CN112794994B - Thiophene unit-based porous organic polymer and preparation method and application thereof - Google Patents
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Abstract
The invention belongs to the technical field of new materials, and particularly relates to a porous organic polymer based on thiophene units, which takes sulfur-containing thiophene monomers with pi conjugated structures and tri (4-boric acid frequency farnesyl ester phenyl) amine as structural units, and the sulfur-containing porous organic polymer is effectively synthesized by a Suzuki coupling reaction one-pot method, and the preparation method comprises the following steps: putting sulfur-containing thiophene monomer with pi conjugated structure and tri (4-boric acid frequency farnesyl alcohol ester phenyl) amine into a prepared reaction container, adding N, N' -dimethylformamide, freezing the mixture by using liquid nitrogen, vacuumizing by using a vacuum pump, introducing nitrogen to normal pressure, and repeating the cycle for three times; adding a catalyst, continuously freezing by using liquid nitrogen, vacuumizing by using a vacuum pump, introducing nitrogen to normal pressure, and repeatedly circulating for three times; thawing and then reacting; washing, purifying and drying to obtain the target product. The adsorbent prepared by the invention has high separation and enrichment efficiency, and can selectively adsorb mercury ions from mixed ion solution. The method is simple to operate, green, pollution-free, wide in application and practical.
Description
Technical Field
The invention belongs to the technical field of new materials, relates to preparation of a porous organic polymer based on thiophene units, and aims to selectively and efficiently adsorb and separate heavy metal mercury ions from sewage.
Background
Mercury is one of the most toxic and harmful heavy metals, and even at low concentration, the mercury seriously threatens human health, so that the central nervous system and endocrine system of the human body are destroyed, and the normal work of each organ of the human body is further influenced. The existence forms of mercury are various, have extremely toxic and difficult to biodegrade, and cause serious pollution to the ecological environment. In natural environments, mercury in its inorganic and organic forms is typically converted to a highly volatile elemental form, and the mercury enters the atmosphere, soil and water, eventually being stored in our food chain in the form of a highly effective neurotoxin methylmercury. Therefore, in consideration of accumulation of mercury in food chains and toxicity thereof to human bodies, it is important to develop an eco-friendly strategy for recovering mercury ions from mine wastewater or industrial and municipal wastewater.
At present, various methods such as a precipitation method, an ion exchange method, a membrane separation method, a coagulation method and the like have been widely applied to separation and enrichment of mercury ions. However, most of them require expensive costs, are complicated to operate, and are particularly inefficient for treating mercury ions at low concentrations. In contrast, adsorption can recover mercury ions from low concentration sources by a relatively simple process. The adsorption method is considered as a green alternative method for separating and adsorbing mercury ions due to the advantages of simple operation, economical process, no toxicity, reusability, high efficiency, relatively less secondary waste generation, various adsorbent types and the like.
Porous Organic Polymers (POPs) are porous materials that are interconnected by strong covalent bonds to form various topologies. POPs are considered as candidate materials for many potential applications, such as gas adsorption and separation, chemical and biological sensors, heterogeneous catalysis, drug delivery, and energy storage, due to their tunable pore structure, high specific surface area, low skeletal density, and excellent physicochemical stability. In recent years, the use of porous organic polymers in sewage treatment has been receiving increasing attention. Compared with the traditional adsorbent, the POPs have the advantages of high specific surface area, adjustable aperture, capability of introducing various functional groups into the framework through post-modification, and the like, so that the POPs are very suitable for being used as a novel solid adsorbent in the field of adsorption and separation of heavy metal ions in sewage. According to literature reports, sulfur-containing groups can form complexes with mercury ions and adsorb the mercury ions. In order to improve the application potential of POPs in heavy metal mercury ion adsorption separation, the invention designs a preparation method of a porous organic polymer based on thiophene units, which directly selects a sulfur-containing organic monomer with pi conjugation, and adopts a one-pot method for preparing a functional porous organic polymer through a Suzuki coupling reaction, so that the steps of complex post-modification and the like are avoided. The prepared material has prolonged pi conjugated skeleton and high-density sulfur active site, and can chelate mercury ions rapidly, and has good adsorption selectivity and high separation efficiency. The catalyst also shows higher adsorption capacity for mercury ions under strong acid, can be recycled, and has practical applicability for treating acidic industrial waste liquid.
