CN115926151A - 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 PDFInfo
- Publication number
- CN115926151A CN115926151A CN202310034688.4A CN202310034688A CN115926151A CN 115926151 A CN115926151 A CN 115926151A CN 202310034688 A CN202310034688 A CN 202310034688A CN 115926151 A CN115926151 A CN 115926151A
- Authority
- CN
- China
- Prior art keywords
- linear
- drying
- preparation
- stabilizer
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003381 stabilizer Substances 0.000 title claims abstract description 41
- 239000013310 covalent-organic framework Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 150000001412 amines Chemical class 0.000 title claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 239000002689 soil Substances 0.000 claims abstract description 16
- 150000004985 diamines Chemical class 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 36
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- 238000001035 drying Methods 0.000 claims description 28
- 238000005406 washing Methods 0.000 claims description 23
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 21
- 239000008367 deionised water Substances 0.000 claims description 21
- 229910021641 deionized water Inorganic materials 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 21
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 20
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 18
- 239000000843 powder Substances 0.000 claims description 16
- 229910001385 heavy metal Inorganic materials 0.000 claims description 13
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 10
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 9
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 4
- 239000012295 chemical reaction liquid Substances 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 2
- 238000011109 contamination Methods 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 claims 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 12
- 239000010802 sludge Substances 0.000 abstract description 12
- 239000012467 final product Substances 0.000 abstract description 6
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 6
- 239000000178 monomer Substances 0.000 abstract description 4
- 230000008439 repair process Effects 0.000 abstract description 4
- 239000000377 silicon dioxide Substances 0.000 abstract description 4
- 239000005543 nano-size silicon particle Substances 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- 231100000419 toxicity Toxicity 0.000 abstract description 2
- 230000001988 toxicity Effects 0.000 abstract description 2
- 238000001179 sorption measurement Methods 0.000 description 27
- 239000000047 product Substances 0.000 description 26
- 239000000463 material Substances 0.000 description 21
- 241000196324 Embryophyta Species 0.000 description 10
- 241000234643 Festuca arundinacea Species 0.000 description 8
- 229910004298 SiO 2 Inorganic materials 0.000 description 8
- 238000000227 grinding Methods 0.000 description 8
- 239000006228 supernatant Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000005067 remediation Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 238000007865 diluting Methods 0.000 description 3
- 150000002193 fatty amides Chemical class 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 238000012805 post-processing Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- UWCPYKQBIPYOLX-UHFFFAOYSA-N benzene-1,3,5-tricarbonyl chloride Chemical compound ClC(=O)C1=CC(C(Cl)=O)=CC(C(Cl)=O)=C1 UWCPYKQBIPYOLX-UHFFFAOYSA-N 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 239000002734 clay mineral Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 230000003203 everyday effect Effects 0.000 description 2
- 230000035784 germination Effects 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- -1 biochar Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000002361 compost Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Images
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a linear organic amine covalent organic framework selective stabilizer, and a preparation method and application thereof. The preparation method comprises the following steps: firstly generating a silicon dioxide nano template under certain conditions by a step-by-step template method, then synthesizing corresponding nano silicon dioxide by an organic linear diamine monomer and 1,3, 5-s-tribenzoyl chloride by the template method, and finally removing the silicon dioxide nano template under the condition of alkaline water bath to obtain a final product. The preparation method is simple, and the reaction conditions are mild; the obtained stabilizer can efficiently, quickly and selectively adsorb Pb, effectively stabilize Pb in soil, reduce toxicity to plants and synergistically repair Pb in sludge by plants.
Description
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 Frameworks (COFs) selective stabilizer, and a preparation method and application thereof.
Background
Along with the continuous advance of the urbanization process of China in recent years, the urban sewage treatment scale is enlarged year by year, and the sludge production quantity of China is increased. The agricultural utilization of the sludge is used as a mode with ecological value and economic sustainability, the problem of disposal of a large amount of sludge is solved, the resource utilization of the sludge is realized, but heavy metals contained in the sludge are easy to accumulate in the soil, and are easy to leach to deeper soil depth when subjected to rain wash, and the pollution risk is formed on the soil, surface water and underground water. Cd, zn, cu, ni and Cr in the compost sludge mainly exist in a residue state, an oxidizable state and a reducible state, the environment migration risk is low due to stable property, and the weak acid extraction state proportion of Pb is higher than that of other heavy metals, so that deep migration is easy to occur in the environment, and the safety of underground water is threatened.
