 10 hours to give UiO-66/CS millimeter composite beads.
Comparative example 3
0.8g of chitosan and 0.8g of UiO-66 were added to 40ml of a 1% hydrochloric acid aqueous solution by volume, and stirred for 6 to 8 hours until a uniform colloidal solution was formed. 0.6g of UiO-66 and 0.3g of sodium tripolyphosphate were added to 30ml of deionized water, and the mixture was sonicated for 5 minutes to mix well. And (3) quickly dropwise adding the prepared uniformly mixed sol into the prepared UiO-66/sodium tripolyphosphate solution by using a burette to immediately form precipitated beads with the particle size of more than 2 mm. After completion of the dropwise addition, the whole was transferred to a water bath constant temperature shaking tank, shaken at 120rpm for 6 hours, filtered to remove beads, and then rinsed three times with deionized water. The wet beads were transferred to a 0.02mol/L glutaraldehyde solution and incubated at 40 ℃ for 12 hours. The resulting beads were filtered again, washed repeatedly with deionized water until the pH of the beads was neutral, and lyophilized at-50 ℃ for 10 hours to give UiO-66/CS @ UiO-66-2 mm composite beads.
It can be seen from figure 1 that the particle size of both beads prepared in example 1 and comparative example 2 was between 1 and 2 mm. However, the beads prepared in comparative example 1 were directly in a half-crushed form, and were crushed into powder with a slight application of pressure, and thus were not used for adsorption. Comparative example 3 beads were prepared having a particle size of between 2mm and 3 mm. As can be seen from FIG. 2, the UiO-66/CS composite beads prepared in comparative example 1 have only the UiO-66 inside and the surface is relatively smooth, while the millimeter composite beads prepared in comparative example 2 and comparative example 3 have similar surface morphologies and have a large number of bumps, namely the UiO-66 fixed on the bead surface after deposition, and the surface appears uneven.
Detection of adsorption Properties
The materials prepared in example 1, comparative example 2 and comparative example 3 were used for the measurement of 2,4-D adsorption performance, as follows:
5mg of adsorbent was weighed in each case into 50ml of 2,4-D solution. After adsorption was complete, the solution was collected using a syringe and passed through a 0.44 μm filter. The residual concentration and the amount of adsorption of 2,4-D were calculated by measuring the absorbance value at 283nm using a UV spectrophotometer.
5mg of the millimetric composite bead UiO-66/CS @ UiO-66 prepared in example 1 were weighed at a temperature of 298K and a pH of 4 and added to 50mL of an initial concentration of 10 mg.L-1、25mg·L-1、50mg·L-1、100mg·L-1And 150 mg. L-1In the 2,4-D solution, a water bath constant temperature oscillator is adopted to oscillate for 12 hours at the rotating speed of 150rpm, and the influence of different initial 2,4-D concentrations on the adsorption performance of the adsorbent is researched. The same experiment was performed using the millimeter composite beads prepared in comparative example 2 and comparative example 3 as a comparison.
As can be seen from FIG. 3, the adsorption capacity of all three beads increases with the increase of the concentration of 2,4-D, but the UiO-66/CS @ UiO-66 composite beads prepared in example 1 have better adsorption capacity.
5mg of the millimetric composite bead UiO-66/CS @ UiO-66 prepared in example 1 are weighed at a pH of 2.8 to 11.3 adjusted with 0.1M HCl and NaOH at a temperature of 298K and added to 50mL of an initial concentration of 100 mg.L-1In the 2,4-D solution, a water bath constant temperature oscillator is adopted to respectively oscillate for 12 hours at the rotating speed of 150rpm, and the influence of different pH values on the adsorption amount of the adsorbent is researched by combining with the Zeta potential of the composite beads.
As can be seen from FIG. 4, the adsorption of 2,4-D by the UiO-66/CS @ UiO-66 beads tended to increase and decrease with increasing pH, with the maximum adsorption being obtained at a pH of 3.5.
