CN112679731B - Covalent organic framework material containing sulfonic acid group and preparation and application thereof - Google Patents
Covalent organic framework material containing sulfonic acid group and preparation and application thereof Download PDFInfo
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Abstract
The invention relates to a compound containing sulfonic acid groupThe covalent organic frame material is prepared by the Schiff base reaction of monomer 1,3, 5-trialdehyde phloroglucinol and sulfonic acid phenylenediamine monomer through a solvothermal method, and finally TJU-COFs-SO containing sulfonic acid groups is prepared 3 H covalent organic framework material for separation or recovery of impurities or contaminants in water. Compared with the prior art, the TJU-COFs-SO provided by the invention 3 The H introduces sulfonic acid groups, not only has the functions of ion exchange and the like, but also has a periodic pore structure and stable chemical characteristics, and compared with COFs without sulfonic acid groups, the performance of separating cations in water is better, particularly separating low-concentration ammonia nitrogen, the method has the characteristics of ultra-fast speed, high adsorption capacity, repeated use and the like, and in addition, the method also has similar effects on other cations in water, such as metal ions and the like.
Description
Technical Field
The invention belongs to the technical field of environmental protection and resource recycling, and particularly relates to a covalent organic framework material containing sulfonic acid groups, and preparation and application thereof.
Background
Nitrogen is an important agricultural production resource, which is synthesized mainly by the Haber-Bosch process, and it is estimated that 12.1kWh of energy is consumed per kilogram of ammonia nitrogen synthesis, which translates to about $ 1.5, and about 1 million tons of agricultural nitrogen fertilizers are used globally per year. About 2000 million tons of active nitrogen are generated in the world every year, and the active nitrogen is estimated to increase to 3500 million tons in 2050 and is discharged into water.
Compared with high-concentration ammonia nitrogen wastewater in industries such as industrial enterprises taking nitrogen as a raw material, landfill leachate and the like, the ammonia nitrogen concentration is high and has economic recovery value, while the ammonia nitrogen concentration in pollution sources such as industrial non-point sources and domestic sewage is low, approximately ranges from 5mg/L to 100mg/L, and is discharged to natural water and atmospheric environment through agricultural non-point sources; the domestic sewage discharge, even if the sewage is strictly treated, the discharge concentration is usually about 10mg/L, and the domestic sewage discharge is also a pollution source of ammonia nitrogen in water environment, and the global nitrogen circulation is seriously unbalanced and the surface water body nitrogen nutritive salt exceeds the standard due to the nitrogen environment discharge, so that water pollution and ecological problems of different degrees are caused. The traditional biological process for treating wastewater mainly converts chemical nitrogen in different forms into nitrogen, requires continuous energy supply and sufficient carbon source, and currently, the biological treatment cost per kilogram of ammonia nitrogen is estimated to be about $ 16.6. Losses caused by agricultural cost ammonia nitrogen emission pollution in the United states and the European Union are 2100 hundred million dollars and 3200 hundred million euros respectively. Thus, traditional bioprocesses are of low commercial value and are not conducive to the benign cycle of nitrogen.
The nitrogen in the water mainly exists in the forms of ammonium ions, nitrate nitrogen, nitrite nitrogen and the like, so that the ion exchange is a promising method for enriching and recovering the nitrogen source. And the traditional adsorbents (such as zeolite, resin and the like) have low ammonia nitrogen adsorption rate and low adsorption capacity, and especially low-concentration ammonia nitrogen has poorer effect. Therefore, a new adsorbent is needed to be designed to overcome the defects of the traditional adsorbent and deal with the application under some special scenes, so as to achieve the purposes of nitrogen removal and recovery of the low-concentration ammonia nitrogen water body.
Disclosure of Invention
The invention aims to overcome the defect that the adsorption rate of a traditional adsorption material to ammonia nitrogen is generally low, and provides a covalent organic framework material containing sulfonic acid groups, and preparation and application thereof in adsorption separation of low-concentration ammonia nitrogen or metal cations. Therefore, the material provided by the invention not only can realize the purpose of quickly separating low-concentration ammonia nitrogen, but also can enrich ammonia nitrogen resources so as to facilitate further recovery and treatment.