Therefore, finding a suitable heavy metal stabilizer to effectively control the migration capability of Pb is a key to realizing the utilization of sludge in parkerizing on a large scale. Among many soil remediation techniques, chemical remediation is widely used because it is simple and effective and suitable for large-area soil remediation, and conventional heavy metal stabilizers applied to soil include phosphate materials, biochar, lime materials, fly ash, clay minerals, and the like. However, these adsorbing materials often need a sufficient dosage to meet the adsorption requirement due to small specific surface area, few binding sites, lack of selectivity, etc., and excessive application of the stabilizer not only increases the repair cost, but also has negative effects on the physicochemical properties of the soil, for example, the problem of leaching of phosphorus easily caused by phosphate treatment, and some stabilizers such as clay minerals are biodegraded to affect their long-term effectiveness when used for fixing metals.
Covalent Organic Frameworks (COFs) material is applied to the field of environmental pollution remediation as a novel environmental functional material, and great progress is made. 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 often have advantages of fast adsorption speed, high adsorption capacity, and the like. In order to improve the selectivity of the COFs materials, the modification of the COFs enables the COFs to have more adsorption sites, and the selective adsorption of target pollutants can be better realized. Therefore, the development and design of the covalent organic framework selective stabilizer aiming at Pb has the characteristics of large adsorption capacity, multiple adsorption sites, long-term stability, specific selectivity and the like, and has great research value.
Disclosure of Invention
The invention aims to overcome at least one of the defects of the prior art and provide a linear organic amine covalent organic framework selective stabilizer, a preparation method and application thereof.
The purpose of the invention is realized based on the following technical scheme:
the invention aims at providing a preparation method of a linear organic amine covalent organic framework selective stabilizer in a first aspect.
Preferably, the preparation method specifically comprises the following steps:
s1: adding a certain amount of ethanol, ammonia water, deionized water and tetraethyl orthosilicate into a reaction vessel in sequence, stirring at constant temperature, standing to obtain reaction liquid, and performing aftertreatment A to obtain pure white powder, namely nano SiO 2 And (5) template.
S2, in ice bath, sequentially adding a certain amount of the nano SiO obtained in the S1 2 Adding a template, dichloromethane, organic linear diamine and 1,3, 5-s-tribenzoyl chloride into a reaction vessel, stirring for reaction for 1-3 h, standing for 1-3 h at normal temperature of 5-35 ℃, and performing post-treatment B to obtain white powder, namely nano SiO 2 @TMC-nD。
S3: will be fixedAmount of NanoSiO obtained in S2 2 @ TMC-nD and sodium hydroxide aqueous solution are put into a reactor, then the temperature is raised to 50-70 ℃, the reaction is carried out for 4-6h under constant temperature stirring, and the final product of the fatty Amide COFs material (Amide polymer material, AP for short) is obtained after the reaction solution is subjected to post-treatment C.
Preferentially, the ammonia water concentration in the step S1 is 25-30% (V/V), and the volume ratio of the ethanol, the ammonia water, the deionized water and the tetraethyl orthosilicate is (18-24): (2.5-3.1): 1: (1.4-2), 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 solution, washing the product by using ethanol, and drying the obtained solid in an 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, the nanoSiO is described in step S2 2 The mass ratio of the template, the dichloromethane and the 1,3, 5-s-tribenzoyl chloride is (1-1.5): (35-45): 1, the molar ratio of the organic linear diamine to the 1,3, 5-tribenzoyl 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 using deionized water, ethanol and acetone in sequence, and drying the obtained solid in a drying oven at the drying temperature of 60-80 ℃.
Preferably, the concentration of the sodium hydroxide aqueous solution in the step S3 is 0.5-1.0 mol/L, and the concentration of the nano SiO is 2 The ratio of @ TMC-nD to the aqueous solution of sodium hydroxide is 1g of nanoSiO 2 @ TMC-nD: 15-25 mL of sodium hydroxide aqueous solution.
Preferably, the post-processing C described in step S3 includes: and (3) centrifuging the reaction solution, washing the product by using deionized water, soaking the washed product in a proper amount of acetone for 8-16 h, and drying in an oven at the drying temperature of 60-80 ℃.
