CN113896849B - Thioether-functionalized porphyrin-structured porous organic polymer, preparation method thereof and application thereof in adsorption of heavy metals in water - Google Patents

Thioether-functionalized porphyrin-structured porous organic polymer, preparation method thereof and application thereof in adsorption of heavy metals in water Download PDF

Info

Publication number
CN113896849B
CN113896849B CN202111327390.XA CN202111327390A CN113896849B CN 113896849 B CN113896849 B CN 113896849B CN 202111327390 A CN202111327390 A CN 202111327390A CN 113896849 B CN113896849 B CN 113896849B
Authority
CN
China
Prior art keywords
thioether
functionalized
organic polymer
porphyrin
porous organic
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.)
Active
Application number
CN202111327390.XA
Other languages
Chinese (zh)
Other versions
CN113896849A (en
Inventor
黄健涵
王立志
周发
王佳佳
王悠
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Central South University
Original Assignee
Central South University
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Central South University filed Critical Central South University
Priority to CN202111327390.XA priority Critical patent/CN113896849B/en
Publication of CN113896849A publication Critical patent/CN113896849A/en
Application granted granted Critical
Publication of CN113896849B publication Critical patent/CN113896849B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
    • C08G12/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
    • B01J20/267—Cross-linked polymers
    • 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
    • C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
    • 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
    • C02F2101/20—Heavy metals or heavy metal compounds
    • 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
    • C02F2101/20—Heavy metals or heavy metal compounds
    • C02F2101/203—Iron or iron compound
    • 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
    • C02F2101/20—Heavy metals or heavy metal compounds
    • C02F2101/206—Manganese or manganese compounds

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Analytical Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

The invention discloses a thioether functionalized porphyrin structure porous organic polymer, a preparation method thereof and application thereof in the aspect of adsorbing heavy metals in water. And performing porphyrin polycondensation reaction on the thioether functionalized terephthalaldehyde monomer and a pyrrole monomer to obtain the thioether functionalized porphyrin structure porous organic polymer. The method realizes effective regulation and control of the polarity and the pore structure of the thioether-functionalized porphyrin-structured porous organic polymer by changing the conditions of thioether-functionalized monomer, the dosage of the thioether-functionalized monomer and the like, thereby endowing the thioether-functionalized porphyrin-structured porous organic polymer with Pb for the Pb 2+ 、Cu 2+ And Hg 2+ The porous organic polymer has the advantages of selective absorption effect, simple synthesis method, low cost and industrial production.

