阅读说明：本技术 具有层级孔道分布的多孔有机聚合物及其制备方法与应用 (Porous organic polymer with hierarchical pore channel distribution and preparation method and application thereof ) 是由 邱挺 娄晓瑜 陈杰 叶长燊 王红星 黄智贤 杨臣 王清莲 于 2021-09-28 设计创作，主要内容包括：本发明公开了一种具有层级孔道分布的多孔有机聚合物的制备方法,其是在多孔有机聚合物的聚合过程中通过间隔投加不同长短的连接子并调控各连接子的投加比例及间隔的投加时间,以实现对多孔有机聚合物的孔道分布和结构的调控,得到具有层级孔道分布的多孔有机聚合物。本发明具有操作简单、条件温和、效果显著、绿色环保等优点,其无需在使用任何额外的模板剂或进行复杂操作的条件下即可实现对多孔有机聚合物孔道结构的调控,并且可有效提高多孔聚合物对金属离子的吸附容量,增强金属离子在多孔聚合物孔道中的扩散传质能力,因而具有广泛的应用前景。(The invention discloses a preparation method of a porous organic polymer with hierarchical pore channel distribution, which comprises the steps of adding different lengths of linkers at intervals and regulating and controlling the adding proportion and the adding time of each linker during the polymerization process of the porous organic polymer so as to realize the regulation and control of the pore channel distribution and the structure of the porous organic polymer and obtain the porous organic polymer with hierarchical pore channel distribution. The method has the advantages of simple operation, mild condition, obvious effect, environmental protection and the like, can realize the regulation and control of the porous organic polymer pore channel structure without using any additional template agent or carrying out complex operation, can effectively improve the adsorption capacity of the porous polymer to metal ions, and enhances the diffusion mass transfer capacity of the metal ions in the porous polymer pore channel, thereby having wide application prospect.)

1. A preparation method of a porous organic polymer with hierarchical pore channel distribution is characterized in that: different linkers from short to long are sequentially introduced in the polymerization process, and the adding proportion and adding interval time of each linker are regulated and controlled so as to effectively regulate and control the pore distribution of a polymer network and construct the porous organic polymer with hierarchical pore distribution.

2. The method of claim 1, wherein the porous organic polymer having hierarchical pore channel distribution comprises: the method comprises the following steps:

1) uniformly mixing a solvent, a core, a catalyst, a ligand, alkali and salt;

2) sequentially adding different linkers with the length from short to long into the mixed solution obtained in the step 1), and reacting for a period of time at intervals after each addition;

3) and (3) after adding the linker with the longest length, continuing to react for a period of time, and performing suction filtration, washing and drying on the product to obtain the porous organic polymer with hierarchical pore channel distribution.

3. The method of claim 2, wherein the porous organic polymer having hierarchical pore channel distribution comprises: the solvent is tetrahydrofuran, 1, 4-dioxane or toluene;

the center is an arylamine compound containing three or more coupling groups;

the catalyst is a palladium catalyst;

the ligand is 2-dicyclohexyl phosphorus-2 ',4',6' -triisopropyl biphenyl;

the alkali is inorganic alkali;

the salt is an inorganic salt.

4. The method of claim 2, wherein the porous organic polymer having hierarchical pore channel distribution comprises: the linker is a chemical substance with two or more linking groups; the different linkers differ by the length of one or two benzene rings.

5. The method of claim 2, wherein the porous organic polymer having hierarchical pore channel distribution comprises: the molar ratio of the linker to the center is 0.1:1-1: 1.

6. The method of claim 2, wherein the porous organic polymer having hierarchical pore channel distribution comprises: the temperature of the interval reaction in the step 2) is 60-67 ℃, and the time is 0-500 min.

7. The method of claim 2, wherein the porous organic polymer having hierarchical pore channel distribution comprises: the reaction temperature in the step 3) is 60-67 ℃, and the reaction time is 100-3000 min.

8. A porous organic polymer having a hierarchical pore distribution prepared according to the method of any one of claims 1 to 7.

9. Use of a porous organic polymer having a hierarchical pore distribution according to claim 8 for metal ion adsorption, wherein: the metal ions are at least one of heavy metal ions or alkaline earth metal ions.

Technical Field

The invention belongs to the field of synthesis of chemical functional materials, and particularly relates to a porous organic polymer with hierarchical pore channel distribution, and preparation and application thereof in metal ion adsorption.