In a second aspect of the invention, the invention provides a linear organic amine covalent organic framework selective stabilizer prepared according to the preparation method.
The third aspect of the invention provides an application of a linear organic amine covalent organic framework selective stabilizer in cooperation with a plant to repair Pb in sludge and control leaching risk of heavy metal Pb in the sludge.
Compared with the prior art, the invention has the following beneficial effects:
1. the method comprises the steps of taking three organic linear diamines (anhydrous ethylenediamine, 1, 4-butanediamine and 1, 6-hexanediamine) and 1,3, 5-tribenzoyl chloride monomers as raw materials, firstly generating a silicon dioxide nano template under certain conditions by a step-by-step template method, then synthesizing corresponding nano silicon dioxide by the organic linear diamine monomers and the 1,3, 5-tribenzoyl chloride through the template method, and finally removing the silicon dioxide nano template under the condition of alkaline water bath to finally obtain the fatty Amide COFs materials (Amide polymer materials, AP materials for short, which are respectively named as AP1, AP2 and AP 3). Compared with the existing metal stabilizer, the linear organic amine covalent organic framework selective stabilizer prepared by the invention can efficiently, quickly and selectively adsorb Pb, effectively stabilize Pb in soil, reduce toxicity to plants and synergistically repair Pb in sludge by plants.
2. The preparation method of the covalent organic framework selective stabilizing agent has the advantages of simple steps, mild and non-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.
FIG. 2 is an XRD pattern of a stabilizing agent of the present invention.
FIG. 3 is a comparison of mixed metal selectivities of the stabilizers of the present invention.
FIG. 4 shows the effect of the stabilizer of the present invention on Pb at various concentrations 2+ The amount of adsorption of (3).
FIG. 5 shows the relationship of the stabilizer of the present invention to Pb 2+ Adsorption kinetics curve of (1).
FIG. 6 is a graph showing the growth of Festuca arundinacea 60 days after the application of the stabilizing agent of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Sequentially adding 90mL of ethanol, 13mL of ammonia water, 5mL of deionized water and 7mL of tetraethyl orthosilicate (TEOS) into a 250mL single-neck flask, stirring at the constant temperature of 20 ℃ for 20min, standing for 1h, taking out the mixed solution, performing centrifugal separation to obtain a product, washing for 3 times by using ethanol, putting the washed product into a 60 ℃ drying oven, and grinding to obtain pure white powder, namely nano SiO 2 And (5) template.
Under ice bath, 1g of nano SiO was added to a 500mL flask 2 Template, 26.25mL of dichloromethane, 0.504mL of ethylenediamine, and 1g of 1,3, 5-trimesoyl chloride (TMC) at a molar ratio of ethylenediamine to TMC of 2:1, stirring and reacting for 1h, standing for 1h at the normal temperature of 25 ℃, taking out the solution, centrifugally collecting, washing with deionized water (to be neutral) twice, washing with ethanol twice and washing with acetone twice, drying in an oven at the temperature of 60 ℃ after washing, drying, and finally grinding to obtain white powder, namely, nano SiO 2 @TMC-nD。
1g of nanoSiO 2 @ TMC-nD and 15mL of 0.5mol/L NaOH solution are put into a flask, the temperature is raised to 50 ℃, the reaction is carried out for 4 hours under constant temperature stirring, the product is collected by centrifugation, washed for 4 times by deionized water, the washed product is soaked in a proper amount of acetone for 8 hours, the product is put into a 60 ℃ drying oven for drying, and the powder substance, namely the final product AP1-1, is obtained after grinding.
Example 2
Sequentially adding 147mL of ethanol, 20mL of ammonia water, 7mL of deionized water and 12mL of tetraethyl orthosilicate (TEOS) into a 250mL single-neck flask, stirring at the constant temperature of 30 ℃ for 30min, standing for 2h, taking out the mixed solution, performing centrifugal separation to obtain a product, washing for 3 times by using ethanol, putting the washed product into a 70 ℃ oven for drying, and grinding to obtain pure white powder, namely nano SiO 2 And (5) template.