Description

Thioether-functionalized porphyrin-structured porous organic polymer, preparation method thereof and application thereof in adsorption of heavy metals in water
Technical Field
The invention relates to an adsorption material, in particular to a thioether functionalized porphyrin structure porous organic polymer obtained by performing porphyrin polycondensation on a thioether functionalized terephthalaldehyde monomer and a pyrrole monomer, and also relates to a preparation method of the thioether functionalized porphyrin structure porous organic polymer and application of the thioether functionalized porphyrin structure porous organic polymer in the aspect of adsorbing heavy metal ions in water, belonging to the technical field of functional polymer synthesis.
Background
Porous Organic Polymers (POPs) are a class of polymers with rich pore channel structures formed by crosslinking light elements (C, H, B, O, N, S, P and the like) through covalent bonds. Has the advantages that (1) the composite material is composed of rigid monomers, and permanent pores are formed in the polymer; (2) the method of bond formation and crosslinking reactions are diverse, resulting in polymers with different topologies and adjustable pore structures; (3) is composed of lighter element cross-linking, which leads to higher adsorption mass capacity of the polymer; (4) is formed by covalent bonds and has good physical and chemical stability. POPs have various assembly and crosslinking methods, and POPs with hierarchical pore structures can be obtained by adjusting reaction conditions. For the adsorption of heavy metal ions, the macropores and the mesopores are beneficial to material transmission, can reduce transmission resistance, accelerate transmission speed and contribute to the rapid diffusion of the heavy metal ions in the adsorbent; the micropores can provide rich specific surface area, provide rich sites for adsorption and obviously increase the adsorption quantity of heavy metal ions. The synergistic effect of the hierarchical pores obviously enhances the adsorption quantity and adsorption kinetics of metal ions.
In the industrial production process, a large amount of heavy metal wastewater is generated, and heavy metals have strong toxicity to human bodies generally, are difficult to degrade in nature, can be enriched in human beings through a biosphere, and bring huge challenges to the ecological environment and human survival. In recent years, adsorption of heavy metal ions has been receiving much attention, and researchers have utilized functional groups containing nitrogen, sulfur, oxygen, and the like to bring a rich heteroatom content to porous materials through pre-modification or post-modification. The chelating resin is relatively common, and can be complexed with metal ions through electrostatic interaction and coordination, so that the metal ions can be well adsorbed and selectively adsorbed, and the application prospect is good. However, the gel-type structure of the chelate resin causes slow adsorption and slow desorption rate, and the chelate resin structure is not stable enough and has poor reusability. Therefore, the structural stability of POPs due to the particularity of the cross-linked structure and the simple and easy functional modification enables the POPs to be widely applied to the selective adsorption of heavy metal ions in water, and has become a hot spot of the current research.
Porphyrins are macromolecular heterocyclic compounds formed by four α -carbon atoms of the pyrromethene group through methylene bridges. A large plane conjugated system is formed by 24 pi electrons, and can form a stable complex with different metal ions, so that the complex is widely used for heavy metal detection. The porphyrin structure is introduced into the POPs, so that the structural stability of the POPs can be obviously improved, and the effect on heavy metal ions can be improved.
Disclosure of Invention
Aiming at the defects that the heteroatom functionalization of the existing porous organic polymer is difficult, the pore structure is difficult to control and the like, the first purpose of the invention is to provide a thioether functionalized porphyrin structure porous organic polymer with thioether functionalized modification and a special hierarchical pore structure, wherein the organic polymer not only has a large plane conjugated system formed by 24 pi electrons and can form stable complexes with different metal ions, but also is modified with thioether functional groups and can regulate and control the pore structure and polarity so as to realize the selective adsorption capacity of different metal ions.
The second purpose of the invention is to provide a preparation method of the thioether-functionalized porphyrin-structured porous organic polymer, the method can realize thioether modification and arbitrary regulation and control of the pore structure, so that the thioether-functionalized porphyrin-structured porous organic polymer meets the application requirement of heavy metal ion adsorption, and the preparation method is simple and convenient to operate, has low cost and can meet industrial production.
The invention aims to provide the application of the porous organic polymer with the thioether functionalized porphyrin structure in absorbing heavy metal ions in water, in particular to metal ions Pb 2+ 、Cu 2+ And Hg 2+ The polymer has a selective adsorption effect, is easy to elute after metal ions are adsorbed, can be repeatedly used for many times, and has a good repeated use effect.
In order to realize the technical purpose, the invention provides a preparation method of a thioether functionalized porphyrin structure porous organic polymer, which comprises the step of carrying out porphyrin polycondensation reaction on a thioether functionalized terephthalaldehyde monomer and a pyrrole monomer to obtain the thioether functionalized porphyrin structure porous organic polymer.
The porous organic polymer in the prior art is resistant to metal ions Pb 2+ 、Cu 2+ And Hg 2+ Etc. have a certain adsorption, but the adsorption amount is small, the adsorption equilibrium is slow, and the selectivity is poor. The main reason is that heteroatom functionalization significantly affects the crosslinking of monomers, resulting in low specific surface area, low pore volume and thus low adsorption capacity; the uncontrollable holes in the synthesis process are distributed unevenly, and the structure is uncontrollable; the post-crosslinking of the porous organic polymer can obviously reduce the specific surface area, and the functionalization degree is lower, and the effect is not ideal enough. Therefore, the existing ultrahigh crosslinked polymer has limited capability of improving functional heteroatoms, the pore structure is difficult to realize adjustment, and the ultrahigh crosslinked polymer with high selective adsorption effect is difficult to obtain. The key point of the technical scheme is that thioether functionalized terephthalaldehyde monomers are adopted as pre-modification monomers to directly perform porphyrin polycondensation with pyrrole in one step to obtain a thioether functionalized porphyrin structure porous organic polymer, the defects of the porous polymer after functional modification can be avoided by adopting the thioether functionalized terephthalaldehyde monomers, and the quantity of thioether functional groups in the thioether functionalized porphyrin structure porous organic polymer can be regulated and controlled by selecting the type, the dosage and the like of the thioether functionalized terephthalaldehyde monomers, so that the polarity and the pore structure of the thioether functionalized porphyrin structure porous organic polymer can be effectively regulated.