Disclosure of Invention
The invention aims to overcome the defects in the prior art, and provides a preparation method of a porous organic polymer based on thiophene units, which is applied to the field of adsorption and separation of heavy metal mercury ions in sewage.
The invention is realized by the following technical scheme: a porous organic polymer based on thiophene units takes sulfur-containing thiophene monomers with pi conjugated structures and tri (4-boric acid farnesyl alcohol ester phenyl) amine (BBA) as structural units, and a one-pot method is used for effectively synthesizing a novel sulfur-containing porous organic polymer through Suzuki coupling reaction, wherein the structures are shown as the formulas (I) and (II):
a method for preparing a porous organic polymer based on thiophene units, comprising the steps of:
1) Putting sulfur-containing thiophene monomer with pi conjugated structure and tri (4-boric acid frequency farnesyl ester phenyl) amine into a prepared reaction container, and adding N, N' -dimethylformamide to dissolve the monomer; the experimental device is connected, the mixture is frozen by using liquid nitrogen, and is vacuumized by a vacuum pump, and nitrogen is introduced to normal pressure, and the mixture is repeatedly circulated for three times;
2) The catalyst is quickly added into the whole reaction system, the liquid nitrogen is continuously used for freezing, a vacuum pump is used for vacuumizing, nitrogen is introduced to normal pressure, and the circulation is repeated for three times; thawing and then reacting;
3) After the reaction, the obtained crude product was filtered and washed with an excessive amount of dichloromethane, deionized water, tetrahydrofuran, and then further purified, and finally, dried in vacuo at 90 ℃ for 12 hours to obtain the objective product.
Preferably, in the above method for preparing a porous organic polymer material based on thiophene units, in step 1), the sulfur-containing thiophene monomer is one of 5,5' -dibromo-2, 2' -bithiophene and 3,3', 5' -tetrabromo-2, 2' -bithiophene.
Preferably, in the above preparation method of the porous organic polymer based on thiophene units, in the step 2), the catalyst is tetra (triphenylphosphine) palladium and 2M potassium carbonate aqueous solution.
Preferably, in the above preparation method of a porous organic polymer based on thiophene units, in step 1), the sulfur-containing thiophene monomer comprises the following components in mass ratio: the tris (4-boronic acid farnesyl ester phenyl) amine is 1-2:1.
Preferably, the preparation method of the porous organic polymer based on thiophene units comprises the following steps of: tetrakis (triphenylphosphine) palladium was 1:0.05-0.06.
Preferably, in the above method for preparing a porous organic polymer based on thiophene units, in the step 2), the reaction temperature is 130 ℃, and the reaction time is 48 hours.
Preferably, the purification is carried out by Soxhlet extraction with tetrahydrofuran and dichloromethane for 48 hours.
The application of the porous organic polymer based on the thiophene unit in adsorbing mercury ions.
Preferably, the application of the porous organic polymer based on thiophene units in adsorbing mercury ions is as follows: a porous organic polymer based on thiophene units as described above is added to a solution containing mercury for adsorption.
The invention has the beneficial effects that:
1) The porous organic polymer containing thiophene units, which is prepared by the invention, has an extended pi conjugated framework and contains rich sulfur active sites, and can form a complex with mercury ions to quickly chelate the mercury ions.
2) The solid adsorbent prepared by the invention has high separation and enrichment efficiency, and can selectively adsorb mercury ions from mixed ion solution. The method disclosed by the invention is simple to operate, green, pollution-free and wide in application range, and has practical applicability.
3) The invention utilizes the advantages of good specific surface area, high thermochemical stability, coordination functionalization with the existing sulfur active site and the metal center of the porous organic polymer, and the like, and the prepared solid adsorbent can be used for recycling heavy metal mercury ions in sewage.
4) The porous organic polymer containing thiophene units, which is prepared by the invention, overcomes the low interaction between the ligand and the target metal caused by an irregular porous structure, and improves the adsorption performance of the adsorbent on mercury ions.
5) The porous organic polymer containing thiophene units prepared by the invention has higher adsorption capacity for mercury ions in solution under strong acid, and has high-density coordination sites, the adsorption process can pre-enrich the mercury ions, the balance time is further reduced, and the porous organic polymer containing thiophene units has practical applicability for treating acidic industrial waste liquid.
6) The porous organic polymer material containing thiophene units prepared by the invention can be recycled in the process of enriching mercury ions.