Under ice bath, 1g of nano SiO was added in turn to a 500mL flask 2 Template, 30mL of dichloromethane, 0.569mL of ethylenediamine and 1g of 1,3, 5-trimesoyl chloride (TMC) in a molar ratio of ethylenediamine to TMC of 2.26:1, stirring and reacting for 2 hours, standing for 2 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 and washing with acetone twice, drying in an oven at the temperature of 70 ℃ after washing, drying, and finally grinding to obtain white powder, namely, nano SiO 2 @TMC-nD。
1g of nanoSiO 2 @ TMC-nD and 20mL0.5mol/L NaOH solution are placed in a flask, the temperature is raised to 60 ℃, the constant temperature is kept for stirring and reacting for 5 hours, products are collected through centrifugation, deionized water is used for washing for 4 times, the washed products are soaked in a proper amount of acetone for 12 hours, the products are placed in a 70 ℃ drying oven for drying, and powder substances, namely the final product AP1-2, are obtained through grinding.
Example 3
Adding 240mL of ethanol, 31mL of ammonia water, 10mL of deionized water and 20mL of tetraethyl orthosilicate (TEOS) into a 250mL single-neck flask in sequence, stirring at the constant temperature of 40 ℃ for 40min, standing for 3h, taking out the mixed solution, performing centrifugal separation to obtain a product, washing for 3 times by using ethanol, putting the washed product into an oven at the temperature of 80 ℃ for drying, and grinding to obtain pure white powder, namely nano SiO 2 And (5) template.
Under ice bath, 1g of nano SiO was added to a 500mL flask 2 Template, 33.75mL of dichloromethane, 0.629mL of ethylenediamine, and 1g of 1,3, 5-s-tribenzoyl 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 and washing with acetone twice in sequence, drying in an oven at 80 ℃ after washing, drying, and finally grinding to obtain white powder, namely, nanoSiO 2 @TMC-nD。
1g of nanoSiO 2 @ TMC-nD and 20mL0.5mol/L NaOH solution are placed into a flask, the temperature is raised to 70 ℃, the reaction is carried out for 6 hours under constant temperature stirring, the product is centrifugally collected, deionized water is used for washing for 4 times, the washed product is soaked in a proper amount of acetone for 16 hours, the product is placed into an oven at the temperature of 80 ℃ for drying, and a powdery substance is obtained after grindingI.e. the final product AP1.
Example 4
In this example, the stabilizer was prepared in substantially the same manner as in example 1, except that: the organic linear diamine added was 0.767ml of 1, 4-butanediamine, the molar ratio of 1, 4-butanediamine to TMC was 2:1. the product obtained is AP2-1.
Example 5
In this example, the preparation of the stabilizer was substantially the same as in 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 obtained product is AP2-2.
Example 6
In this example, the stabilizer was prepared in substantially the same manner as in example 3, except that: the organic linear diamine was added at 0.959mL of 1, 4-butanediamine, the molar ratio of 1, 4-butanediamine to TMC was 2.5:1. the obtained product is AP2-3.
Example 7
In this example, the stabilizer was prepared in substantially the same manner as in example 1, except that: the added organic linear diamine was 0.974mL of 1, 6-hexanediamine, the molar ratio of 1, 6-hexanediamine to TMC was 2:1. the product obtained is C.
Example 8
In this example, the stabilizer was prepared in substantially the same manner as in example 1, except that: the organic linear diamine added was 1.101mL of 1, 6-hexanediamine, the molar ratio of 1, 6-hexanediamine to TMC was 2.26:1. the product obtained is AP3-2.
Example 9
In this example, the preparation of the stabilizer was substantially the same as in example 1, except that: 1.218mL of 1, 6-hexanediamine was added as organic linear diamine, with a 1, 6-hexanediamine to TMC molar ratio of 2.5:1. the obtained product is 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 were added to 20mL of a mixed heavy metal solution (Cu, zn, pb, cd, ni) having a concentration of 1mmol/L at 25 deg.CShaking for 2.5h, collecting appropriate amount of supernatant, filtering with 0.45 μm filter membrane, diluting the supernatant with certain times, and measuring Cu 2+ 、Zn 2+ 、Pb 2 + 、Cd 2+ 、Ni 2+ Concentration of Cu at different concentrations 2+ 、Zn 2+ 、Pb 2+ 、Cd 2+ 、Ni 2+ The amount of adsorption. Fig. 3 is plotted according to the adsorption amounts of the three stabilizers to the five metals.