As a preferred embodiment, the thioether-functionalized terephthalaldehyde monomer includes at least one of 1, 2-dimethylthio-terephthalaldehyde, 2, 5-diethylthio-terephthalaldehyde, 2,3,5, 6-tetramethylthio-terephthalaldehyde, and 2, 5-di ((methylthio) methyl) terephthalaldehyde. The positions and the number of the dimethylthio groups in the thioether functionalized terephthalaldehyde monomers are different, and the polarity and the pore structure of the thioether functionalized porphyrin structure porous organic polymer can be directionally regulated and controlled by selecting different thioether functionalized terephthalaldehyde monomers or combining and matching several thioether functionalized terephthalaldehyde monomers.
As a preferable scheme, the molar percentage composition of the thioether functionalized terephthalaldehyde monomer and the pyrrole monomer is (10-50%): 50-90%.
As a preferred embodiment, the conditions of the porphyrin polycondensation reaction are as follows: reacting for 6-48 h at 50-180 ℃ under the action of a Lewis acid catalyst. Under the optimized reaction condition, the efficient condensation reaction between the thioether functionalized terephthalaldehyde monomer and the pyrrole monomer can be realized.
In a preferred embodiment, the lewis acid catalyst is at least one of ferric trichloride, trifluoroacetic acid and propionic acid, and these catalysts are commonly used in the condensation reaction process, and the amount of the catalyst is the conventional amount.
In a preferred embodiment, the porphyrin polycondensation reaction is carried out in at least one solvent selected from acetic acid, propionic acid and dichloromethane. The carboxylic acid and propionic acid may be used as both a solvent and a catalyst.
As a preferred scheme, the thioether-functionalized terephthalaldehyde monomer and the pyrrole monomer are respectively dissolved in a solvent to obtain a thioether-functionalized terephthalaldehyde monomer solution and a pyrrole monomer solution, and the thioether-functionalized terephthalaldehyde monomer solution is slowly added into the pyrrole monomer solution to perform porphyrin polycondensation reaction, or the pyrrole monomer solution is slowly added into the thioether-functionalized terephthalaldehyde monomer solution to perform porphyrin polycondensation reaction.
The invention provides a thioether functionalized porphyrin structure porous organic polymer, which is prepared by the preparation method.
The thioether-functionalized porphyrin-structured porous organic polymer has a porphyrin structure unit, porphyrin has a large plane conjugated system formed by 24 pi electrons, and can form a stable complex with various heavy metal ions to be assembled in a polymer framework, but the adsorption selectivity is poor, and the pore structure and the polarity can be regulated by further introducing thioether functional groups, so that the selective adsorption capacity of different metal ions can be realized, for example, the polarity and the pore structure of the thioether-functionalized porphyrin-structured porous organic polymer can be effectively regulated by controlling the number and the positions of the introduced thioether groups.
Preferably, the sulfur content is 3-20% by mass, and the specific surface area is 100-800 m 2 A pore volume of 0.1 to 1.0 cm/g 3 (ii)/g, the average pore diameter is 0.5 to 4.0 nm.
The invention also provides application of the thioether functionalized porphyrin structure porous organic polymer as an adsorption material to adsorption of heavy metal ions in water.
The thioether functionalized porphyrin structure porous organic polymer can be applied to Pb in water 2+ 、Cu 2+ And Hg 2+ Selection of plasma metal ionsThe thioether functionalized porphyrin structure porous organic polymer is easy to elute after adsorbing heavy metals, good in reusability and stable in structure, and can be widely applied to the fields of heavy metal adsorption, substance component analysis and the like. Specifically, the thioether functionalized porphyrin structure porous organic polymer adsorbed with heavy metal ions can be desorbed by adopting a mixed solution of thiourea and HCl (the thiourea concentration is 5mol/L, and the HCl concentration is 1 mol/L). Good elution effect and good reusability.
The controllable synthesis method of the thioether functionalized porphyrin structure porous organic polymer comprises the following specific steps:
thioether functionalized terephthalaldehyde is used as a monomer, pyrrole is used as a crosslinking reagent, and a catalyst is added into a solvent to prepare the thioether functionalized porphyrin structure porous organic polymer. The method comprises the following specific steps: under the nitrogen atmosphere, dissolving thioether functionalized terephthalaldehyde in 30mL of solvent, adding a catalyst, heating to reflux (50-180 ℃), dissolving pyrrole in 30mL of solvent, slowly dropwise adding by using a constant-pressure dropping funnel, refluxing for 6-48 h after complete addition, cooling to room temperature, performing suction filtration, repeatedly washing with methanol, ethanol, water and tetrahydrofuran, and performing Soxhlet extraction for 8-24 h by using methanol and tetrahydrofuran respectively to obtain the thioether functionalized porphyrin structure porous organic polymer. The thioether functionalized terephthalaldehyde is at least one of 2, 3-dimethylthio-terephthalaldehyde, 2, 5-diethylthio-terephthalaldehyde, 2,3,5, 6-tetramethylthio-terephthalaldehyde and 2, 5-di ((methylthio) methyl) terephthalaldehyde as a monomer; the catalyst is FeCl 3 At least one of trifluoroacetic acid, propionic acid, etc.; the amount of the catalyst is 2-10 times of the molar weight of the porphyrin monomer unit, and the solvent is acetic acid, propionic acid or dichloromethane. The BET specific surface area of the prepared thioether-functionalized porphyrin-structured porous organic polymer is 100-800 m 2 A pore volume of 0.1 to 1.0 cm/g 3 (ii)/g, the average pore diameter is 0.5 to 4.0 nm.
Compared with the prior art, the technical scheme of the invention has the beneficial technical effects that:
1) according to the technical scheme, the pore size of the thioether-functionalized porphyrin-structured porous organic polymer and the random regulation and control of the modification of the functional monomer can be realized by selecting different thioether-functionalized terephthalaldehyde monomers and the dosage and the like. On one hand, the reduction of the specific surface area caused by post modification is avoided by adopting the pre-modification of the functional group; on the other hand, by utilizing the condensation polymerization reaction of porphyrin, the defect that functional monomers are difficult to highly crosslink is avoided, and the preparation of the porphyrin structure porous organic polymer with high specific surface area and high sulfur content is successfully realized.