In conclusion, the solid adsorbent prepared by the invention can effectively adsorb and separate mercury ions, and is convenient to prepare, high in adsorption efficiency, green, pollution-free and practical in application.
Drawings
FIG. 1-1 is an infrared spectrum of a thiophene unit-containing porous organic polymer LNU-48 of the present invention and a reactive monomer;
FIGS. 1-2 are IR spectra of porous organic polymers LNU-49 containing thiophene units and reactive monomers of the present invention;
FIG. 2-1 is a scanning electron microscope image of a porous organic polymer LNU-48 containing thiophene units according to the present invention;
FIG. 2-2 is a scanning electron microscope image of a porous organic polymer LNU-49 containing thiophene units according to the present invention;
FIG. 3-1 is a transmission electron microscopy image of a porous organic polymer containing thiophene units LNU-48 of the present invention;
FIG. 3-2 is a transmission electron microscopy image of a porous organic polymer containing thiophene units LNU-49 of the present invention;
FIG. 4 is a thermogram of porous organic polymers containing thiophene units LNU-48 and LNU-49 of the present invention;
FIG. 5-1 is a nitrogen adsorption-desorption isotherm of a thiophene unit-containing porous organic polymer LNU-48 of the present invention;
FIG. 5-2 is a nitrogen adsorption-desorption isotherm of the thiophene unit-containing porous organic polymer LNU-49 of the present invention;
FIG. 6-1 is a pore size distribution plot of a thiophene unit-containing porous organic polymer LNU-48 of the present invention;
FIG. 6-2 is a pore size distribution plot of a thiophene unit-containing porous organic polymer LNU-49 of the present invention;
FIG. 7-1 is a graph showing the adsorption performance test of mercury ions at various pH values for the thiophene unit-containing porous organic polymers LNU-48 of the present invention;
FIG. 7-2 is a graph showing the adsorption performance test of mercury ions at various pH values for the thiophene unit-containing porous organic polymers LNU-49 of the present invention;
FIG. 8-1 is a equilibrium adsorption test of a porous organic polymer containing thiophene units LNU-48 of the present invention;
FIG. 8-2 is a equilibrium adsorption test of the thiophene unit-containing porous organic polymers LNU-49 of the present invention;
FIG. 9-1 is a cycle performance test of a porous organic polymer containing thiophene units LNU-48 of the present invention;
FIG. 9-2 is a cycle performance test of the thiophene unit-containing porous organic polymers LNU-49 of the present invention.
Detailed Description
EXAMPLE 1 preparation of porous organic Polymer containing thiophene units LNU-48
400mg (0.641 mmoL) of tris (4-borate-frequency-farnesyl-phenyl) amine and 312mg (0.962 mmoL) of 5,5' -dibromo-2, 2' -bithiophene were added to a round-bottomed flask containing 60mL of an N, N ' -dimethylformamide solution under a nitrogen atmosphere, and then the whole system was frozen with liquid nitrogen and deaerated by a vacuum pump and re-aerated three times repeatedly, 5mL of an aqueous potassium carbonate solution having a concentration of 2M and 40mg of tetrakis (triphenylphosphine) palladium were rapidly added to the reaction system, the freezing-deaeration-aeration process was repeated three times, and the reaction was allowed to stand for thawing, and the temperature was raised to 130℃with stirring for 48 hours. After the reaction has ended, the reactants are filtered off with suction, leaving behind solid insoluble materials, which are washed several times with excess amounts of dichloromethane, water and tetrahydrofuran solvent, respectively, for removing unreacted monomers or catalyst residues which may be present. The crude product was further purified by soxhlet extraction with dichloromethane and tetrahydrofuran, respectively. Finally, drying the mixture in a vacuum drying oven at 90 ℃ for 12 hours to obtain yellow powder which is the target porous organic polymer LNU-48 containing thiophene units.