The purpose of the invention can be realized by the following technical scheme:
one of the objects of the present invention is to provide: a covalent organic framework material containing sulfonic acid groups is called TJU-COFs-SO 3 H。
The covalent organic framework material is shown as the following formula I or formula II:
formula I:
wherein R and R1 represent-HSO 3 Or H;
formula II:
wherein R and R1 represent-HSO 3 Or H.
The TJU-COFs-SO3H is in a nanowire shape structure, the length is 10-100 micrometers, and the width is 10-100 nm.
The TJU-COFs-SO3H has a microporous structure, and the pore diameter is 0.8-10 nm.
The second object of the present invention is to provide: the covalent organic framework material is prepared by taking 1,3, 5-trialdehyde phloroglucinol and sulfonic acid phenylenediamine monomers as reactants and taking mesitylene, 1, 4-dioxane and acetic acid as reaction solvents through Schiff base reaction. The method specifically comprises the following steps:
(1) adding 1,3, 5-trialdehyde phloroglucinol and a sulfonic acid phenylenediamine monomer into a reactor, then adding a reaction solvent, and carrying out ultrasonic treatment for 5-10 minutes to fully mix a reactant and the solvent;
(2) circularly degassing the mixture in the reactor by adopting liquid nitrogen until no bubbles are generated;
(3) carrying out vacuum sealing on the mixture subjected to circular degassing, placing the mixture in a vacuum condition of 80-120 ℃ for reaction for 3 days, and filtering to obtain a coarse sulfonic acid covalent organic framework;
(4) and cleaning the obtained sulfonic acid covalent organic framework crude body with an organic solvent, and activating for 12-24 hours at the temperature of 80-180 ℃ in vacuum to finally obtain the sulfonic acid group-containing covalent organic framework material.
The molar ratio of the 1,3, 5-trialdehyde phloroglucinol to the sulfonic acid phenylenediamine monomer is 1: 1.5-2;
the dosage of mesitylene and 1, 4-dioxane in the reaction solvent is as follows: 10-30 mL of reactants are added per gram, the concentration of acetic acid is 3-6 mol/L, and the dosage is as follows: adding 1-6 mL of reactants per gram;
the sulfoacid phenylenediamine monomer comprises any one of 2, 5-diaminobenzene sulfonic acid, 2, 5-diaminobenzene-1, 4-disulfonic acid, 4,4 '-diamino [1,1' -biphenyl ] -3-sulfonic acid and 4,4 '-diamino-3, 3' -biphenyl disulfonic acid.
And (2) the circulating degassing is to circularly freeze, pump and unfreeze the mixture.
The organic solvent for cleaning in the step (4) is two optional compounds of dimethylformamide, acetone and dichloromethane, and the use amount of the organic solvent is as follows: 5-20 mL of the product per gram is added.
The third object of the present invention is to provide: the application of a covalent organic framework material containing sulfonic acid groups is used for separating or recovering impurities or pollutants in water, and can quickly adsorb and separate ammonia nitrogen ions and cations in water, wherein the cations comprise metal ions. Especially has good enrichment capacity to low-concentration ammonia nitrogen (less than 10 mg/L).
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention synthesizes a novel ammonia nitrogen adsorption material, can realize the enrichment of low-concentration ammonia nitrogen in water by the characteristics of rapidness and high adsorption capacity, obtains high-concentration ammonia nitrogen resources, can realize the cyclic utilization of the adsorption material, and reduces the cost. The method breaks through the dilemma of ammonia nitrogen recovery, realizes the control of ammonia nitrogen pollution and the win-win pattern of reducing the production amount of ammonia nitrogen, and has important significance for controlling global nitrogen emission.
(2) The organic covalent framework material containing sulfonic acid group is prepared by introducing strong acid group-HSO on the covalent organic framework structure for the first time 3 The material is a material which is overlapped and stacked layer by layer, has a periodic pore structure and stable chemical property, has excellent ammonia nitrogen adsorption performance, and particularly shows short-time rapid adsorption and low-concentration ammonia nitrogen removal. The experimental result shows that the ammonia nitrogen adsorption capacity of the material can reach 70% of the equilibrium adsorption capacity within 10s, and the ammonia nitrogen removal of low concentration (less than 10mg/L)Except that more than 50 percent, the material has great application potential in the ammonia nitrogen control at the tail end of a pipe network.