2) The technical scheme of the invention can regulate and control the quantity and the pore size of thioether groups of the thioether functionalized porphyrin structure porous organic polymer so as to endow the thioether functionalized porphyrin structure porous organic polymer with metal ions Pb 2+ 、Cu 2+ And Hg 2+ And the like, as well as selective adsorption. The porphyrin structure in the polymer not only has a plane conjugated structure, but also has rich nitrogen atoms, and has better effect with heavy metal ions; abundant thioether functional groups can realize the reaction to metal ions Pb 2+ 、Cu 2+ And Hg 2+ Etc. selective adsorption; the structure of the hierarchical pores remarkably improves the adsorption kinetics of the polymer. So that the thioether functionalized porphyrin structure porous organic polymer overcomes the metal ion pollutants (metal ions Pb) existing in the ultrahigh cross-linked polymer reported in the prior art 2+ 、Cu 2+ And Hg 2+ Etc.) the adsorption effect and selectivity are not ideal.
3) The thioether functionalized porphyrin structure porous organic polymer is easy to elute after adsorbing heavy metal ions, has good reusability and stable structure, and can be widely applied to the fields of heavy metal adsorption, substance component analysis and the like.
4) The method for preparing the thioether functionalized porphyrin structure porous organic polymer is simple, has lower cost and can be industrially produced.
Drawings
Fig. 1 is an infrared spectrum of the thioether-functionalized porphyrin-structured porous organic polymer PPLS prepared in example 1 of the present invention.
FIG. 2 shows N of a thioether-functionalized porphyrin-structured porous organic polymer PPLS prepared in example 1 of the present invention 2 Adsorption and desorption curves and pore size distribution maps.
FIG. 3 shows that the thioether-functionalized porphyrin-structured porous organic polymer PPLS prepared in example 1 of the present invention has a reaction value at 298K to metal ions Hg 2+ Isothermal adsorption profile.
FIG. 4 shows that the thioether-functionalized porphyrin-structured porous organic polymer PPLS prepared in example 1 of the present invention adsorbs metal ions Hg at 298K 2+ Graph of the dynamics of (a).
Fig. 5 is a selectivity graph of different metal ions adsorbed by the thioether-functionalized porphyrin-structured porous organic polymer PPLS prepared in example 1 of the present invention. Testing of adsorption selectivity at 298K for mixed metal ion solutions containing Hg 2+ 、Fe 3+ 、Cu 2+ 、Mn 2+ 、Pb 2+ 、Cd 2+ 、Zn 2+ And Mg 2+ The initial concentration of each metal ion was 500 mg/L.
Fig. 6 is a selectivity graph of different metal ions adsorbed by the thioether-functionalized porphyrin-structured porous organic polymer PPLTS prepared in example 2 of the present invention; testing of adsorption Selectivity at 298K for Mixed Metal ion solutions containing Fe 3+ 、Cu 2+ 、Mn 2+ 、Pb 2+ 、Cd 2+ 、Zn 2+ 、Ca 2+ And Mg 2+ The initial concentration of each metal ion was 500 mg/L.
FIG. 7 shows that the thioether-functionalized porphyrin-structured porous organic polymer PPLS prepared in example 1 of the present invention reacts with metal ions Hg 2+ The performance graph for the adsorption was used repeatedly.
Fig. 8 is a structural diagram of a thioether-functionalized terephthalaldehyde monomer.
Fig. 9 is a schematic structural diagram of a thioether-functionalized porphyrin-structured porous organic polymer prepared in example 1 of the present invention.
Detailed Description
The following examples are intended to further illustrate the present invention, but are not intended to limit the scope of the claims.
Example 1
Preparation of thioether functionalized porphyrin structure porous organic polymer PPLS:
placing a 100mL three-neck round-bottom flask on an oil bath device provided with an electric stirrer, a reflux condenser tube, a constant-pressure dropping funnel and a thermometer, dissolving 2, 5-dimethylthioterephthalaldehyde (2mmol) in 30mL propionic acid under the nitrogen atmosphere, heating to 150 ℃, dissolving pyrrole (4mmol) in 30mL propionic acid, slowly dropwise adding by using the constant-pressure dropping funnel, refluxing for 48 hours after completely adding, cooling to room temperature, carrying out suction filtration, repeatedly washing by using methanol, ethanol, water and tetrahydrofuran, carrying out Soxhlet extraction for 24 hours by using methanol and tetrahydrofuran respectively, drying for 12 hours at 120 ℃, and carrying out vacuum drying for 24 hours to obtain the thioether functionalized porphyrin structure porous organic polymer. The infrared characterization is shown in the specification, the infrared characterization is shown in the specification after the reaction, and 1691cm after the reaction -1 The absorption peak of aldehyde group C ═ O is obviously weakened and is 3407cm -1 The absorption peak of N-H appears at 2918cm -1 A C-H absorption peak appears. Thus indicating the success of the reaction. The specific surface area of the prepared PPLS can reach 554m 2 /g。
Example 1 preparation of functional heteroatom-modified thioether-functionalized porphyrin-structured porous organic polymer for Metal ions Hg 2+ Isothermal adsorption test of (1): when Hg is contained 2+ At an initial concentration of 500mg/L, for Hg 2+ The maximum adsorption amount of the adsorbent is 972mg/g, the adsorption is quick, and the adsorption can reach 600mg/g within 5min when Hg is used 2+ At an initial concentration of 10mg/L, for Hg 2+ The maximum adsorption removal rate of the adsorbent can reach 99 percent.
Example 1 preparation of thioether functionalized porphyrin-structured porous organic polymer for Metal ions Hg 2+ Solution (Hg) 2+ Initial concentration of 500mg/L) is subjected to adsorption-desorption for 5 times, and the super-crosslinked polymer still has the reuse rate of more than 90 percent. In practical applications, the polymer can be reused many times.
The thioether-functionalized porphyrin-structured porous organic polymer prepared in example 1 has selective adsorption effect on metal ions: testing the adsorption selectivity of the thioether functionalized porphyrin structure porous organic polymer on mixed metal ion solution containing Hg at 298K 2+ 、Fe 3+ 、Cu 2+ 、Mn 2+ 、Pb 2+ 、Cd 2+ 、Zn 2+ And Mg 2+ The initial concentration of each metal ion was 500mg/L, and the test results are shown in FIG. 5 after the adsorption reached equilibrium. The thioether functionalized porphyrin structure porous organic polymer prepared in the example has high selectivity on mercury adsorption.
Example 2
Preparation of thioether functionalized porphyrin structure porous organic polymer PPLTS:
placing a 100mL three-neck round-bottom flask on an oil bath device provided with an electric stirrer, a reflux condenser tube, a constant pressure dropping funnel and a thermometer, dissolving 2,3,5, 6-tetramethylthio terephthalaldehyde (2mmol) in 30mL dichloromethane in a nitrogen atmosphere, adding propionic acid (20mmol), heating to 50 ℃, dissolving pyrrole (8mmol) in 30mL dichloromethane, slowly dropping by using the constant pressure dropping funnel, refluxing for 24h after complete addition, cooling to room temperature, performing suction filtration, repeatedly washing by using methanol, ethanol, water and tetrahydrofuran, performing Soxhlet extraction for 24h by using methanol and tetrahydrofuran respectively, drying for 12h at 120 ℃, and performing vacuum drying for 24h to obtain the thioether functionalized porphyrin structure porous organic polymer. The infrared characterization is shown, 1691cm after reaction -1 The absorption peak of aldehyde group C ═ O is obviously weakened and is 3407cm -1 The absorption peak of N-H appears at 2917cm -1 A C-H absorption peak appears. Thus indicating the success of the reaction.