The reaction equation for the porous organic polymers LNU-48 is as follows:
EXAMPLE 2 preparation of porous organic Polymer containing thiophene units LNU-49
400mg (0.641 mmoL) of tris (4-borate-frequency-farnesyl-phenyl) amine and 412mg (0.855 mmoL) of 3,3', 5' -tetrabromo-2, 2 '-bithiophene were added to a round-bottomed flask containing 60mL of an N, N' -dimethylformamide solution under a nitrogen atmosphere, and then the whole system was frozen with liquid nitrogen and deaerated and re-aerated by a vacuum pump repeatedly for three times, 5mL of an aqueous potassium carbonate solution having a concentration of 2M and 40mg of tetrakis (triphenylphosphine) palladium were rapidly added to the reaction system, the freezing-deaeration-aeration process was repeated three times, and the system was allowed to thaw, and the reaction was stirred at 130℃for 48 hours. After the reaction has ended, the reactants are filtered off with suction, leaving behind solid insoluble materials, which are washed several times with excess amounts of dichloromethane, water and tetrahydrofuran solvent, respectively, for removing unreacted monomers or catalyst residues which may be present. The crude product was further purified by soxhlet extraction with dichloromethane and tetrahydrofuran, respectively. Finally, drying the mixture in a vacuum drying oven at 90 ℃ for 12 hours to obtain green powder, namely the porous organic polymer LNU-49 containing thiophene units.
The reaction equation for the porous organic polymers LNU-49 is as follows:
example 3 characterization
1. And (3) infrared spectrum analysis: as shown in figures 1-1 to 1-2, the porous organic polymers LNU-48 and LNU-49 containing thiophene units and corresponding monomers prepared in the examples 1 and 2 of the present invention have infrared spectra, and in each figure, the curve a is the infrared spectrum of the polymer, and the curves b and c belong to the monomers. From the figure, the C-B characteristic absorption peak (1417 cm) -1 ) And a B-O characteristic absorption peak (1351 cm -1 ) C-Br characteristic absorption peak (500 cm) -1 ) The above results indicate that the polymerization reaction occurred and that the target porous organic polymer containing thiophene units was successfully obtained.
2. Scanning electron microscope analysis: as a result of observing the porous organic polymers LNU-48 and LNU-49 containing thiophene units prepared in example 1 and example 2 by using a scanning electron microscope, it can be seen that LNU-48 and LNU-49 are each formed by stacking irregular granular solids as shown in FIG. 2-1 and FIG. 2-2. The particle size of the polymers LNU-48 was found to be about 40nm and the particle size of the polymers LNU-49 was found to be about 25 nm.
3. Transmission electron microscopy analysis: the porous organic polymers LNU-48 and LNU-49 containing thiophene units prepared in example 1 and example 2 were observed by using a transmission electron microscope, and as a result, as shown in fig. 3-1 and 3-2, it can be seen that the pore channels of both materials exhibited disordered worm-like structures.
4. Thermogravimetric analysis: for the porous organic polymer LNU containing thiophene units prepared in example 1 and example 248 and LNU-49 in air atmosphere at 5deg.C for min -1 Thermogravimetric analysis was performed under the test conditions and the thermogravimetric curve is shown in fig. 4. From the figure we can see that these polymer backbones are very stable in air and do not start to decompose until 300 ℃ and end at around 500 ℃, indicating that the polymer has very good thermal stability. Meanwhile, the samples are found not to be dissolved or decomposed in common organic solvents (methanol, ethanol, methylene dichloride, chloroform, tetrahydrofuran, acetone, N' -dimethylformamide and the like), and the polymer is proved to have very good chemical stability.
5. Nitrogen adsorption analysis: the porous organic polymers LNU-48 and LNU-49 containing thiophene units prepared in example 1 and example 2 were subjected to a nitrogen adsorption-desorption isothermal curve test, and the results are shown in FIGS. 5-1 and 5-2, to obtain polymers LNU-48 and LNU-49 having BET specific surface areas of 21m, respectively 2 g -1 And 200m 2 g -1 。
6. Pore size distribution: as can be seen from FIGS. 6-1 and 6-2, the pore size distribution of the porous organic polymers LNU-48 and LNU-49 containing thiophene units prepared in example 1 and example 2 is mainly macropores, and the pore size distribution of LNU-49 is mainly micropores and mesopores, as calculated according to the non-local density functional theory method.
EXAMPLE 4 use of porous organic Polymer containing thiophene units for adsorption of Mercury ions
10mg of the thiophene unit-containing porous organic polymers LNU-48 and LNU-49 were each added to 10mL of 100ppm mercury solution at different pH values (pH=2 to 10) at room temperature, and the effect of the different pH values on the adsorbent was tested. As shown in fig. 7-1 and 7-2, the results indicate that the two adsorbents adsorb most effectively at ph=3. The result proves that the porous organic polymer containing thiophene units is very suitable for adsorption and separation treatment of heavy metal mercury ions in acidic sewage.
1. Equilibrium adsorption test: at a selected ph=3, the equilibrium isotherms of the two polymers for adsorption of mercury ions were tested at room temperature, and as can be seen from fig. 8-1 and 8-2, the adsorption conforms to the Langmuir model, with a maximum adsorption capacity of 295mg/g for LNU-48 and 374mg/g for LNU-49. Because LNUs have prolonged pi conjugated frameworks and sulfur active sites with high density, mercury ions can be quickly chelated, the adsorption selectivity is good, and the high adsorption capacity is shown for the mercury ions.
2. And (3) testing the cycle performance: the porous organic polymers LNU to 48 and LNU to 49 containing thiophene units prepared in example 1 and example 2 were subjected to cycle performance test as follows: the LNU-48 and LNU-49 after adsorbing mercury ions are respectively dispersed in 6M HCl aqueous solution and stirred, and demetallization reaction is carried out to remove the mercury ions adsorbed in the porous organic polymer skeleton. And then stirring, washing and drying the sample, and carrying out mercury ion adsorption on the regenerated porous organic polymer in the next round. As can be seen from FIGS. 9-1 and 9-2, the adsorption efficiencies of the adsorbents LNU-48 and LNU-49 after 5 cycles are 89.07% and 92.48%, respectively, can be recycled, and has a good application prospect for treating acidic industrial waste liquid.
Claims (8)
1. Use of a porous organic polymer based on thiophene units for the adsorption of mercury ions, characterized in that the method comprises the following steps: adding a porous organic polymer based on thiophene units into a solution containing mercury for adsorption; the porous organic polymer based on thiophene units is prepared by taking sulfur-containing thiophene monomers with pi conjugated structures and tris (4-boric acid frequency farnesyl ester phenyl) amine (BBA) as structural units, and effectively synthesizing the sulfur-containing porous organic polymer by a Suzuki coupling reaction one-pot method, wherein the structures are shown as the formulas (I) and (II):
, (Ⅰ) (Ⅱ)。
2. a method for preparing a porous organic polymer based on thiophene units, comprising the steps of:
1) Putting sulfur-containing thiophene monomer with pi conjugated structure and tri (4-boric acid frequency farnesyl ester phenyl) amine into a prepared reaction container, and adding N, N' -dimethylformamide to dissolve the monomer; the experimental device is connected, the mixture is frozen by using liquid nitrogen, and is vacuumized by a vacuum pump, and nitrogen is introduced to normal pressure, and the mixture is repeatedly circulated for three times;
2) The catalyst is quickly added into the whole reaction system, the liquid nitrogen is continuously used for freezing, a vacuum pump is used for vacuumizing, nitrogen is introduced to normal pressure, and the circulation is repeated for three times; thawing and then reacting;
3) After the reaction, the obtained crude product was filtered and washed with an excessive amount of dichloromethane, deionized water, tetrahydrofuran, and then further purified, and finally, dried in vacuo at 90 ℃ for 12 hours to obtain the objective product.
3. A method for preparing a porous organic polymer based on thiophene units according to claim 2, wherein: in the step 1), the sulfur-containing thiophene monomer is one of 5,5' -dibromo-2, 2' -bithiophene and 3,3', 5' -tetrabromo-2, 2' -bithiophene.
4. A method for preparing a porous organic polymer based on thiophene units according to claim 2, wherein: in the step 2), the catalyst is tetra (triphenylphosphine) palladium and 2M potassium carbonate aqueous solution.
5. A method for preparing a porous organic polymer based on thiophene units according to claim 2, wherein: in the step 1), according to the mass ratio, the sulfur-containing thiophene monomer: the tris (4-boronic acid farnesyl ester phenyl) amine is 1-2:1.
6. A method for preparing a porous organic polymer based on thiophene units according to claim 2, wherein: in terms of mass ratio, tris (4-borate frequency farnesyl ester phenyl) amine: tetrakis (triphenylphosphine) palladium was 1:0.05-0.06.
7. A method for preparing a porous organic polymer based on thiophene units according to claim 2, wherein: in step 2), the temperature of the reaction is 130 ℃ and the reaction time is 48 hours.
8. A method for preparing a porous organic polymer based on thiophene units according to claim 2, wherein: the purification is carried out by Soxhlet extraction for 48 hours by adopting tetrahydrofuran and dichloromethane.
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