(3) The covalent organic framework has the characteristics of special framework structure, easy design and the like, the sulfonic acid covalent organic framework material increases strong acid functional groups on the premise of not changing the original covalent organic framework, has a periodic pore structure and stable chemical characteristics, has ion exchange capacity and rapid separation capacity, has better performance than COFs (chemical organic frameworks) without sulfonic acid groups for separating cations, particularly has the characteristics of high speed, good effect and repeated use in the field of low-concentration ammonia nitrogen adsorption separation, and has similar effects on other cations in water, such as metal ions and the like.
Drawings
FIG. 1 is a schematic diagram of a synthetic route of a sulfonic acid group-containing adsorbing material TpBSA-1 prepared in example 1 of the present invention.
FIG. 2 is a three-dimensional structural drawing of a covalent organic framework containing sulfonic acid groups (TpBSA-1) prepared in example 1 of the present invention.
FIG. 3 is an X-ray powder diffraction pattern of the adsorbent TpBSA-1 prepared in example 1 of the present invention.
FIG. 4 is a scanning electron micrograph of the adsorbent TpBSA-1 prepared in example 1 of the present invention.
FIG. 5 is a thermogravimetric analysis chart of the adsorbent TpBSA-1 prepared in example 1 of the present invention.
FIG. 6 is a schematic diagram of the synthetic route of the adsorption material TpBSA-2 containing sulfonic acid group prepared in example 2 of the present invention.
FIG. 7 is a three-dimensional structural drawing of a covalent organic framework containing sulfonic acid groups (TpBSA-2) prepared in example 2 of the present invention.
FIG. 8 is an X-ray powder diffraction pattern of the adsorbent TpBSA-2 prepared in example 2 of the present invention.
FIG. 9 is a scanning electron micrograph of the adsorbent TpBSA-2 prepared in example 2 of the present invention.
FIG. 10 is a thermogravimetric analysis chart of the adsorbent TpBSA-2 prepared in example 2 of the present invention.
Fig. 11 is a schematic diagram of a synthetic route of the adsorption material tpbsda-1 containing sulfonic acid groups prepared in example 3 of the present invention.
FIG. 12 is a three-dimensional structural view of a covalent organic framework containing sulfonic acid groups (TpBDSA-1) prepared in example 3 of the present invention.
FIG. 13 is an X-ray powder diffraction pattern of the adsorbent TpBDSA-1 prepared in example 3 of the present invention.
FIG. 14 is a scanning electron microscope photograph of the adsorbent TpBDSA-1 prepared in example 3 of the present invention.
FIG. 15 is a thermogravimetric analysis chart of the adsorbent TpBDSA-1 prepared in example 3 of the present invention.
Fig. 16 is a schematic diagram of a synthetic route of the adsorption material tpbsda-2 containing sulfonic acid groups prepared in example 4 of the present invention.
FIG. 17 is a three-dimensional structural drawing of a covalent organic framework containing sulfonic acid groups (TpBDSA-2) prepared in example 4 of the present invention.
FIG. 18 is an X-ray powder diffraction pattern of the adsorbent TpBDSA-2 prepared in example 4 of the present invention.
FIG. 19 is a scanning electron microscope photograph of the adsorbent TpBDSA-2 prepared in example 4 of the present invention.
FIG. 20 is a thermogravimetric analysis chart of the adsorbent TpBDSA-2 prepared in example 4 of the present invention.
FIG. 21 is a diagram of ammonia nitrogen adsorption equilibrium experiment for each of the materials prepared in examples 1-4.
FIG. 22 is a pseudo second order kinetic fit plot of the material TpBSA-1 prepared in example 1.
FIG. 23 is a pseudo second order kinetic fit plot of the material TpBSA-2 prepared in example 2.
FIG. 24A pseudo-second order kinetic fit plot of the material TpBDSA-1 prepared in example 3.
FIG. 25 pseudo second order kinetic fit plot of material TpBDSA-2 prepared in example 4.
FIG. 26 is an adsorption isotherm plot of the material prepared in example 1.
FIG. 27 is a plot of the adsorption isotherm Langmuir model fitted to the material prepared in example 1.
FIG. 28 is a graph of the adsorption capacity of the regenerated adsorption experiment for the material prepared in example 1.
FIG. 29 is a graph showing the effect of removing metal ions from the material prepared in example 1.
Detailed Description
The technical solution of the present invention is further described in detail below with reference to specific examples. Finally, it should be noted that the following examples are only for illustrating the technical solutions of the present invention and not for limiting, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention and shall be covered by the claims of the present invention.