Example 2 preparation of functional heteroatom-modified thioether-functionalized porphyrin-structured porous organic Polymer for Metal ion Pb 2+ Isothermal adsorption test of (1): when it is Pb 2+ Initial concentration of 500mg/L for Pb 2+ The maximum adsorption amount of (A) is 214mg/g, the adsorption is rapid, and the adsorption can reach the balance within 10 min.
Example 2 preparation of thioether-functionalized porphyrin-structured porous organic Polymer for Metal ion Pb 2+ Solution (Pb) 2+ Initial concentration of 500mg/L) is subjected to adsorption-desorption for 5 times, and the super-crosslinked polymer still has the reuse rate of over 91 percent. In practical applications, the polymer can be reused many times.
The thioether-functionalized porphyrin-structured porous organic polymer prepared in example 2 has a selective adsorption effect on metal ions: testing thioether functionalizationThe porphyrin structure porous organic polymer has adsorption selectivity of mixed metal ion solution at 298K, and the mixed metal ion solution contains Fe 3+ 、Cu 2+ 、Mn 2+ 、Pb 2+ 、Cd 2+ 、Zn 2+ 、Ca 2+ And Mg 2+ The initial concentration of each metal ion was 500mg/L, and the test results are shown in FIG. 6 after the adsorption reached equilibrium. The thioether-functionalized porphyrin-structured porous organic polymer prepared in the example has high selectivity on the adsorption of lead.
Example 3
Preparation of thioether functionalized porphyrin structure porous organic polymer:
placing a 100mL three-neck round-bottom flask on an oil bath device provided with an electric stirrer, a reflux condenser tube, a constant-pressure dropping funnel and a thermometer, dissolving 2, 3-dimethylthioterephthalaldehyde (2mmol) in 30mL propionic acid under the nitrogen atmosphere, adding trifluoroacetic acid (4mmol), heating to 150 ℃, dissolving pyrrole (6mmol) in 30mL propionic acid, slowly dropping by using the constant-pressure dropping funnel, refluxing for 6h after the complete addition, cooling to room temperature, performing suction filtration, repeatedly washing by using methanol, ethanol, water and tetrahydrofuran, performing Soxhlet extraction for 24h by using methanol and tetrahydrofuran respectively, drying for 12h at 120 ℃, and performing vacuum drying for 24h to obtain the thioether functionalized porphyrin structure porous organic polymer. The infrared characterization is shown, 1691cm after reaction -1 The absorption peak of aldehyde group C ═ O is obviously weakened and is 3407cm -1 The absorption peak of N-H appears at 2918cm -1 A C-H absorption peak appears. Thus indicating the success of the reaction.
Example 3 preparation of functional heteroatom-modified thioether-functionalized porphyrin-structured porous organic Polymer for Metal ion Cu 2+ Isothermal adsorption test of (1): when Cu 2+ At an initial concentration of 500mg/L, for Cu 2+ The maximum adsorption amount of the adsorbent is 112mg/g, the adsorption is rapid, and the adsorption can reach balance within 10 min.
Example 3 preparation of thioether-functionalized porphyrin-structured porous organic Polymer vs. Metal ion Cu 2+ Solution (Cu) 2+ Initial concentration of 500mg/L) is subjected to adsorption-desorption for 5 times, and the super-crosslinked polymer still has the reuse rate of more than 90 percent. In practical applicationThe polymer may be reused several times.
The thioether-functionalized porphyrin-structured porous organic polymer prepared in example 3 has high selective adsorption on copper.
Example 4
Preparation of thioether functionalized porphyrin structure porous organic polymer:
placing a 100mL three-neck round-bottom flask on an oil bath device provided with an electric stirrer, a reflux condenser tube, a constant-pressure dropping funnel and a thermometer, dissolving 2, 5-dimethylthioterephthalaldehyde (2mmol) in 30mL acetic acid under the nitrogen atmosphere, adding trifluoroacetic acid as a catalyst, heating to 120 ℃, dissolving pyrrole (4mmol) in 30mL acetic acid, slowly dropping by using the constant-pressure dropping funnel, refluxing for 36h after the pyrrole is completely added, cooling to room temperature, performing suction filtration, repeatedly washing by using methanol, ethanol, water and tetrahydrofuran, performing Soxhlet extraction for 24h by using methanol and tetrahydrofuran respectively, drying for 12h at 120 ℃, and performing vacuum drying for 24h to obtain the thioether functionalized porphyrin structure porous organic polymer. The infrared characterization is shown, 1691cm after reaction -1 The absorption peak of aldehyde group C ═ O is obviously weakened and is 3407cm -1 The absorption peak of N-H appears at 2917cm -1 A C-H absorption peak appears. Thus indicating the success of the reaction.
Example 4 preparation of functional heteroatom-modified thioether-functionalized porphyrin-structured porous organic polymer for Metal ions Hg 2+ Isothermal adsorption test of (1): when Hg is contained 2+ At an initial concentration of 500mg/L, for Hg 2+ The maximum adsorption amount of the adsorbent is 719mg/g, the adsorption is rapid, and the adsorption can reach balance within 10 min.
Example 4 preparation of thioether functionalized porphyrin-structured porous organic Polymer for Metal ions Hg 2+ Solution (Hg) 2+ Initial concentration of 500mg/L) is subjected to adsorption-desorption for 5 times, and the super-crosslinked polymer still has a reuse rate of more than 90%. In practical applications, the polymer can be reused many times.
The thioether-functionalized porphyrin-structured porous organic polymer prepared in example 4 has high selective adsorption on mercury.
Example 5
Preparation of thioether functionalized porphyrin structure porous organic polymer:
placing a 100mL three-neck round-bottom flask on an oil bath device provided with an electric stirrer, a reflux condenser tube, a constant-pressure dropping funnel and a thermometer, dissolving 2, 5-diethylthioterephthalaldehyde (2mmol) in 30mL propionic acid under nitrogen atmosphere, adding FeCl 3 Heating to 180 ℃ as a catalyst, dissolving pyrrole (3mmol) in 30mL of propionic acid, slowly dropwise adding by using a constant-pressure dropping funnel, refluxing for 24h after completely adding, cooling to room temperature, performing suction filtration, repeatedly washing by using methanol, ethanol, water and tetrahydrofuran, performing Soxhlet extraction for 24h by using methanol and tetrahydrofuran respectively, drying for 12h at 120 ℃, and performing vacuum drying for 24h to obtain the thioether functionalized porphyrin structure porous organic polymer. The infrared characterization is shown, 1691cm after reaction -1 The absorption peak of aldehyde group C ═ O is obviously weakened and is 3407cm -1 The absorption peak of N-H appears at 2917cm -1 A C-H absorption peak appears. Thus indicating the success of the reaction.
Example 5 preparation of functional heteroatom-modified thioether-functionalized porphyrin-structured porous organic Polymer for Metal ion Pb 2+ Isothermal adsorption test of (1): when it is Pb 2+ Initial concentration of 500mg/L for Pb 2+ The maximum adsorption amount of the adsorbent is 614mg/g, the adsorption is rapid, and the adsorption can reach the balance within 10 min.
Example 5 preparation of thioether-functionalized porphyrin-structured porous organic Polymer for Metal ion Pb 2+ Solution (Pb) 2+ Initial concentration of 500mg/L) is subjected to adsorption-desorption for 5 times, and the super-crosslinked polymer still has a reuse rate of more than 90%. In practical applications, the polymer can be reused many times.
The thioether-functionalized porphyrin-structured porous organic polymer prepared in example 5 mainly has high selective adsorption on mercury.