0.01g of AP1-2 prepared in example 2, AP2-2 prepared in example 5, and AP3-2 prepared in example 8 was added with 20mL of Pb 2+ Shaking the solution with concentration of 0.125, 0.25, 0.375, 0.5, 0.75, 1, 1.25, 1.5mmol/L at 25 deg.C for 2.5h, filtering the supernatant with 0.45 μm filter membrane, diluting the supernatant by a certain times, and measuring Pb 2+ And (4) concentration. Separately calculate Pb at different concentrations 2+ The amount of adsorption. According to Pb 2+ Concentration and corresponding Pb 2+ And (5) drawing an adsorption equilibrium curve according to the adsorption amount.
0.01g of AP1-2 prepared in example 2, AP2-2 prepared in example 5, and AP3-2 prepared in example 8 were each charged with 20mL of Pb 2+ Shaking 0.5mmol/L solution at 25 deg.C for 2.5h, collecting appropriate amount of supernatant, filtering with 0.45 μm filter membrane at intervals of 1, 2, 5, 10, 20, 30, 50, 70, 90, 120, and 150 min, diluting the supernatant with a certain multiple, and measuring Pb 2+ And (4) concentration. According to the measured Pb 2+ The concentration was plotted as adsorption kinetics.
Example 11
And 3 pots of a control group are set in the pot experiment stage, and no stabilizer is added. The experimental treatment groups are respectively provided with 4 gradient addition amounts of 0.5, 1.0, 1.5 and 2.0g/kg for the AP1-2 prepared in the three stabilizer examples 2, the AP2-2 prepared in the example 5 and the AP3-2 prepared in the example 8, 3 parallel samples are respectively arranged in each experimental treatment group, 12 basins are arranged in each AP material treatment group, and the total number of the three AP material experimental treatment groups is 36 basins. 1kg of soil is put into each pot, the quality is kept consistent, the sludge nutrient soil and the corresponding stabilizer are uniformly stirred and then put into a flowerpot, 5g of tall fescue seeds are uniformly sowed at a position which is about 1-2 cm under the soil, and a proper amount of deionized water is poured on time every day to wait for germination. The total growth period is 60 days from the first day of germination of festuca arundinacea. During the growth period of the festuca arundinacea, equal amount of deionized water is poured every day or every other day according to the soil moisture condition.
After the plants are harvested, the plants are washed clean by deionized water, put into an oven, de-enzymed for 30min at 105 ℃, then the temperature is adjusted to 60 ℃, and the plants are continuously dried for 24h, and the dry weights of the festuca arundinacea samples of the overground part and the underground part are measured, and the results are shown in table 1.
After digesting and removing acid from the plant sample, the Pb content in the plant was determined, and the results are shown in table 1.
TABLE 1 average biomass of Festuca arundinacea and Pb concentration in plants
From experimental results, the stabilizing agent not only promotes the biomass of the festuca arundinacea to different degrees, but also reduces the concentration of Pd in the festuca arundinacea, which shows that the stabilizing agent successfully stabilizes Pb in soil and reduces the toxic effect of the Pb on plants.
The invention relates to a linear organic amine covalent organic framework selective stabilizer which is nano SiO 2 Is a template agent. Firstly, ethanol, ammonia water, deionized water and tetraethoxysilane are taken as raw materials to prepare the template agent (nanoSiO) 2 ) (step S1), linear organic amine and TMC (1, 3, 5-sym-triphenylformyl chloride) are used for reacting on the surface of a template agent to obtain a material (nanoSiO) containing the template agent 2 @ TMC-nD) (step S2), siO is finally washed off with aqueous sodium hydroxide solution 2 And (3) obtaining a template agent to obtain the fatty Amide COFs material (Amide polymer material, AP for short) (step S3). FIG. 1 is the topography of the final product AP; FIG. 2 is the XRD pattern of the product, which shows only one broad peak, indicating that the material has uniform pore size.
As shown in FIG. 1, AP1-2 is shown as a large range of sheets stacked on each other under a Scanning Electron Microscope (SEM) and gaps are formed between the stacked sheets, and a part of small particles are attached to the surface; AP2-2 is a sheet 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 appears as a thick buildup layer with fewer gaps formed by buildup than the first two. The three materials all belong to amorphous nano interlayer structures, and the formed interlayer gaps and channels provide large-area exposed points for amide groups playing the adsorption capacity, so that the chemical adsorption process is facilitated when the adsorbent adsorbs heavy metal ions, and meanwhile, sufficient adsorption space is provided by the obvious interlayer structures.