Example 1: preparation of covalent organic framework Polymer containing sulfonic acid groups (TpBSA-1)
Weighing 63mg (0.3mmol) of 1,3, 5-trialdehyde phloroglucinol (Tp) and 84.69mg (0.45mmol) of 2, 5-diaminobenzene sulfonic acid (BSA-1) and respectively adding the weighed materials into a customized test tube, then sequentially adding 1.5mL of mesitylene, 1.5mL of 1, 4-dioxane and 0.5mL of 3mol/L acetic acid solution and carrying out ultrasonic treatment for 10min to fully mix reactants and a solvent; connecting the test tube with a vacuumizing device, freezing in liquid nitrogen, and repeating the steps of vacuumizing, degassing and unfreezing for 3 times to ensure that no bubbles are generated in the solvent; carrying out vacuum sealing on the test tube by using an alcohol blast lamp, and finally placing the test tube in a 120 ℃ oven for reaction for 3 days; after the reaction is finished, carrying out centrifugal filtration to obtain a dark red precipitate, washing the precipitate for 5-6 times by using acetone and DMF (dimethyl formamide), and washing the precipitate for several times by using THF (tetrahydrofuran) as a solvent; finally, the red precipitate is dried in a vacuum drying oven at 180 ℃ for 24 hours, and finally the crystal powder of the organic covalent framework polymer (TpBSA-1) containing the sulfonic acid group is obtained, and the yield is 90.1 percent. The specific synthetic route is shown in figure 1, the structural schematic diagram of TpBSA-1 is shown in figure 2, the X-ray diffraction pattern is shown in figure 3, and the TpBSA-1 prepared in the embodiment is a material with crystallinity as can be seen from figure 3. FIG. 4 is a scanning electron micrograph of TpBSA-1, which shows that the material is composed of irregular nanowire-like structures and contains a large number of micropores. Thermogravimetric analysis (TGA) (FIG. 5) shows that TpBSA-1 can maintain more than 80% of its mass before 200 ℃ and 60% of its mass even at 400 ℃ and has good thermal stability.
Example 2: preparation of covalent organic framework Polymer containing sulfonic acid groups (TpBSA-2)
Weighing 63mg (0.3mmol) of 1,3, 5-trialdehyde phloroglucinol (Tp) and 120.72mg (0.45mmol) of 2, 5-diaminobenzene-1, 4-disulfonic acid (BSA-2) into a custom-made test tube respectively, then sequentially adding 1.5mL of mesitylene, 1.5mL of 1, 4-dioxane and 0.5mL of 3mol/L acetic acid solution, and carrying out ultrasonic treatment for 10min to fully mix reactants and a solvent; connecting the test tube with a vacuumizing device, freezing in liquid nitrogen, and repeating the steps of vacuumizing, degassing and unfreezing for 3 times to ensure that no bubbles are generated in the solvent; carrying out vacuum sealing on the test tube by using an alcohol blast lamp, and finally placing the test tube in a 120 ℃ oven for reaction for 3 days; after the reaction is finished, carrying out centrifugal filtration to obtain a dark red precipitate, washing the precipitate for 5-6 times by using acetone and DMF (dimethyl formamide), and washing the precipitate for several times by using THF (tetrahydrofuran) as a solvent; finally, the red precipitate is dried in a vacuum drying oven at 180 ℃ for 24 hours, and finally the crystal powder of the organic covalent framework polymer (TpBSA-2) containing the sulfonic acid group is obtained, and the yield is 81.7 percent. The specific synthetic route is shown in figure 6, the structural schematic diagram of TpBSA-2 is shown in figure 7, the X-ray diffraction pattern is shown in figure 8, and the TpBSA-2 prepared in the embodiment is a material with crystallinity. The scanning electron microscope image is shown in FIG. 9, from which it can be seen that the material has a petal-shaped sheet structure. The thermogravimetric analysis (TGA) is shown in FIG. 10, from which it can be seen that TpBSA-2 can maintain more than 80% of the mass at about 200 deg.C, and the mass is maintained at about 50% after the temperature reaches 450 deg.C, with good thermal stability.