Example 6
Preparation of thioether functionalized porphyrin structure porous organic polymer:
placing a 100mL three-neck round-bottom flask on an oil bath device provided with an electric stirrer, a reflux condenser tube, a constant-pressure dropping funnel and a thermometer, and reacting under nitrogen atmosphereDissolving 2, 5-bis ((methylthio) methyl) terephthalaldehyde (2mmol) in 30mL acetic acid, heating to 140 ℃, dissolving pyrrole (4mmol) in 30mL acetic acid, slowly dripping by using a constant-pressure dropping funnel, refluxing for 24h after the pyrrole is completely added, cooling to room temperature, performing suction filtration, repeatedly washing by using methanol, ethanol, water and tetrahydrofuran, performing Soxhlet extraction for 24h by using methanol and tetrahydrofuran respectively, drying at 120 ℃ for 12h, and performing vacuum drying for 24h to obtain the thioether functionalized porphyrin structure porous organic polymer. The infrared characterization is shown, 1691cm after reaction -1 The absorption peak of aldehyde group C ═ O is obviously weakened and is 3407cm -1 The absorption peak of N-H appears at 2917cm -1 A C-H absorption peak appears. Thus indicating the success of the reaction.
Example 6 preparation of functional heteroatom-modified thioether-functionalized porphyrin-structured porous organic Polymer for Metal ion Cu 2+ Isothermal adsorption test of (1): when Cu 2+ At an initial concentration of 500mg/L, for Cu 2+ The maximum adsorption amount of the adsorbent is 124mg/g, the adsorption is rapid, and the adsorption can reach the balance within 10 min.
Example 6 preparation of thioether-functionalized porphyrin-structured porous organic Polymer vs. Metal ion Cu 2+ Solution (Cu) 2+ Initial concentration of 500mg/L) is subjected to adsorption-desorption for 5 times, and the super-crosslinked polymer still has the reuse rate of more than 90 percent. In practical applications, the polymer can be reused many times.
The thioether-functionalized porphyrin-structured porous organic polymer prepared in example 6 mainly has high selective adsorption on copper.
Example 7
Preparation of thioether functionalized porphyrin structure porous organic polymer:
a100 mL three-neck round-bottom flask was placed in an oil bath equipped with an electric stirrer, reflux condenser, constant pressure dropping funnel and thermometer, pyrrole (6mmol) was dissolved in 30mL acetic acid under nitrogen atmosphere, and FeCl was added 3 Heating to 180 deg.C as catalyst, dissolving 2, 5-dimethylthioterephthalaldehyde (2mmol) in 30mL acetic acid, slowly dripping with constant pressure dropping funnel, refluxing for 24 hr after adding completely, cooling to room temperature, vacuum filtering, adding methanol, ethanol, water, and tetrahydrofuranRepeatedly washing, respectively extracting with methanol and tetrahydrofuran by Soxhlet extraction for 24h, drying at 120 ℃ for 12h, and vacuum drying for 24h to obtain the thioether functionalized porphyrin structure porous organic polymer. The infrared characterization is shown, 1691cm after reaction -1 The absorption peak of aldehyde group C ═ O is obviously weakened and is 3407cm -1 The absorption peak of N-H appears at 2917cm -1 A C-H absorption peak appears. Thus indicating the success of the reaction.
Example 7 preparation of functional heteroatom-modified thioether-functionalized porphyrin-structured porous organic Polymer for treating Metal ions Hg 2+ Isothermal adsorption test of (1): when Hg is contained 2+ At an initial concentration of 500mg/L, for Hg 2+ The maximum adsorption amount of the adsorbent is 654mg/g, the adsorption is rapid, and the adsorption can reach the adsorption balance within 10 min.
Example 7 preparation of thioether functionalized porphyrin-structured porous organic Polymer for Metal ions Hg 2+ Solution (Hg) 2+ Initial concentration of 500mg/L) is subjected to adsorption-desorption for 5 times, and the super-crosslinked polymer still has the reuse rate of more than 90 percent. In practical applications, the polymer can be reused many times.
The thioether-functionalized porphyrin-structured porous organic polymer prepared in example 7 has high selective adsorption on mercury.
Example 8
The heavy metal ion adsorption performance of the thioether-functionalized porphyrin-structured porous organic polymer prepared in the embodiment 1-7 was tested.
(1) Isothermal adsorption:
selecting metal ion Cu 2+ 、Pb 2+ And Hg 2+ And the prepared thioether-functionalized porphyrin-structured porous organic polymer is compared with adsorbates in an aqueous solution by taking the prepared thioether-functionalized porphyrin-structured porous organic polymer as adsorbates and configuring corresponding metal ions into gradient solutions of 100, 200, 300, 400 and 500 mg/L. The specific operation method comprises the following steps:
a set of conical flasks (150mL) with a stopper was filled with about 0.020g of polymer and 50.0mL of different concentration gradients of the adsorbate in water, and placed in a water bath shaker and shaken at 25 ℃ for 2h to allow the adsorption to equilibrate. By atomic absorption spectroscopyMeasuring absorbance of the residue at the maximum absorption wavelength of the adsorbate, and converting into equilibrium concentration C of the adsorbate e The amount of adsorption was calculated according to equation 1:
q e ＝(C 0 -C e ) V/W equation 1
Wherein: q. q.s e To balance the amount of adsorption (mg/g), C 0 、C e The concentrations (mg/L) of heavy metal ions in the aqueous solution before and after adsorption, V is the volume (L) of the adsorption solution, and W is the mass (g) of the polymer. At equilibrium concentration C e As abscissa, adsorption quantity q e Plotting the ordinate to obtain the adsorption isotherm.
(2) Adsorption kinetics:
approximately 0.1g of the polymer was weighed into a 500mL Erlenmeyer flask with a stopper, and 250.0mL of metal ion Pb at a concentration of 500mg/L was added 2+ 、Cu 2+ And Hg 2+ And (4) putting the conical flask into a constant-temperature oscillator for shaking. After the solution is added, the shaking is started rapidly, the time is counted, 1mL of the adsorption solution is transferred into a volumetric flask at a certain time, and the residual metal ion concentration of the adsorption solution at different time points is measured by an atomic absorption spectrometer. The solution concentration was calculated from the standard curve equation. Then calculating the adsorption quantity q of the polymer at the time t according to the formula 1 t And drawing an adsorption kinetic curve of the polymer on the metal ions by taking t (min) as an abscissa and qt (mg/g) as an ordinate.
(3) The repeated use performance is as follows:
taking a 500mL conical flask with a plug, adding about 0.10g of polymer, and respectively adding 250.0mL of metal ion Pb with the original concentration of 500mg/L 2+ 、Cu 2+ And Hg 2+ And (3) solution. Placing into a constant temperature water bath oscillator at 25 ℃ and oscillating for 2 h. And after the adsorption is balanced, filtering, and obtaining the balanced adsorption capacity of the polymer from the filtrate by an atomic absorption spectrometer. The polymer on the filter paper is added with 250mL of desorption agent (5mol/L thiourea, 1mol/L HCl), shaken for 12h, filtered, washed with water and ethanol for multiple times, and dried for recycling. Repeating the steps for five times, measuring the absorbance value of adsorbate in the solution after adsorption, and calculating the equilibrium adsorption quantity of each time.

