CN114618403B - Preparation method of ferrocene hybridized chitosan-based aerogel, product and application thereof - Google Patents
Preparation method of ferrocene hybridized chitosan-based aerogel, product and application thereof Download PDFInfo
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- CN114618403B CN114618403B CN202210203332.4A CN202210203332A CN114618403B CN 114618403 B CN114618403 B CN 114618403B CN 202210203332 A CN202210203332 A CN 202210203332A CN 114618403 B CN114618403 B CN 114618403B
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/0091—Preparation of aerogels, e.g. xerogels
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28047—Gels
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
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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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/105—Phosphorus compounds
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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
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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Abstract
The invention discloses a preparation method and a product of ferrocene hybridized chitosan-based aerogel and application thereof, wherein chitosan is dissolved in acetic acid water solution and then mixed with ferrocene formaldehyde alcohol solution, and the mixture reacts for 1 to 5 hours at a temperature of between 20 and 80 ℃ to obtain hydrogel; soaking the hydrogel in alkali liquor for 3-12 hours, taking out, and freeze-drying to obtain the ferrocene hybridized chitosan-based aerogel. The preparation method of the ferrocene hybridized chitosan-based aerogel does not need chemical crosslinking, and can be prepared only by soaking in alkali liquor and freeze-drying; the ferrocene hybridized chitosan-based aerogel prepared by the invention not only has excellent phosphate adsorption performance, but also can rapidly degrade organic dye, and the degradation rate can reach 95% within 1 hour.
Description
Technical Field
The invention belongs to the technical field of aerogel preparation, and particularly relates to a preparation method and a product of ferrocene hybridized chitosan-based aerogel and application thereof.
Background
The aerogel has a large specific surface area, an easily-modified surface and a unique porous structure, so that the aerogel becomes an ideal adsorbent for treating wastewater, and can be used for adsorbing oils, dyes and heavy metal ions.
The chitosan aerogel is a biomass aerogel material prepared by chemical crosslinking or physical crosslinking, has the characteristics of large specific surface area and high porosity of the porous aerogel material, and is an environment-friendly oil absorption material with great development potential after the surface hydrophobization treatment.
However, conventional chitosan aerogels tend to have poor adsorption properties for phosphates and do not have the ability to degrade dyes.
Accordingly, there is a need in the art for a novel chitosan-based aerogel having excellent adsorption properties to phosphate while being capable of degrading organic dyes.
Disclosure of Invention
This section is intended to outline some aspects of embodiments of the invention and to briefly introduce some preferred embodiments. Some simplifications or omissions may be made in this section as well as in the description summary and in the title of the application, to avoid obscuring the purpose of this section, the description summary and the title of the invention, which should not be used to limit the scope of the invention.
The present invention has been made in view of the above and/or problems occurring in the prior art.
Therefore, the invention aims to overcome the defects in the prior art and provide a preparation method of ferrocene hybridized chitosan-based aerogel.
In order to solve the technical problems, the invention provides the following technical scheme: a preparation method of ferrocene hybridized chitosan-based aerogel comprises the following steps,
dissolving chitosan in acetic acid water solution, mixing with alcohol solution of ferrocene formaldehyde, and reacting at 20-80 ℃ for 1-5 hours to obtain hydrogel;
soaking the hydrogel in alkali liquor for 3-12 hours, taking out, and freeze-drying to obtain the ferrocene hybridized chitosan-based aerogel.
As a preferred scheme of the preparation method of the ferrocene hybridized chitosan-based aerogel, disclosed by the invention, the preparation method comprises the following steps: the mass ratio of the chitosan to the ferrocenyl formaldehyde is 1:0.5-1:4.
As a preferred scheme of the preparation method of the ferrocene hybridized chitosan-based aerogel, disclosed by the invention, the preparation method comprises the following steps: the mass ratio of the chitosan to the ferrocenyl formaldehyde is 1:2.
As a preferred scheme of the preparation method of the ferrocene hybridized chitosan-based aerogel, disclosed by the invention, the preparation method comprises the following steps: the alkali liquor is any one or two of sodium hydroxide solution and sodium borohydride solution.
As a preferred scheme of the preparation method of the ferrocene hybridized chitosan-based aerogel, disclosed by the invention, the preparation method comprises the following steps: the weight average molecular weight of the chitosan is 30000-500000.
As a preferred scheme of the preparation method of the ferrocene hybridized chitosan-based aerogel, disclosed by the invention, the preparation method comprises the following steps: the aqueous acetic acid solution had a concentration of 1wt%.
The invention further aims to overcome the defects in the prior art and provide an application of a product prepared by the preparation method of the ferrocene hybridized chitosan-based aerogel in adsorbing organic dye molecules in water and degrading dye in the presence of hydrogen peroxide, wherein the pH of the degraded dye is 4-7, and the hydrogen peroxide content of the degraded dye is 0.3-5 wt%.
It is another object of the present invention to overcome the deficiencies of the prior art and to provide a use of ferrocene-hybridized chitosan-based aerogel product for adsorbing phosphate in water, wherein the maximum adsorption capacity of the aerogel to phosphate can reach 1596mg/g.
The invention has the beneficial effects that:
the preparation method of the ferrocene hybridized chitosan-based aerogel does not need chemical crosslinking, and can be prepared only by soaking in alkali liquor and freeze-drying; the ferrocene hybridized chitosan-based aerogel prepared by the invention not only has excellent phosphate adsorption performance, but also can rapidly degrade organic dye, and the degradation rate can reach 95% within 1 hour.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the description of the embodiments will be briefly described below, it being obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art. Wherein:
FIG. 1 is a photograph of ferrocene hybridized chitosan-based aerogel prepared in example 1 of the present invention.
FIG. 2 is a scanning electron microscope of ferrocene hybridized chitosan-based aerogel prepared in example 1 of the present invention.
Detailed Description
In order that the above-recited objects, features and advantages of the present invention will become more apparent, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways other than those described herein, and persons skilled in the art will readily appreciate that the present invention is not limited to the specific embodiments disclosed below.
Further, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic can be included in at least one implementation of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
Example 1
1 g of chitosan with weight average molecular weight of 100000 is dissolved in 1wt% acetic acid aqueous solution, then mixed with methanol solution (concentration 0.25 g/ml) containing 2 g of ferrocene formaldehyde, and reacted at 50 ℃ for 5 hours to obtain hydrogel;
and then the hydrogel is directly immersed in sodium hydroxide-sodium borohydride mixed alkali liquor (the mass ratio is 1:1, the concentration is 5 wt%) for 6 hours, and the ferrocene hybridized chitosan aerogel is obtained by freeze drying after being taken out, and the prepared ferrocene hybridized chitosan-based aerogel photograph is shown in figure 1.
Example 2
1 g of chitosan with a weight average molecular weight of 50000 was dissolved in 1wt% aqueous acetic acid, and then mixed with an ethanol solution (concentration 0.25 g/ml) containing 1 g of ferrocene formaldehyde, and reacted at 80℃for 2 hours to obtain a hydrogel;
and then the hydrogel is directly immersed into sodium hydroxide solution (the concentration is 5 wt%) for soaking for 12 hours, and the ferrocene hybridized chitosan aerogel can be obtained after the hydrogel is taken out and freeze-dried.
Example 3
1 g of chitosan having a weight average molecular weight of 300000 was dissolved in a 1wt% aqueous acetic acid solution, and then mixed with a methanol solution (concentration 0.25 g/ml) containing 3 g of ferrocene formaldehyde, and reacted at 30℃for 5 hours to obtain a hydrogel;
and then the hydrogel is directly immersed into sodium borohydride solution (the concentration is 5 wt%) for soaking for 10 hours, and the ferrocene hybridized chitosan aerogel can be obtained after the hydrogel is taken out and freeze-dried.
Example 4
1 g of chitosan having a weight average molecular weight of 500000 was dissolved in a 1wt% aqueous acetic acid solution, and then mixed with an ethanol solution (concentration 0.25 g/ml) containing 4 g of ferrocene formaldehyde, and reacted at 60℃for 4 hours to obtain a hydrogel;
and then the hydrogel is directly immersed in sodium hydroxide-sodium borohydride mixed alkali liquor (the mass ratio is 1:1, the concentration is 5 wt%) for 8 hours, and the ferrocene hybrid chitosan aerogel can be obtained after taking out and freeze-drying.
Example 5
(1) Structural characterization of ferrocene hybrid chitosan aerogel:
the ferrocene-hybrid chitosan aerogel prepared in example 1 was structurally characterized by scanning electron microscopy and BET technique and compared to a chitosan aerogel that was not ferrocene-hybrid. The results are shown in FIG. 2 and Table 1.
(2) Adsorption performance of ferrocene hybridized chitosan aerogel on phosphate:
0.05 g of the ferrocene hybrid chitosan aerogel prepared in examples 1 to 4 was weighed into 50 ml of a potassium dihydrogen phosphate aqueous solution (ph=5) having a concentration of 250 mg/l, and stirred at 30 ℃ for 1 hour. And then taking the solution, filtering, and measuring the content of phosphorus by using a plasma inductively coupled plasma mass spectrum, thereby calculating the amount of the phosphate adsorbed by the aerogel. The control sample was a chitosan aerogel without ferrocene hybridization. The results are shown in Table 2.
(3) Degradation performance of ferrocene hybrid chitosan aerogel on methylene blue dye:
0.03 g of ferrocene hybridized chitosan aerogel prepared in examples 1-4 is weighed and put into 50 ml of methylene blue water solution with the concentration of 50 mg/L, hydrogen peroxide with the mass fraction of 0.3-5wt% is added, meanwhile, the pH is adjusted to be between 4 and 7, and then the mixture is stirred for 1 hour at the temperature of 30 ℃. The control sample was a chitosan aerogel without ferrocene hybridization.
The methylene blue content of the solution was detected by spectrophotometry.
The results are shown in Table 3.
TABLE 1
| Aperture (nanometer) | Area of hole (square meter/g) | Pore volume (cc/g) | |
| Comparative example | 11.49 | 21.71 | 0.062 |
| Example 1 | 6.32 | 5.00 | 0.0079 |
TABLE 2
TABLE 3 Table 3
As can be seen from fig. 2, the structure of the chitosan aerogel after ferrocene hybridization is loose, and more lamellar structures rather than porous structures are present.
The BET results set forth in Table 1 reveal a significant decrease in pore size, pore area and pore volume relative to the ferrocene prior to hybridization, particularly in pore volume and pore area. Theoretically, this suggests that the adsorption sites of the ferrocene hybridized chitosan aerogel may be reduced, which is disadvantageous for improving ion adsorption.
However, the results in table 2 show that the ferrocene-hybridized chitosan aerogel exhibited extremely high saturated adsorption amount to phosphate, relative to the control. In particular, in example 1, the saturated adsorption amount of phosphate was 20 times or more that of the comparative example. More importantly, the saturated adsorption capacity of the ferrocene hybridized chitosan aerogel prepared by the method for the phosphate is far more than the reported value of the existing literature.
As can be seen from Table 3, the ferrocene hybrid chitosan aerogel prepared in the embodiments 1-4 of the invention has higher degradation capability to methylene blue in the presence of hydrogen peroxide, the degradation rate of 1 hour can reach more than 92%, and especially the degradation rate of the embodiment 1 in 1 hour can reach more than 95%. Under the same conditions, the degradation rate of the comparative example on methylene blue is only 13%.
From the above results, although the structure of the chitosan aerogel becomes more loose after ferrocene hybridization modification, the pore volume and the pore area are greatly reduced, but the adsorption of phosphate and the degradation of methylene blue are greatly improved.
It should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted without departing from the spirit and scope of the technical solution of the present invention, which is intended to be covered in the scope of the claims of the present invention.
Claims (7)
1. A preparation method of ferrocene hybridized chitosan-based aerogel is characterized by comprising the following steps: comprising the steps of (a) a step of,
dissolving chitosan in acetic acid aqueous solution, mixing the chitosan with ferrocene formaldehyde alcohol solution, and reacting for 1-5 hours at 20-80 ℃ to obtain hydrogel, wherein the mass ratio of the chitosan to the ferrocene formaldehyde is 1:0.5-1:4, the weight average molecular weight of the chitosan is 30000-500000, and the concentration of the acetic acid aqueous solution is 1wt%;
soaking the hydrogel in alkali liquor for 3-12 hours, taking out, and freeze-drying to obtain the ferrocene hybridized chitosan-based aerogel.
2. The method for preparing the ferrocene hybridized chitosan-based aerogel according to claim 1, wherein: the mass ratio of the chitosan to the ferrocenyl formaldehyde is 1:2.
3. A method for preparing the ferrocene hybridized chitosan-based aerogel according to claim 1 or 2, wherein: the alkali liquor is any one or two of sodium hydroxide solution and sodium borohydride solution.
4. A product made by the method for preparing a ferrocene hybridized chitosan-based aerogel according to any one of claims 1-3.
5. The use of the product of claim 4 for adsorbing organic dye molecules in water and degrading the dye in the presence of hydrogen peroxide.
6. The use according to claim 5, characterized in that: the pH of the degradation dye is 4-7, and the hydrogen peroxide content of the degradation dye is 0.3-5 wt%.
7. Use of the product according to claim 4 for adsorbing phosphate in water, characterized in that: the maximum adsorption capacity of the aerogel to phosphate can reach 1596mg/g.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1606472A (en) * | 2001-12-21 | 2005-04-13 | 室町化学株式会社 | Adsorbent for phosphoric acid |
| US9181486B2 (en) * | 2006-05-25 | 2015-11-10 | Aspen Aerogels, Inc. | Aerogel compositions with enhanced performance |
| CN103424449B (en) * | 2013-07-30 | 2015-06-03 | 浙江理工大学 | Ferrocene grafted chitosan-carbon nanotube-enzyme composite membrane modified three-dimensional graphene composite material and preparation method thereof |
| CN108421534B (en) * | 2018-02-08 | 2020-10-20 | 中山大学 | Chitosan gel material, preparation method thereof, wastewater treatment method and application |
| CN111393707A (en) * | 2020-04-08 | 2020-07-10 | 江西理工大学 | Preparation method of chitosan hybrid aerogel |
| CN113185749A (en) * | 2021-04-22 | 2021-07-30 | 长沙理工大学 | Preparation method of high-adsorbability chitosan aerogel |
| CN113754032B (en) * | 2021-08-25 | 2022-06-21 | 同济大学 | Ferrocene modified polyaniline/carbon nanotube composite electrode for selectively removing phosphate ions and preparation method and application thereof |
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