Background

The Porous Organic Polymers (POPs) refer to a class of organic polymers with rich pore channels, wherein Microporous Conjugated polymers (CMP) are porous organic polymers with Conjugated structures and an important subclass of porous materials, rigid aromatic groups are coupled and connected through covalent bonds to form a network structure with pi-Conjugated units and rich micropores, and therefore the porous organic polymers have important characteristics of considerable specific surface area, micropore controllability, high thermal stability, chemical stability and the like. Meanwhile, the microporous conjugated polymer also has the characteristic of modularized polymerization coupling, and various building units can be introduced into a network structure as required to regulate and control functions and the network structure. At present, CMPs are widely applied to a plurality of fields such as gas adsorption and separation, chemical adsorption and the like. It is worth mentioning that the CMPs have the advantages of large specific surface area, abundant conjugated groups, high porosity and the like, so the CMPs also have wide application prospects in the aspect of water treatment.

However, current CMPs areA problem still remains to be solved in water treatment applications, namely that when shorter linkers are used, the CMPs have larger specific surface area and larger storage space from a thermodynamic perspective than CMPs using long linkers, but the pore size is usually smaller, so that M (H) is used as the M (H) in the adsorption process of the CMPs on metal ions in water₂O)_X ⁿ⁺The metal ions in the hydrated form are difficult to effectively diffuse in the microporous pore channel, so that the problems that the internal pore channel cannot be fully utilized and the like exist, and finally, the adsorption quantity is low and the diffusion rate is slow are caused.

On the basis of the molecular structural formula of CMPs, from the aspect of dynamics, the invention constructs a pore channel structure with hierarchical distribution from inside to outside by gradually introducing short-to-long connectors in the preparation process, and finally realizes the effective diffusion of hydrated metal ions from outside to inside in the pore channel and the improvement of the utilization rate of the internal pore channel by using the pore channel with smaller inner layer size as a storage pore channel while using the pore channel with larger outer layer size as a diffusion pore channel, thereby improving the adsorption rate and the adsorption capacity of the porous organic polymer to pollutants such as heavy metal mercury ions and the like and overcoming the defects of the existing material.

Disclosure of Invention

Aiming at the challenges and the defects, the invention aims to provide a porous organic polymer with hierarchical pore channel distribution and a preparation method and application thereof, which improve the adsorption capacity of the porous organic polymer material on pollutants such as mercury ions and the like by constructing and optimizing the pore channel structure of the porous organic polymer material, and solve the problems that the internal pore channels of the porous organic polymer cannot be fully utilized, the adsorption mass transfer is poor and the like.

In order to achieve the purpose, the invention adopts the following technical scheme:

the first purpose of the invention is to protect a preparation method of a porous organic polymer with hierarchical pore channel distribution, which comprises the steps of sequentially introducing different linkers from short to long in the polymerization process, and regulating and controlling the adding proportion and adding interval time of each linker so as to effectively regulate and control the pore channel distribution of a polymer network and construct the porous organic polymer with hierarchical pore channel distribution.

The method specifically comprises the following steps:

1) uniformly mixing a solvent, a core, a catalyst, a ligand, alkali and salt;

2) sequentially adding different linkers with the length from short to long into the mixed solution obtained in the step 1), and reacting for a period of time at intervals after each addition;

3) and (3) after adding the linker with the longest length, continuing to react for a period of time, and performing suction filtration, washing and drying on the product to obtain the porous organic polymer with hierarchical pore channel distribution.

Further, the solvent in step 1) is an organic solvent such as tetrahydrofuran, 1, 4-dioxane or toluene, which can dissolve the above chemical substances or dissolve a small amount of the above chemical substances.

Further, the core is an arylamine compound containing three or more coupling groups of-Br, -Cl, -I and the like, and can be selected from tri (4-bromophenyl) amine and the like.

Further, the catalyst is a palladium-based catalyst, which may be selected from bis (benzylidene acetone) palladium and the like.

Further, the ligand is 2-dicyclohexyl phosphorus-2 ',4',6' -triisopropyl biphenyl.

Further, the base is an inorganic base, which may be selected from sodium tert-butoxide.

Further, the salt is an inorganic salt, which may optionally be NaF.

Further, the linker is a linker having two or more-NH groups₂Chemical species of the linking group; the difference between different linkers is the length of one benzene ring or two benzene rings; the matching mode of different adopted connectors is as follows: p-phenylenediamine with a shorter length and 4, 4' -diaminodiphenylamine with a longer length; tris (4-aminophenyl) amine, p-phenylenediamine and 4, 4' -diaminodiphenylamine which are sequentially increased in length.

Furthermore, the molar ratio of the used linker to the centre is 0.1:1 to 1: 1.

Further, the temperature of the interval reaction in the step 2) is 60-67 ℃, and the time is 0-500 min.

Further, the temperature of the reaction in the step 3) is 60-67 ℃, and the time is 100-3000 min.

The second object of the present invention is to protect the porous organic polymer having hierarchical pore distribution prepared by the above method.

The third purpose of the invention is to protect the application of the porous organic polymer with hierarchical pore channel distribution in adsorbing metal ions in water or organic solvent, wherein the metal ions are mercury ions, lead ions, copper ions and the like, and the density of the metal ions is more than 4.5 g/cm³Preferably, the metal ion(s) is/are at least one of a heavy metal ion(s), an alkaline earth metal ion(s), such as a sodium ion or a calcium ion, and preferably a mercury ion.

The invention adopts an interval adding method, namely, gradually introducing the linker from short to long in a certain interval time to construct the porous organic polymer with a hierarchical pore channel distribution structure from inside to outside, wherein the porous organic polymer can promote more hydrated metal ions to enter the pore channels by utilizing the pore channels with larger outer layers and store more metal ions by utilizing the pore channels with smaller inner layers as storage spaces, so that the adsorption mass transfer and diffusion capacity of the porous organic polymer is improved, and the high-efficiency adsorption of the porous organic polymer on pollutants such as the metal ions is realized.

The invention has the following remarkable advantages: the method has the advantages of simple operation, mild condition, obvious effect, environmental protection and capability of realizing the regulation and control of the distribution of the polymer pore structure without any additional template agent or complex operation condition, and the prepared polymer can increase the adsorption quantity of Hg ions by more than 100 percent in the treatment of the mercury-containing wastewater, thereby having wide application prospect.

Drawings

FIG. 1 is an infrared spectrum of CMPA-M-1(1: X: Y) obtained by polymerizing CMPA-2 and CMPA-3 with linkers in different ratios in example 1;

FIG. 2 is a graph showing the nitrogen adsorption and desorption curves and the pore size distribution of CMPA-M-1(1: X: Y) obtained by polymerizing CMPA-2 and CMPA-3 with linkers in different ratios in example 1;

FIG. 3 is an infrared spectrum of CMPA-M-2 and reverse CMPA-M-3 obtained by polymerization with three linkers added at intervals;

FIG. 4 is a nitrogen adsorption-desorption curve diagram and an aperture distribution diagram of CMPA-M-2 obtained by adding three linkers at intervals for polymerization;

FIG. 5 is a graph of adsorption kinetics of a hierarchical microporous conjugated polymer material for mercury ions;

fig. 6 is a model diagram of intra-particle diffusion obtained by fitting the adsorption kinetic data of mercury ions by the hierarchical microporous conjugated polymer material.

Detailed Description

In order to make the present invention more comprehensible, the technical solutions of the present invention are further described below with reference to specific embodiments, but the present invention is not limited thereto.

For convenient comparison, CMPA-1, CMPA-2 and CMPA-3 are synthesized by the following specific synthesis processes: 1.0 mmol of tris (4-bromophenyl) amine as the core was mixed with 1.0 mmol of tris (4-aminophenyl) amine, 1.5 mmol of p-phenylenediamine and 1.5 mmol of 4, 4' -diaminodiphenylamine, respectively, and 5 mol% of Pd (dba)₂Adding 9 mol% of xPhos, 7 eq. NaOtBu and 1 mmol of NaF into 50 mL of tetrahydrofuran (solvent), reacting at 66 ℃ for 48 h, filtering the obtained product, soaking and washing the product with chloroform, ethanol and other solutions respectively, and drying in vacuum to obtain polymers CMPA-1, CMPA-2 and CMPA-3 respectively.

Mercury adsorption experiments: 10 mg of adsorbing material is added into 1000mg/L solution containing metal mercury, and the adsorbing material is used for adsorbing for 24 hours under the conditions that the oscillation speed is 200 rpm and the temperature is 25 ℃. Separating the adsorbent after adsorption, and detecting the concentration of metallic mercury in the clear liquid by adopting ICP-9000.