Claims (8)

1. A preparation method of a thioether functionalized porphyrin structure porous organic polymer is characterized by comprising the following steps: performing porphyrin polycondensation reaction on the thioether functionalized terephthalaldehyde monomer and a pyrrole monomer to obtain a thioether functionalized porphyrin structure porous organic polymer; the thioether-functionalized terephthalaldehyde monomer comprises at least one of 2, 3-dimethylthio-terephthalaldehyde, 2, 5-diethylthio-terephthalaldehyde, 2,3,5, 6-tetramethylthio-terephthalaldehyde and 2, 5-di ((methylthio) methyl) terephthalaldehyde; the molar percentage composition of the thioether functionalized terephthalaldehyde monomer and the pyrrole monomer is (10-50%) (50-90%).
2. The method for preparing a thioether-functionalized porphyrin-structured porous organic polymer according to claim 1, wherein: the conditions of the porphyrin polycondensation reaction are as follows: reacting for 6-48 h at 50-180 ℃ under the action of a Lewis acid catalyst.
3. The method for preparing the thioether-functionalized porphyrin-structured porous organic polymer according to claim 2, wherein the method comprises the following steps: the Lewis acid catalyst is at least one of ferric trichloride, trifluoroacetic acid and propionic acid.
4. The method for preparing a thioether-functionalized porphyrin-structured porous organic polymer according to claim 1, wherein: the porphyrin polycondensation reaction is carried out in at least one solvent of acetic acid, propionic acid and dichloromethane.
5. The method for preparing a thioether-functionalized porphyrin-structured porous organic polymer according to claim 1, wherein: respectively dissolving thioether-functionalized terephthalaldehyde monomers and pyrrole monomers in a solvent to obtain thioether-functionalized terephthalaldehyde monomer solution and pyrrole monomer solution, slowly adding the thioether-functionalized terephthalaldehyde monomer solution into the pyrrole monomer solution to perform porphyrin polycondensation reaction, or slowly adding the pyrrole monomer solution into the thioether-functionalized terephthalaldehyde monomer solution to perform porphyrin polycondensation reaction.
6. A thioether functionalized porphyrin structure porous organic polymer is characterized in that: the preparation method of any one of claims 1 to 5.
7. The thioether-functionalized porphyrin-structured porous organic polymer of claim 6, wherein: the sulfur content is 3-20% by mass, and the specific surface area is 100-800 m 2 A pore volume of 0.1 to 1.0 cm/g 3 (ii)/g, the average pore diameter is 0.5 to 4.0 nm.
8. The use of a thioether-functionalized, porphyrin-structured porous organic polymer according to claim 6 or 7, wherein: the adsorbent is used for adsorbing heavy metal ions in water.
CN202111327390.XA 2021-11-10 2021-11-10 Thioether-functionalized porphyrin-structured porous organic polymer, preparation method thereof and application thereof in adsorption of heavy metals in water Active CN113896849B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202111327390.XA CN113896849B (en) 2021-11-10 2021-11-10 Thioether-functionalized porphyrin-structured porous organic polymer, preparation method thereof and application thereof in adsorption of heavy metals in water