And (4) measuring the Zeta potential. A sample of the powder of UiO-66/CS @ UiO-66 was dispersed in pre-adjusted ultra-pure water (pH 2.5-9.5) at 8 different pH values, and then its Zeta potential was measured.
As can be seen in FIG. 5, the UiO-66/CS @ UiO-66 bead surface charge decreases with increasing pH, and is 0 at pH 5.8.
The effect of the number of cycles on the adsorbent loading was studied, each cycle being carried out at a temperature of 298K and a pH of 4, using a ratio of 3: 7 ethanol: the aqueous solution desorbs the adsorbent.
As can be seen from FIG. 6, after continuous adsorption-desorption-adsorption cycles, the UiO-66/CS @ UiO-66 composite beads still maintain higher adsorption capacity, and after 5 cycles, the adsorption capacity can still reach more than 85% of the original adsorption capacity.
It should be emphasized that the above-described embodiments are merely examples for clearly illustrating the present invention, but the present invention is not limited to the above-described embodiments. Other variants will be apparent to those skilled in the art on the basis of the foregoing description, and it is not necessary to exemplify all the embodiments herein, but rather obvious variations are contemplated which are within the scope of the invention.
Claims (4)
1. A preparation method of sandwich type UiO-66/chitosan @ UiO-66 composite beads is characterized in that: the preparation method comprises the following specific steps:
(1) adding chitosan and UiO-66 with the same mass into hydrochloric acid aqueous solution with the volume fraction of 1%, and mechanically stirring for 6-8 hours until uniform mixed colloidal solution is formed;
(2) adding UiO-66 and sodium tripolyphosphate with the mass ratio of 2:1 into deionized water, carrying out ultrasonic treatment for 5 minutes, and uniformly mixing to obtain a UiO-66/sodium tripolyphosphate solution;
(3) slowly dripping the uniformly mixed colloidal solution prepared in the step (1) into the UiO-66/sodium tripolyphosphate solution prepared in the step (2) by using a burette to immediately form 1-2mm precipitated beads;
the dropping speed is slower than 3 seconds per drop;
(4) after the dropwise adding is finished, the whole body is transferred into a water bath constant temperature oscillation box, oscillation is carried out for 6 hours at 120rpm, and the beads are filtered, taken out and washed with deionized water for three times;
the temperature in the water bath constant temperature oscillation box is kept at 30 ℃;
(5) the wet beads were transferred to a 0.02mol/L glutaraldehyde solution and incubated at 40 ℃ for 12 hours;
(6) the resulting beads were filtered again, washed repeatedly with deionized water until the beads had a neutral pH, and freeze-dried to give UiO-66/CS @ UiO-66 mm composite beads.
2. The method of claim 1, wherein: the mechanical stirring speed of the step (1) is 100rpm-200 rpm.
3. The method of claim 1, wherein: the ultrasonic power in the step (2) is 250-500W.
4. The method of claim 1, wherein: the freeze drying in the step (6) is freeze drying at minus 50 +/-20 ℃ for more than 8 hours.
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| CN113388479A (en) * | 2021-06-29 | 2021-09-14 | 黔南民族师范学院 | Rosa roxburghii fruit wine composite clarifying agent and preparation method thereof |
| CN115505134B (en) * | 2022-09-21 | 2023-06-20 | 江苏第二师范学院 | Phosphorus oxychloride modified UiO-66-NH 2 Preparation and application of material |
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| CN101301604A (en) * | 2008-06-04 | 2008-11-12 | 哈尔滨工程大学 | Method for preparing magnetic powder heavy metal ion blotting chitosan compound adsorbing agent |
| WO2017133324A1 (en) * | 2016-02-04 | 2017-08-10 | Nanjing Normal University | Synthesis and application of mofs/natural polymers composite beads adsorbents |
| CN107824163A (en) * | 2017-11-23 | 2018-03-23 | 浙江海洋大学 | A kind of MIL 125 (Ti)/chitosan compound microsphere of arsenic-adsorbing |
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