Example 1:

p-phenylenediamine with short length and 4, 4' -diaminodiphenylamine with long length are used as linkers, the adding proportion is regulated and controlled, and a BH coupling method is adopted for polymerization, so that the influence of the adding proportion on the pore structure is inspected:

0.3 mmol, 0.4 mmol, 0.5 mmol and 0.6 mmol of p-phenylenediamine as the first linker were added to a solution containing 1.0 mmol of tris (4-bromophenyl) amine (center), 5 mol% of Pd (dba)₂、9 mol% xPhos、7 eq. NaOtBu、1 mmol of NaF and 20 mL of tetrahydrofuran (solvent) at 66 ℃ for 0.5h, correspondingly adding 0.7 mmol, 0.6 mmol, 0.5 mmol and 0.4 mmol of 4, 4' -diaminodiphenylamine as a second linker, continuously reacting for 48 h at 66 ℃, filtering the obtained product, soaking and washing the product with chloroform, ethanol and other solutions respectively, drying the product in vacuum, thus obtaining a series of hierarchical microporous conjugated polyaniline materials CMPA-M-1(1: X: Y) (wherein 1 is the molar ratio of the center seed, X is the molar ratio of the shorter-length linker to the center seed, and Y is the molar ratio of the longer-length linker to the center seed, namely CMPA-M-1(1:0.3:0.7), CMPA-M-1(1:0.4:0.6), CMPA-M-1(1: 0.5: 0.5) and CMPA-M-1(1: 0.6: 0.4) respectively).

FIG. 1 is an infrared spectrum of CMPA-M-1(1: X: Y) obtained by polymerizing CMPA-2 and CMPA-3 with linkers in different ratios. As can be seen from the figure, the CMPA-M-1 spectrum has a central tris (4-bromophenyl) amine at 710, 1004 and 1070 cm^-1The characteristic vibration peak of C-Br bond and the spectrogram of the linker p-phenylenediamine and 4, 4' -diaminodiphenylamine are at 3400-^-1NH of (C)₂The characteristic vibration peak of the key was not observed, but it was at 1500 cm^-1A new peak of C-N bond appeared nearby, indicating efficient coupling of tris (4-bromophenyl) amine to both linkers and successful preparation of CMPA-M-1.

FIG. 2 is a graph showing the nitrogen adsorption and desorption curves and the pore size distribution of CMPA-M-1(1: X: Y) obtained by polymerizing CMPA-2 and CMPA-3 with linkers in different ratios. As can be seen from the figure, the CMPA-M-1 thus obtained showed a nitrogen adsorption/desorption curve of type I, indicating that CMPA-M-1 has a large number of micropores and a large specific surface area. The pore structure data are shown in table 1. The result shows that the specific surface area, the pore size distribution and the pore channel structure of the porous polymer can be regulated and controlled by changing the ratio of the two linkers. And as the proportion of the inner layer short linker increases, the amount of micropores also shows a rising trend from 0.1003 cm³Increase in the amount of/g to 0.1741 cm³(ii) in terms of/g. The experiment on mercury adsorption shows that the regulation of the proportion of the linker can also effectively regulate the adsorption capacity of the material on mercury ions, and the regulation proves that the invention can effectively increase the diffusion pore and the storage space of the material.

TABLE 1 pore Structure data for CMPA-M-1 obtained by linker polymerization at different ratios

Example 2:

the molar ratio of 1:0.5:0.5 is used as the adding amount, the adding time interval (0.5 h, 1.0 h and 2.0 h respectively) of the two linkers with different configurations and lengths in example 1 is regulated and controlled, and a BH coupling method is adopted for polymerization to examine the influence of the adding time interval on the pore channel structure:

0.5 mmol of p-phenylenediamine as a first linker was added to 1.0 mmol of tris (4-bromophenyl) amine (center) and reacted with 5 mol% Pd (dba)₂Adding 9 mol% of xPhos, 7 eq. NaOtBu and 1 mmol of NaF into 20 mL of tetrahydrofuran (solvent) together, reacting at 66 ℃ for 0.5h, 1.0 h and 2.0 h respectively, adding 0.5 mmol of 4, 4' -diaminodiphenylamine serving as a second linker, continuing reacting at 66 ℃ for 48 h, filtering the obtained product, soaking and washing the product with chloroform, ethanol and other solutions respectively, and drying in vacuum to obtain the hierarchical microporous conjugated polyaniline material.