As shown in FIG. 2, AP1-2, AP2-2, and AP3-2 show relatively strong peaks at 23.43 °, 22.18 °, and 21.47 °, respectively, which corresponds to the (001) reflection of the resulting layered COFs. Furthermore, the broad peaks in the XRD patterns reflect the relatively low crystallinity of the COFs prepared herein.
As shown in FIG. 3, in the mixed heavy metal system with different concentrations, AP material is used for heavy metal Pb 2+ The adsorption of (A) is far higher than that of other four heavy metals. AP1-2 and AP3-2 to Pb 2+ The adsorption capacity is 0.379mmol/g and 0.446mmol/g respectively, and the maximum adsorption capacity of AP2-2 is 0.531mmol/g.
As shown in FIG. 4, the three AP materials follow the initial Pb 2+ The adsorption capacity of the solution is gradually increased due to the increase of the concentration of the solution, and finally the maximum adsorption capacity of AP1-2, AP2-2 and AP3-2 respectively reaches 163.3, 189.6 and 170.2mg/g.
As shown in FIG. 5, three AP material pairs for Pb 2+ All have faster adsorption speed, basically reach adsorption balance within 60min, and have good adsorption rate and adsorption capacity, which shows that the prepared AP material can adsorb Pb in stable environmental pollution 2+ Has good application prospect.
Claims (10)
1. The preparation method of the linear organic amine covalent organic framework selective stabilizer is characterized by comprising the following steps of:
s1: sequentially adding ethanol, ammonia water, deionized water and tetraethyl orthosilicate into a reaction vessel, stirring at constant temperature, standing to obtain reaction liquid, and performing aftertreatment A to obtain pure white powder;
s2, under ice bath, sequentially adding the pure white powder obtained in the step S1, dichloromethane, organic linear diamine and 1,3, 5-S-tribenzoyl chloride into a reaction container, stirring for reaction for 1-3 h, standing for 1-3 h at 5-35 ℃, and performing aftertreatment B to obtain white powder;
s3: and (3) putting the white powder obtained in the step (S2) and the sodium hydroxide aqueous solution into a reactor, heating to 50-70 ℃, stirring at a constant temperature for reaction for 4-6 hours, and carrying out post-treatment C on the reaction liquid to obtain the linear organic amine covalent organic framework selective stabilizer.
2. The preparation method according to claim 1, wherein in step S1, the ammonia water has a volume percentage concentration of 25% to 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: the temperature is 20-40 ℃, and the stirring time is 20-40 min at constant temperature;
the standing time is 1-3 h.
3. The method according to claim 1, wherein the post-treatment a in step S1 comprises: and (3) centrifuging the reaction solution, washing the product by using ethanol, and drying the obtained solid in an 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 method according to claim 1, wherein in step S2, the mass ratio of the pure white powder, the dichloromethane and the 1,3, 5-S-tribenzoyl chloride is (1-1.5): (35-45): 1;
the molar ratio of the organic linear diamine to the 1,3, 5-sym-tribenzoyl chloride is (2-2.5): 1.
6. the method according to claim 1, wherein the post-treatment B in step S2 comprises: and (3) centrifuging the reaction solution, washing the product by using deionized water, ethanol and acetone in sequence, and drying the obtained solid in a drying oven at the drying temperature of 60-80 ℃.
7. The method according to claim 1, wherein in step S3, the concentration of the aqueous sodium hydroxide solution is 0.5 to 1.0mol/L;
the ratio of white powder to sodium hydroxide aqueous solution is 1g: 15-25 mL.
8. The method according to claim 1, wherein the post-treatment C in step S3 comprises: and (3) centrifuging the reaction solution, washing the product by using deionized water, soaking the washed product in a proper amount of acetone for 8-16 h, and drying in an oven at the drying temperature of 60-80 ℃.
9. A linear organic amine covalent organic framework selective stabilizer, characterized in that it is prepared according to the preparation method of any one of claims 1 to 8.