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111327390.XA CN113896849B (en) 2021-11-10 2021-11-10 Thioether-functionalized porphyrin-structured porous organic polymer, preparation method thereof and application thereof in adsorption of heavy metals in water

Publications (2)

Publication Number Publication Date
CN113896849A CN113896849A (en) 2022-01-07
CN113896849B true CN113896849B (en) 2022-09-27

Family

ID=79194029

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111327390.XA Active CN113896849B (en) 2021-11-10 2021-11-10 Thioether-functionalized porphyrin-structured porous organic polymer, preparation method thereof and application thereof in adsorption of heavy metals in water

Country Status (1)

Country Link
CN (1) CN113896849B (en)

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9688686B2 (en) * 2013-06-21 2017-06-27 Council Of Scientific And Industrial Research Porphyrin containing covalent organic frameworks and process for the preparation thereof
CN110746602B (en) * 2019-10-29 2021-04-20 大连理工大学 Metal cobalt porphyrin-based porous organic polymer and preparation method and application thereof
CN112321824A (en) * 2020-10-09 2021-02-05 华中科技大学 Preparation method of imidazole type ionic liquid porous organic polymer

Also Published As

Publication number Publication date
CN113896849A (en) 2022-01-07

Similar Documents

Publication Publication Date Title
Han et al. Acetylcysteine-functionalized microporous conjugated polymers for potential separation of uranium from radioactive effluents
Cui et al. Magnetic surface molecularly imprinted polymer for selective adsorption of quinoline from coking wastewater
Zhang et al. Amino modification of rice straw-derived biochar for enhancing its cadmium (II) ions adsorption from water
Ren et al. N-doped porous carbons with exceptionally high CO2 selectivity for CO2 capture
Bai et al. A novel functional porous organic polymer for the removal of uranium from wastewater
Srivastava et al. A comparative evaluation for adsorption of dye on Neem bark and mango bark powder
Liu et al. Synthesis of porous acrylonitrile/methyl acrylate copolymer beads by suspended emulsion polymerization and their adsorption properties after amidoximation
Shen et al. One-pot synthesis of a highly porous anionic hypercrosslinked polymer for ultrafast adsorption of organic pollutants
Zhang et al. Enhancement of CO2 adsorption on high surface area activated carbon modified by N2, H2 and ammonia
Wang et al. Removal of uranium (VI) from aqueous solution using iminodiacetic acid derivative functionalized SBA-15 as adsorbents
Liu et al. Control of porosity of novel carbazole-modified polytriazine frameworks for highly selective separation of CO 2–N 2
Zhu et al. Poly (N, N-dimethylaminoethyl methacrylate) modification of activated carbon for copper ions removal
Hongjie et al. Preparation of organically functionalized silica gel as adsorbent for copper ion adsorption
Wang et al. Polymer monoliths with chelating functionalities for solid phase extraction of metal ions from water
Hassanzadeh et al. An effective approach for fast selective separation of Cr (VI) from water by ion-imprinted polymer grafted on the electro-spun nanofibrous mat of functionalized polyacrylonitrile
Li et al. Fabrication of porous resins via solubility differences for adsorption of cadmium (II)
Bai et al. N2 plasma treatment on activated carbon fibers for toxic gas removal: Mechanism study by electrochemical investigation
Parambadath et al. Concentration-dependant selective removal of Cr (III), Pb (II) and Zn (II) from aqueous mixtures using 5-methyl-2-thiophenecarboxaldehyde Schiff base-immobilised SBA-15
Fang et al. Development of an anion imprinted polymer for high and selective removal of arsenite from wastewater
Rong et al. Fabrication of ultramicroporous triphenylamine-based polyaminal networks for low-pressure carbon dioxide capture
Pan et al. Novel sulfhydryl functionalized covalent organic frameworks for ultra-trace Hg2+ removal from aqueous solution
Dong et al. Fabrication of two dual-functionalized covalent organic polymers through heterostructural mixed linkers and their use as cationic dye adsorbents
CN112892501A (en) Double-imidazole polyionic liquid and metal organic framework composite material as well as preparation method and application thereof
CN113372524B (en) Non-reversible thiourea-linked covalent organic framework capable of rapidly removing mercury, and preparation method and application thereof
Sun et al. Using a novel adsorbent macrocyclic compound cucurbit [8] uril for Pb2+ removal from aqueous solution

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