Table 2 shows the pore structure data of the polymer materials prepared by adding at different time intervals. The result shows that the specific surface area, the pore size distribution and the pore structure of the material can be further regulated and controlled by regulating and controlling the interval adding time. And the amount of micropores appeared to be from 0.1448 cm with increasing interval time from 0.5h to 1.0 h³Increase in the amount of/g to 0.1560 cm³And/g, indicating that the prolonged interval favors the aggregate growth of the first linker and reduces the competitive aggregation of the two linkers. Through the adsorption experiment on mercury, the adsorption capacity of the material can be improved to 495 mg/g by increasing the interval time from 0.5h to 1.0 h, and the effectiveness of the material in improving the adsorption capacity of the material on mercury ions is further illustrated.

TABLE 2 pore structure data of BH coupling polymerization before and after different interval dosing time regulation

Example 3:

1. in order to further improve the adsorption capacity for mercury ions, a shorter linker was further introduced into the innermost layer to form a polymer with a larger specific surface area and more internal storage space, i.e., three linkers (tris (4-aminophenyl) amine, p-phenylenediamine, 4' -diaminodiphenylamine, respectively) with short to long lengths were introduced at intervals, and polymerization was performed by the BH coupling method to examine the universality of the method:

0.3 mmol of tris (4-aminophenyl) amine as first linker was added to 1.0 mmol of tris (4-bromophenyl) amine (centre) and this was reacted with 5 mol% Pd (dba)₂Adding 9 mol% of xPhos, 7 eq. NaOtBu and 1 mmol of NaF into 20 mL of tetrahydrofuran (solvent), reacting at 66 ℃ for 1.0 h, adding 0.3 mmol of p-phenylenediamine as a second linker, continuing to react for 1.0 h, adding 0.3 mmol of 4, 4' -diaminodiphenylamine as a third linker, continuing to react at 66 ℃ for 48 h, filtering and separating the obtained product, soaking and washing the product with chloroform, ethanol and other solutions respectively, and drying in vacuum to obtain the hierarchical microporous conjugated polyaniline material CMPA-M-2.

FIG. 3 is an infrared spectrum of CMPA-M-2 formed after the introduction of three linkers. From the spectrum of CMPA-M-2, the central seed of tris (4-bromophenyl) amine was found at 710, 1004 and 1070 cm^-1The characteristic vibration peak of C-Br bond at (C-Br) and the linker at 3400-^-1NH of (C)₂The key characteristic vibration peak is not observed in the spectrogram of the polymer, but is 1500 cm^-1A new peak of C-N bond appeared nearby, indicating efficient coupling of tris (4-bromophenyl) amine to the three linkers and successful preparation of CMPA-M-2.

FIG. 4 is a nitrogen adsorption and desorption curve diagram and an aperture distribution diagram of CMPA-M-2 obtained after three linkers are added at intervals. The results show that the prepared CMPA-M-2 shows a nitrogen adsorption and desorption curve of the type I, and the CMPA-M-2 is provided with a large number of micropores and a large specific surface area. And the obvious discovery from the pore size distribution diagram shows that after the connectors from short to long are introduced layer by layer, obvious pore size distribution areas appear at three positions of 0.7 nm, 0.8 nm and 1.4 nm, which proves that the method can successfully construct and regulate the molecular pore path of the microporous conjugated polymer material. The adsorption capacity of the porous organic polymer is further improved to 746 mg/g through the mercury adsorption experiment, which shows that the invention is effective for improving the mercury ion adsorption capacity of the porous organic polymer.

2. In order to prove that a hierarchical pore distribution structure from inside to outside has a good effect on adsorption diffusion by gradually introducing short-to-long linkers, a group of control experiments are carried out, wherein the shortest linker is constructed on the outermost layer to form a reverse construction, and polymerization is carried out by a BH coupling method, and the specific steps are as follows:

0.3 mmol of p-phenylenediamine as a first linker was added to 1.0 mmol of tris (4-bromophenyl) amine (centre) and this was reacted with 5 mol% Pd (dba)₂Adding 9 mol% of xPhos, 7 eq. NaOtBu and 1 mmol of NaF into 20 mL of tetrahydrofuran (solvent), reacting at 66 ℃ for 1.0 h, adding 0.3 mmol of second linker 4, 4' -diaminodiphenylamine, continuing to react for 1.0 h, introducing 0.3 mmol of the third shortest linker tri (4-aminophenyl) amine, continuing to react at 66 ℃ for 48 h, filtering the obtained product, soaking and washing the product with chloroform, ethanol and other solutions respectively, and performing vacuum drying to obtain the reverse-level microporous polyaniline conjugated material (CMPA-M-3).

As can be seen from FIG. 3, CMPA-M-3 has the same FTIR spectrum as CMPA-M-2, due to the fact that both molecular structures are identical, confirming successful polymerization of CMPA-M-3.

Table 3 shows the pore structure data of the obtained hierarchical pore conjugated microporous polymer materials CMPA-M-2 and CMPA-M-3. The result shows that the mesoporous amount of the microporous conjugated polymer CMPA-M-2 obtained by introducing three linkers layer by layer according to the length is increased to 0.2039 cm³And/g, it proves that the introduction of the longest linker in the outermost layer is advantageous for the establishment of diffusion channels.

TABLE 3 introduction of linkers in different sequences to obtain pore structure data for hierarchical microporous conjugated polymer materials

FIGS. 5 and 6 are model diagrams of the intra-particle diffusion obtained by fitting the kinetics data and the adsorption kinetics of the hierarchical microporous conjugated polymer materials CMPA-M-2 and CMPA-M-3 to mercury ions, respectively. As can be seen from FIG. 5, in the mercury ion solution with the initial concentration of 50mg/L, the CMPA-M-2 constructed by the invention can reach the adsorption equilibrium within about 20 min. The reverse CMPA-M-3 constructed in the reverse step can reach adsorption balance after 1.0 h, and the method provided by the invention is proved to have important influence on improving the diffusion of metal ions in the pore channel. FIG. 6 further reveals the effect of the diffusion channel constructed by the present invention (the fitting data are shown in Table 4), which indicates that heavy metal ions only undergo peripheral liquid film diffusion and do not undergo intra-channel diffusion in the adsorption process of CMPA-1 and reverse CMPA-M-3 having smaller-sized channels; and the heavy metal ions have an intragranular diffusion stage besides liquid film diffusion in the adsorption process of CMPA-3 and CMPA-M-2 with larger-sized pore passages on the outer layer.

TABLE 4 intraparticle diffusion kinetics model fitting data

In conclusion, the preparation method provided by the invention can effectively construct a diffusion channel, can remarkably improve the diffusion and storage of heavy metal ions in the pore channel, and has important significance for practical application of wastewater adsorption treatment and the like.

The application example is as follows:

in order to further examine the adsorption effect of the hierarchical microporous conjugated polymer material on metal ions, an adsorption experiment of various metal ions is carried out, and the specific steps are as follows:

10 mg of CMPA-1, CMPA-2 and CMPA-3, CMPA-M-1(1: 0.5: 0.5) prepared in example 1, CMPA-M-1 (1.0 h) prepared in example 2 and CMPA-M-3 prepared in example 3 were added to 10 mL of water to be treated containing 1000mg/L of metal mercury ions, respectively, and adsorbed at a shaking speed of 200 rpm at a temperature of 25 ℃ for 24 h. And (4) separating the adsorbent by using a filter head after adsorption, and detecting the concentration of the metal in the treated water body by using ICP-9000 to obtain a clarified liquid.

The test result shows that after 24 hours of adsorption, the adsorption capacities of CMPA-1, CMPA-2, CMPA-3, CMPA-M-1(1: 0.5: 0.5), CMPA-M-1 (1.0 hour) and CMPA-M-3 to Hg (II) are 438 mg/g, 430 mg/g, 375 mg/g, 441 mg/g, 495 mg/g and 547 mg/g respectively; and the adsorption capacity of the hierarchical microporous conjugated polymer material CMPA-M-2 to mercury ions can reach 746 mg/g, and compared with CMPA-3, the adsorption capacity is improved by nearly 100%, which shows that the prepared hierarchical microporous conjugated polymer material CMPA-M-2 has obvious superiority in mercury ion adsorption.

Meanwhile, in order to embody the advancement of the invention in practical adsorption, a mixed ion competitive adsorption experiment is carried out, and the specific experimental steps are as follows:

10 mg of CMPA-M-2 material prepared in example 3 was added to 10 mL of a mixed metal solution containing 100mg/L of Hg (II), Ni (II), La (III), Pb (II), and adsorbed at a shaking speed of 200 rpm at a temperature of 25 ℃ for 24 hours. And (4) separating the adsorbent by using a filter head after adsorption, and detecting the concentration of the metal in the treated water body by using ICP-9000 to obtain a clarified liquid.

The test result shows that after 24 hours of adsorption, the hierarchical microporous conjugated polymer material only shows the adsorption capacity to Hg (II), and the removal rate is as high as 93%. The hierarchical microporous conjugated polymer material prepared by the invention has excellent adsorption selectivity in mixed ion competitive adsorption, and has important significance for adsorption treatment of Hg (II) in complex water bodies.

The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.