10. Use of a linear organic amine covalent organic framework selective stabilizer according to claim 9 in the treatment of heavy metal contamination of soil.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310034688.4A CN115926151B (en) | 2023-01-10 | 2023-01-10 | Linear organic amine covalent organic framework selective stabilizer and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310034688.4A CN115926151B (en) | 2023-01-10 | 2023-01-10 | Linear organic amine covalent organic framework selective stabilizer and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115926151A true CN115926151A (en) | 2023-04-07 |
| CN115926151B CN115926151B (en) | 2024-05-17 |
Family
ID=86550757
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310034688.4A Active CN115926151B (en) | 2023-01-10 | 2023-01-10 | Linear organic amine covalent organic framework selective stabilizer and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115926151B (en) |
Citations (4)
| 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 |
| US20200261885A1 (en) * | 2017-08-21 | 2020-08-20 | Ecole Polytechnique Federale De Lausanne (Epfl) | New composites for extraction of metal or contaminating chemical species |
| CN112642411A (en) * | 2020-12-17 | 2021-04-13 | 江苏大学 | Preparation method and application of porous/ion-rich channel microsphere adsorbent |
-
2023
- 2023-01-10 CN CN202310034688.4A patent/CN115926151B/en active Active
Patent Citations (4)
| 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 |
| US20200261885A1 (en) * | 2017-08-21 | 2020-08-20 | Ecole Polytechnique Federale De Lausanne (Epfl) | New composites for extraction of metal or contaminating chemical species |
| CN112642411A (en) * | 2020-12-17 | 2021-04-13 | 江苏大学 | Preparation method and application of porous/ion-rich channel microsphere adsorbent |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115926151B (en) | 2024-05-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105175295B (en) | A kind of preparation of mercapto-functionalized MOFs materials and its application of Adsorption Heavy Metals in Waters ion | |
| Liu et al. | Composting enhances the removal of lead ions in aqueous solution by spent mushroom substrate: Biosorption and precipitation | |
| CN103894407B (en) | A kind of method of restoration of soil polluted by heavy metal | |
| CN112679731B (en) | Covalent organic framework material containing sulfonic acid group and preparation and application thereof | |
| CN111389367A (en) | Metal sludge-based biochar, preparation method and application in removing nitrogen and phosphorus in water body | |
| CN111333200B (en) | Embedded immobilized microorganism particles, preparation method and sewage treatment method | |
| Liu et al. | Radiation synthesis and performance of novel cellulose-based microsphere adsorbents for efficient removal of boron (III) | |
| CN110292912B (en) | MOF-derived clustered cerium-based phosphorus removal adsorbent and preparation method thereof | |
| CN110303035A (en) | A kind of method that the modified rice hull carbon of manganese repairs cadmium arsenic combined contamination soil and reduces cadmium arsenic in rice | |
| Stirk et al. | Removal of heavy metals from solution using dried brown seaweed material | |
| CN113083230A (en) | Modified rice straw biochar adsorbing material, preparation method and application | |
| CN107051393A (en) | Magnesium silicate hydro-thermal carbon composite and its preparation method and application | |
| CN108911009B (en) | Method for removing antibiotics in water body by using nickel-doped metal organic framework material | |
| CN118222297A (en) | Saline-alkali soil conditioner and preparation method and use method thereof | |
| CN110683729A (en) | Sludge recycling method based on charcoal firing and application thereof | |
| CN110882678A (en) | Preparation method of modified waste hydrophobic fiber oil absorption material | |
| CN113880383A (en) | Polluted water body sediment remediation method | |
| CN115926151B (en) | Linear organic amine covalent organic framework selective stabilizer and preparation method and application thereof | |
| Adeogun et al. | Biosorption of Lead Ions on Biosorbent Prepared from Plumb Shells (Spondias mombin): Kinetics and Equilibrium Studies: Biosorbent Prepared from Spondias mombin | |
| CN107381821A (en) | A kind of method that exceeded mercury in seawater is handled using microalgae | |
| CN114988514B (en) | Method for removing penicillin potassium in water body by using composite biochar and application | |
| CN106378115A (en) | Hierarchical-porous-structure bamboo charcoal/bentonite composite material and application thereof | |
| Godjevargova et al. | Fixed-bed biosorption of Cu2+ by polyacrylonitrile-immobilized dead cells of Saccharomyces cerevisiae | |
| CN114887602A (en) | Cellulose/polydopamine/lanthanum hydroxide composite material for efficiently removing phosphorus from water body | |
| CN110681344B (en) | Zirconium series nano hybrid material and application method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |