CN115926151B - Linear organic amine covalent organic framework selective stabilizer and preparation method and application thereof - Google Patents

Linear organic amine covalent organic framework selective stabilizer and preparation method and application thereof Download PDF

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CN115926151B
CN115926151B CN202310034688.4A CN202310034688A CN115926151B CN 115926151 B CN115926151 B CN 115926151B CN 202310034688 A CN202310034688 A CN 202310034688A CN 115926151 B CN115926151 B CN 115926151B
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CN115926151A (en
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李非里
吴家豪
金辉
贾建洪
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Zhejiang University of Technology ZJUT
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Abstract

The invention discloses a linear organic amine covalent organic framework selective stabilizer, a preparation method and application thereof. The preparation method comprises the following steps: the method comprises the steps of firstly generating a silica nano template under a certain condition by a step template method, then synthesizing the corresponding nano silica by using an organic linear diamine monomer and 1,3, 5-trimesic acid chloride by the template method, and finally removing the silica nano template under an alkaline water bath condition to obtain a final product. The preparation method is simple, and the reaction condition is mild; the obtained stabilizer can efficiently, quickly and selectively adsorb Pb, can effectively stabilize Pb in soil, reduce toxicity to plants, and can cooperate with plants to repair Pb in sludge.

Description

Linear organic amine covalent organic framework selective stabilizer and preparation method and application thereof
Technical Field
The invention relates to the field of heavy metal stabilizers in soil heavy metal pollution treatment, in particular to a linear organic amine covalent organic framework (Covalent-Organic Frameworks, COFs) selective stabilizer, a preparation method and application thereof.
Background
In recent years, with the continuous promotion of urban process in China, the scale of urban sewage treatment is enlarged year by year, and the sludge production in China is also increased. The agricultural utilization of the sludge is used as a mode with ecological value and economic sustainability, and the recycling of the sludge is realized although the treatment problem of a large amount of sludge is solved, heavy metals contained in the sludge are easy to accumulate in soil and are easy to be leached to deeper soil depth when being subjected to rain wash, and pollution risks are formed for the soil, surface water and groundwater. Cd, zn, cu, ni, cr in the compost sludge mainly exists in a form of a residue state, an oxidizable state and a reducible state, the property is stable, the environment migration risk is low, the proportion of the weak acid extraction state of Pb is higher than that of other heavy metals, the deep migration is easy to occur in the environment, and the safety of underground water is threatened.
Therefore, searching for a suitable heavy metal stabilizer to effectively control the migration capacity of Pb is a key for realizing the garden utilization of the sludge on a large scale. Among the numerous soil remediation technologies, chemical remediation is widely adopted because it is simple and effective, and is suitable for large-area soil remediation, and conventional heavy metal stabilizers applied to soil are phosphate materials, biochar, lime materials, fly ash, clay minerals, and the like. However, these adsorption materials often need a sufficient amount of additive to meet the adsorption requirement due to small specific surface area, few binding sites, lack of selectivity, and the like, and excessive application of the stabilizer not only increases the repair cost, but also can negatively affect the physicochemical properties of the soil, for example, the leaching problem of phosphorus which is easily caused after the application of the phosphate treatment, and part of the stabilizer such as clay minerals can be biodegraded when used for fixing metals, thereby affecting the long-term effectiveness thereof.
The application of Covalent Organic Frameworks (COFs) as a novel environment functional material in the field of environmental pollution remediation has greatly progressed. COFs materials are periodic covalent porous polymers composed of various light elements (i.e., C, H, O, N, B) by simultaneous polymerization and crystallization of monomer building blocks, and generally have excellent stability, and COFs materials tend to have advantages of fast adsorption rate, high adsorption capacity, and the like. In order to improve the selectivity of the COFs material, the COFs is modified to have more adsorption sites, so that the selective adsorption of target pollutants can be better realized. Therefore, the development and design of the covalent organic framework selective stabilizer aiming at the characteristics of large adsorption capacity, multiple adsorption sites, long-term stability, specific selectivity and the like of Pb have great research value.
Disclosure of Invention
The invention aims to overcome at least one of the defects and shortcomings of the prior art, and provides a linear organic amine covalent organic framework selective stabilizer, a preparation method and application thereof.
The invention is realized based on the following technical scheme:
the object of the invention is in a first aspect to provide a method for preparing a linear organic amine covalent organic framework selective stabilizer.
Preferably, the preparation method specifically comprises the following steps:
s1: sequentially adding a certain amount of ethanol, ammonia water, deionized water and tetraethyl orthosilicate into a reaction container, stirring at a constant temperature, standing to obtain a reaction solution, and performing aftertreatment A to obtain pure white powder, namely nanoSiO 2 template.
S2, adding a certain amount of nanoSiO 2 templates, methylene dichloride, organic linear diamine and 1,3, 5-trimesic acid chloride obtained in the step S1 into a reaction container in sequence under ice bath, stirring and reacting for 1-3 hours, standing for 1-3 hours at normal temperature of 5-35 ℃, and obtaining white powder, namely nanoSiO 2 @TMC-nD after post-treatment B.
S3: and (3) putting a certain amount of nanoSiO 2 @TMC-nD obtained in the step (S2) and sodium hydroxide aqueous solution into a reactor, heating to 50-70 ℃, stirring at constant temperature for reacting for 4-6 hours, and performing post-treatment on the reaction solution C to obtain the final product of the aliphatic amide COFs material (Amide polymer material, AP for short).
Preferably, the concentration of the ammonia water in the step S1 is 25% -30% (V/V), and the volume ratio of the ethanol to the ammonia water to the deionized water to the tetraethyl orthosilicate is (18-24): (2.5-3.1): 1: (1.4-2), wherein the temperature is 20-40 ℃, the constant-temperature stirring time is 20-40 min, and the standing time is 1-3 h.
Preferably, the post-processing a described in step S1 includes: and (3) centrifuging the reaction liquid, washing the product by using ethanol, and drying the obtained solid in a drying oven at the drying temperature of 60-80 ℃.
Preferably, the organic linear diamine in step S2 comprises one of ethylenediamine, 1, 4-butanediamine, and 1, 6-hexanediamine
Preferably, in the step S2, the mass ratio of the nanoSiO 2 template to the dichloromethane to the 1,3, 5-trimesic acid chloride is (1-1.5): (35-45): 1, the molar ratio of the organic linear diamine to the 1,3, 5-trimesic acid chloride is (2-2.5): 1.
Preferably, the post-processing B described in step S2 includes: and (3) centrifuging the reaction solution, washing the product by deionized water, ethanol and acetone in sequence, and drying the obtained solid in a drying oven at the temperature of 60-80 ℃.
Preferably, in the step S3, the concentration of the sodium hydroxide aqueous solution is 0.5-1.0 mol/L, and the ratio of nanoSiO 2 @TMC-nD to the sodium hydroxide aqueous solution is 1g nanoSiO 2 @TMC-nD: 15-25 mL sodium hydroxide aqueous solution.
Preferably, the post-processing C in step S3 includes: and (3) centrifuging the reaction solution, washing the product by deionized water, soaking the washed product in a proper amount of acetone for 8-16 hours, and drying in a drying oven at the temperature of 60-80 ℃.
In a second aspect of the object of the present invention, there is provided a linear organic amine covalent organic framework selective stabilizer, obtainable according to the above-described preparation method.
The invention aims at a third aspect, and provides an application of a linear organic amine covalent organic framework selective stabilizer in cooperation with Pb in phytoremediation sludge to control the leaching risk of heavy metal Pb in the sludge.
Compared with the prior art, the invention has the following beneficial effects:
1. According to the invention, three organic linear diamine (anhydrous ethylenediamine, 1, 4-butanediamine, 1, 6-hexanediamine) and 1,3, 5-trimellitic chloride monomers are used as raw materials, a silica nano template is firstly generated under a certain condition by a step template method, then the organic linear diamine monomers and the 1,3, 5-trimellitic chloride are synthesized into corresponding nano silica by a template method, and finally the silica nano template is removed under an alkaline water bath condition to finally obtain the aliphatic amide COFs material (Amide polymer material, AP material for short, which is named as AP1, AP2 and AP3 respectively). Compared with the existing metal stabilizer, the linear organic amine covalent organic framework selective stabilizer prepared by the invention can efficiently, rapidly and selectively adsorb Pb, can effectively stabilize Pb in soil, reduces toxicity to plants, and can be used for synergistic plant restoration of Pb in sludge.
2. The preparation method of the covalent organic framework selective stabilizer has the advantages of simple steps, mild and not harsh reaction conditions, safe process and no need of a specific reaction device.
Drawings
FIG. 1 is an SEM image of a stabilizer of the present invention.
Figure 2 is an XRD pattern for a stabiliser according to the invention.
FIG. 3 is a comparison of mixed metal selectivities of stabilizers of the present invention.
FIG. 4 shows the adsorption amount of Pb 2+ by the stabilizer of the present invention at various concentrations.
FIG. 5 is a graph showing adsorption kinetics of Pb 2+ by the stabilizer of the present invention.
FIG. 6 is a graph showing growth of festuca arundinacea 60 days after application of the stabilizer of the present invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all embodiments of the invention. 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
90ML of ethanol, 13mL of ammonia water, 5mL of deionized water and 7mL of tetraethyl orthosilicate (TEOS) are sequentially added into a 250mL single-neck flask, the mixture is stirred at a constant temperature of 20 ℃ for 20min and then is kept stand for 1h, the mixed solution is taken out, centrifugal separation is carried out to obtain a product, the product is washed with ethanol for 3 times, the product is put into a 60 ℃ oven for drying, and pure white powder, namely nanoSiO 2 template, is finally obtained after grinding.
To a 500mL flask, under an ice bath, was added sequentially 1g nanoSiO 2 template, 26.25mL dichloromethane, 0.504mL ethylenediamine, and 1g 1,3, 5-trimesic chloride (TMC), the molar ratio of ethylenediamine to TMC being 2:1, stirring and reacting for 1h, standing at the normal temperature of 25 ℃ for 1h, taking out the solution, centrifugally collecting, washing with deionized water (to be neutral) twice, washing with ethanol twice, washing with acetone twice, drying in a 60 ℃ oven after washing is finished, and finally grinding to obtain white powder, namely nanoSiO 2 @TMC-nD.
Putting 1g nanoSiO 2 @TMC-nD and 15mL of 0.5mol/L NaOH solution into a flask, heating to 50 ℃, stirring at constant temperature for reaction for 4 hours, centrifugally collecting a product, washing with deionized water for 4 times, soaking the washed product in a proper amount of acetone for 8 hours, drying in a 60 ℃ oven, and grinding to obtain a powdery substance, namely a final product AP1-1.
Example 2
147ML of ethanol, 20mL of ammonia water, 7mL of deionized water and 12mL of tetraethyl orthosilicate (TEOS) are sequentially added into a 250mL single-neck flask, the mixture is stirred at a constant temperature of 30 ℃ for 30min and then is kept stand for 2h, the mixed solution is taken out, centrifugal separation is carried out to obtain a product, the product is washed with ethanol for 3 times, the product is put into a 70 ℃ oven for drying, and pure white powder, namely nanoSiO 2 template, is finally obtained after grinding.
To a 500mL flask, under an ice bath, was added sequentially 1g nanoSiO 2 template, 30mL dichloromethane, 0.569mL ethylenediamine, and 1g 1,3, 5-trimesic chloride (TMC), the molar ratio of ethylenediamine to TMC being 2.26:1, stirring and reacting for 2 hours, standing at the normal temperature of 25 ℃ for 2 hours, taking out the solution, centrifugally collecting, washing with deionized water (to be neutral) twice, washing with ethanol twice, washing with acetone twice, drying in a 70 ℃ oven after washing is finished, and finally grinding to obtain white powder, namely nanoSiO 2 @TMC-nD.
Putting 1g nanoSiO 2 @TMC-nD and 20ml of 0.5mol/L NaOH solution into a flask, heating to 60 ℃, stirring at constant temperature for reacting for 5 hours, centrifuging to collect a product, washing with deionized water for 4 times, soaking the washed product in a proper amount of acetone for 12 hours, drying in a 70 ℃ oven, and grinding to obtain a powdery substance, namely a final product AP1-2.
Example 3
240ML of ethanol, 31mL of ammonia water, 10mL of deionized water and 20mL of tetraethyl orthosilicate (TEOS) are sequentially added into a 250mL single-neck flask, the mixture is stirred at the constant temperature of 40 ℃ for 40min and then is kept stand for 3h, the mixed solution is taken out, centrifugal separation is carried out to obtain a product, the product is washed with ethanol for 3 times, the product is put into an oven at 80 ℃ for drying, and pure white powder, namely nanoSiO 2 template, is finally obtained after grinding.
To a 500mL flask, under an ice bath, was added sequentially 1g nanoSiO 2 template, 33.75mL dichloromethane, 0.629mL ethylenediamine, and 1g 1,3, 5-trimesic chloride (TMC), the molar ratio of ethylenediamine to TMC being 2.5:1, stirring and reacting for 3 hours, standing for 3 hours at the normal temperature of 25 ℃, taking out the solution, centrifugally collecting, washing with deionized water (to be neutral) twice, washing with ethanol twice, washing with acetone twice, drying in an oven at 80 ℃ after washing is finished, and finally grinding to obtain white powder, namely nanoSiO 2 @TMC-nD.
Putting 1g nanoSiO 2 @TMC-nD and 20ml of 0.5mol/L NaOH solution into a flask, heating to 70 ℃, stirring at constant temperature for reaction for 6 hours, centrifugally collecting a product, washing with deionized water for 4 times, soaking the washed product in a proper amount of acetone for 16 hours, drying in an oven at 80 ℃, and grinding to obtain a powdery substance, namely a final product AP1.
Example 4
In this example, the preparation method of the stabilizer was basically the same as that of example 1, except that: the added organic linear diamine was 0.767mL of 1, 4-butanediamine, the molar ratio of 1, 4-butanediamine to TMC was 2:1. the product was obtained as AP2-1.
Example 5
In this example, the preparation method of the stabilizer was basically the same as that of example 2, except that: the organic linear diamine added was 0.867ml of 1, 4-butanediamine, the molar ratio of 1, 4-butanediamine to TMC was 2.26:1. the product was obtained as AP2-2.
Example 6
In this example, the preparation method of the stabilizer was basically the same as that of example 3, except that: the organic linear diamine added was 0.959ml of 1, 4-butanediamine, the molar ratio of 1, 4-butanediamine to TMC was 2.5:1. the product was obtained as AP2-3.
Example 7
In this example, the preparation method of the stabilizer was basically the same as that of example 1, except that: the organic linear diamine added was 0.974mL of 1, 6-hexamethylenediamine, the molar ratio of 1, 6-hexamethylenediamine to TMC being 2:1. the product was obtained as C.
Example 8
In this example, the preparation method of the stabilizer was basically the same as that of example 1, except that: the organic linear diamine added was 1.101mL 1, 6-hexamethylenediamine, the molar ratio of 1, 6-hexamethylenediamine to TMC was 2.26:1. the product was obtained as AP3-2.
Example 9
In this example, the preparation method of the stabilizer was basically the same as that of example 1, except that: the organic linear diamine added was 1.218mL of 1, 6-hexamethylenediamine, the molar ratio of 1, 6-hexamethylenediamine to TMC being 2.5:1. the product was obtained as AP3-3.
Example 10
0.01G of AP1-2 prepared in example 2, AP2-2 prepared in example 5 and AP3-2 prepared in example 8 are respectively added into 20mL of mixed heavy metal solution (Cu, zn, pb, cd, ni) with the concentration of 1mmol/L, shaking is carried out for 2.5 hours at 25 ℃, a proper amount of supernatant is taken to pass through a 0.45 mu m filter membrane, the concentration of Cu 2+、Zn2+、Pb2 +、Cd2+、Ni2+ is respectively measured after the supernatant subjected to membrane filtration is diluted by a certain multiple, and the Cu 2+、Zn2+、Pb2+、Cd2+、Ni2+ adsorption amounts under different concentrations are respectively calculated. FIG. 3 is a plot of the adsorption of five metals by three stabilizers.
0.01G of AP1-2 prepared in example 2, AP2-2 prepared in example 5 and AP3-2 prepared in example 8 were added to 20mL of Pb 2+ in the respective solutions of 0.125, 0.25, 0.375, 0.5, 0.75, 1, 1.25 and 1.5mmol/L, and after shaking at 25℃for 2.5 hours, a proper amount of the supernatant was filtered through a 0.45 μm filter membrane, and the Pb 2+ concentration was measured by diluting the supernatant after the filtration by a predetermined factor. And (5) respectively calculating Pb 2+ adsorption amounts under different concentrations. And drawing an adsorption equilibrium curve according to the Pb 2+ concentration and the corresponding Pb 2+ adsorption quantity.
0.01G of AP1-2 prepared in example 2, AP2-2 prepared in example 5 and AP3-2 prepared in example 8 were added to 20mL of a Pb 2+ concentration solution of 0.5mmol/L, respectively, and the mixture was shaken at 25℃for 2.5 hours, and a proper amount of supernatant was taken every 1, 2, 5, 10, 20, 30, 50, 70, 90, 120, 150 minutes and passed through a 0.45 μm filter membrane, and the Pb 2+ concentration was measured after diluting the supernatant after the membrane filtration by a certain multiple. And drawing an adsorption kinetic curve according to the measured Pb 2+ concentration.
Example 11
The pot experiment stage is provided with 3 pots of a control group without adding a stabilizer. The experimental treatment groups were respectively provided with 4 gradient addition amounts of 0.5 g/kg, 1.0 g/kg, 1.5 g/kg and 2.0g/kg for the AP1-2 prepared in example 2, the AP2-2 prepared in example 5 and the AP3-2 prepared in example 8 of the three stabilizers, 3 parallel samples were respectively provided for each experimental treatment group, 12 pots were used for each AP material treatment group, and 36 pots were used for the three AP material experimental treatment groups. 1kg of soil is placed in each basin, the quality is kept consistent, the sludge nutrient soil and the corresponding stabilizing agent are stirred uniformly, then the soil is placed in the flowerpot, 5g of festuca arundinacea seeds are uniformly sown to the position about 1-2 cm below the soil, and a proper amount of deionized water is poured on time every day to wait for germination. A total of 60 days of growth period, from the first day of festuca arundinacea germination. During the growth of festuca arundinacea, an equal amount of deionized water was poured daily or every other day, depending on the soil moisture conditions.
After harvesting the plants, washing the plants with deionized water, placing the plants in an oven, deactivating enzymes at 105 ℃ for 30min, then adjusting the temperature to 60 ℃ and continuously drying the plants for 24h, and measuring the dry weight of the goats Mao Yangpin on the overground part and the underground part of the plants, wherein the results are shown in table 1.
After digestion and acid removal of the plant samples, pb content in the plants was measured and the results are shown in table 1.
TABLE 1 average biomass of festuca arundinacea and Pb concentration in plants
From the experimental results, the stabilizing agent not only promotes the biomass of festuca arundinacea to different degrees, but also reduces the concentration of Pd in festuca arundinacea, which proves that the stabilizing agent successfully stabilizes Pb in soil and reduces the toxic action of the stabilizing agent on plants.
The invention relates to a linear organic amine covalent organic framework selective stabilizer which takes nano SiO 2 as a template agent. The preparation method comprises the steps of preparing a template agent (nanoSiO 2) by using ethanol, ammonia water, deionized water and tetraethyl orthosilicate as raw materials (step S1), then reacting linear organic amine and TMC (1, 3, 5-trimesic acid chloride) on the surface of the template agent to obtain a material (nanoSiO 2 @TMC-nD) containing the template agent (step S2), and finally washing the SiO 2 template agent by using a sodium hydroxide aqueous solution to obtain the fatty amide COFs material (Amide polymer material, abbreviated as AP) (step S3). FIG. 1 is a topography of the final product AP; figure 2 is an XRD pattern of the product with only one broad peak, illustrating the uniformity of the pore size of the material.
As shown in fig. 1, AP1-2 is shown under a Scanning Electron Microscope (SEM) as a large range of sheets stacked on each other with gaps formed between the stacks, with small particles attached to the surface; AP2-2 is in a sheet shape with a large area, the surfaces of the single sheets are uneven, and a certain number of channels are formed by stacking the single sheets; AP3-2 exhibited a thick stack with less gaps formed by the stack than the former two. All three materials belong to amorphous nano interlayer structures, and the formed interlayer gaps and channels provide large-area exposed points for amide groups with adsorption capacity, so that the chemical adsorption process of the adsorbent for adsorbing heavy metal ions is facilitated, and meanwhile, the obvious interlayer structures also provide sufficient adsorption space.
As shown in fig. 2, AP1-2, AP2-2, AP3-2 show relatively strong peaks at 23.43 °, 22.18 °, 21.47 °, respectively, which corresponds to the (001) reflection of the resulting layered COFs material. Furthermore, the broad peaks in the XRD pattern reflect the relatively low crystallinity of COFs prepared herein.
As shown in fig. 3, in the mixed heavy metal system with different concentrations, the AP material adsorbs far more heavy metal Pb 2+ than the other four heavy metals. The adsorption capacity of the AP1-2 and the AP3-2 to Pb 2+ is respectively 0.379mmol/g and 0.446mmol/g, and the maximum adsorption capacity of the AP2-2 is 0.531mmol/g.
As shown in FIG. 4, the adsorption amount of the three AP materials gradually increases with the increase of the initial Pb 2+ solution concentration, and the maximum adsorption amounts of the final AP1-2, AP2-2 and AP3-2 reach 163.3, 189.6 and 170.2mg/g respectively.
As shown in FIG. 5, the three AP materials have high adsorption speed to Pb 2+, can basically reach adsorption balance within 60min, and have good adsorption rate and adsorption capacity, so that the prepared AP material has good application prospect for adsorbing Pb 2+ in stable environmental pollution.

Claims (10)

1. A method for preparing a linear organic amine covalent organic framework selective stabilizer, comprising the steps of:
S1: sequentially adding ethanol, ammonia water, deionized water and tetraethyl orthosilicate into a reaction container, stirring at constant temperature, standing to obtain a reaction solution, and performing aftertreatment A to obtain pure white powder;
S2, under ice bath, sequentially adding the pure white powder obtained in the step S1, methylene dichloride, organic linear diamine and 1,3, 5-trimesic acid chloride into a reaction vessel, stirring and reacting for 1-3 h, then standing for 1-3 h at 5-35 ℃, and obtaining white powder after post-treatment B;
S3: and (2) placing the white powder obtained in the step (S2) and a sodium hydroxide aqueous solution into a reactor, heating to 50-70 ℃, stirring at constant temperature for reaction for 4-6h, and performing aftertreatment C on the reaction solution to obtain the linear organic amine covalent organic framework selective stabilizer.
2. The preparation method according to claim 1, wherein in the step S1, the ammonia water volume percentage concentration is 25% -30%;
The volume ratio of the ethanol to the ammonia water to the deionized water to the tetraethyl orthosilicate is (18-24): (2.5-3.1): 1: (1.4-2);
The constant temperature stirring conditions are as follows: stirring at constant temperature of 20-40 ℃ for 20-40 min;
the standing time is 1-3 h.
3. The method according to claim 1, wherein in step S1, the post-treatment a includes: and (3) centrifuging the reaction liquid, washing the product by using ethanol, and drying the obtained solid in a drying oven at the drying temperature of 60-80 ℃.
4. The method according to claim 1, wherein in step S2, the organic linear diamine is one of ethylenediamine, 1, 4-butanediamine, and 1, 6-hexanediamine.
5. The preparation method according to claim 1, wherein in the step S2, the mass ratio of the pure white powder, the dichloromethane to the 1,3, 5-trimesic chloride is (1-1.5): (35-45): 1, a step of;
The molar ratio of the organic linear diamine to the 1,3, 5-trimesic acid chloride is (2-2.5): 1.
6. The method according to claim 1, wherein in step S2, the post-treatment B includes: and (3) centrifuging the reaction solution, washing the product by deionized water, ethanol and acetone in sequence, and drying the obtained solid in a drying oven at the temperature of 60-80 ℃.
7. The method according to claim 1, wherein in the step S3, the concentration of the aqueous sodium hydroxide solution is 0.5 to 1.0mol/L;
The ratio of the white powder to the sodium hydroxide aqueous solution is 1g: 15-25 mL.
8. The method according to claim 1, wherein in step S3, the post-treatment C comprises: and (3) centrifuging the reaction solution, washing the product by deionized water, soaking the washed product in a proper amount of acetone for 8-16 hours, and drying in a drying oven at the temperature of 60-80 ℃.
9. A linear organic amine covalent organic framework selective stabiliser, characterized in that it is obtainable by a preparation process according to any one of claims 1 to 8.
10. Use of the linear organic amine covalent organic framework selective stabilizer of claim 9 in the treatment of heavy metal pollution of soil.
CN202310034688.4A 2023-01-10 2023-01-10 Linear organic amine covalent organic framework selective stabilizer and preparation method and application thereof Active CN115926151B (en)

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Publication number Priority date Publication date Assignee Title
CN102794116A (en) * 2012-06-06 2012-11-28 复旦大学 Mesoporous silicon dioxide sphere-polymer nano composite nano-filtration membrane and preparation method thereof
CN106076256A (en) * 2016-07-06 2016-11-09 中山大学 A kind of preparation method and applications of nanometer Fe (0) porous mud material with carbon element
CN112642411A (en) * 2020-12-17 2021-04-13 江苏大学 Preparation method and application of porous/ion-rich channel microsphere adsorbent

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