Example 3: preparation of covalent organic framework Polymer containing sulfonic acid group (TpBDSA-1)
Weighing 63mg (0.3mmol) of 1,3, 5-trialdehyde phloroglucinol (Tp) and 118.53mg (0.45mmol) of 4,4 '-diamino [1,1' -biphenyl ] -3-sulfonic acid (BDSA-1) into a customized test tube respectively, then sequentially adding 1.5mL of mesitylene, 1.5mL of 1, 4-dioxane and 0.5mL of 3mol/L acetic acid solution, and carrying out ultrasonic treatment for 10min to ensure that reactants and a solvent are fully mixed; connecting the test tube with a vacuumizing device, freezing in liquid nitrogen, and repeating the steps of vacuumizing, degassing and unfreezing for 3 times to ensure that no bubbles are generated in the solvent; carrying out vacuum sealing on the test tube by using an alcohol blast lamp, and finally placing the test tube in a 120 ℃ oven for reaction for 3 days; after the reaction is finished, carrying out centrifugal filtration to obtain a dark red precipitate, washing the precipitate for 5-6 times by using acetone and DMF (dimethyl formamide), and washing the precipitate for several times by using THF (tetrahydrofuran) as a solvent; finally, the red precipitate is dried in a vacuum drying oven at 180 ℃ for 24 hours, and finally organic covalent framework polymer (TpBDSA-1) crystal powder containing sulfonic acid groups is obtained, and the yield is 86.1%. The specific synthetic route is shown in figure 11, the structural schematic diagram of TpBDSA-1 is shown in figure 12, the X-ray diffraction pattern is shown in figure 13, and the TpBDSA-1 prepared in the embodiment is a material with crystallinity. The scanning electron microscope is shown in FIG. 14, and it can be seen that the material has a nano-linear structure and contains a large number of micropores. The thermogravimetric analysis is shown in figure 15, and it can be seen that the material can keep more than 80% of mass before 200 ℃ and still keep about 50% of mass after the temperature is raised to 450 ℃, and has certain thermal stability.
Example 4: preparation of covalent organic framework Polymer containing sulfonic acid group (TpBDSA-2)
Weighing 63mg (0.3mmol) of 1,3, 5-trialdehyde phloroglucinol (Tp) and 118mg (0.45mmol) of 4,4 '-diamino-3, 3' -biphenyldisulfonic acid (BDSA-2) into a custom-made test tube respectively, and then sequentially adding 1.5mL of mesitylene, 1.5mL of 1, 4-dioxane and 0.5mL of 3mol/L acetic acid solution and carrying out ultrasonic treatment for 10min to fully mix reactants and a solvent; connecting the test tube with a vacuumizing device, freezing in liquid nitrogen, and repeating the steps of vacuumizing, degassing and unfreezing for 3 times to ensure that no bubbles are generated in the solvent; carrying out vacuum sealing on the test tube by using an alcohol blast lamp, and finally placing the test tube in a 120 ℃ oven for reaction for 3 days; after the reaction is finished, carrying out centrifugal filtration to obtain a dark red precipitate, cleaning the precipitate for 5-6 times by using acetone and DMF (dimethyl formamide), and cleaning the precipitate for several times by using THF as a solvent; and finally, drying the red precipitate in a vacuum drying oven at 180 ℃ for 24 hours to finally obtain organic covalent framework polymer (TpBSA-2) crystal powder containing sulfonic acid groups, wherein the yield is 74.6%. The specific synthetic route is shown in figure 16, the structural schematic diagram of TpBSA-2 is shown in figure 17, the X-ray diffraction pattern is shown in figure 18, and the TpBDSA-2 prepared in the embodiment is a material with crystallinity. Scanning electron microscopy as shown in fig. 19, it can be seen that the material has a mica-like structure as well as some nanoparticulate structure. The thermogravimetric analysis curve is shown in fig. 20, and it can be seen that the material maintains good thermal stability before 300 ℃, and the material can maintain about 60% of mass after the temperature reaches 400 ℃, and the thermal stability is good.
The adsorption capacity of the covalent organic framework material containing sulfonic acid groups prepared in the above examples 1-4 for adsorbing ammonia nitrogen was tested:
adsorption kinetics is an important indicator of the adsorption performance of an adsorbent. The conditions of the adsorption kinetics experiment are as follows: the initial concentration of ammonia nitrogen is 10mg/L, the temperature is 25 ℃ (room temperature), the pH is 5-6, and the adding ratio of the adsorbent is 0.5 g/L. The ammonia nitrogen adsorption equilibrium process of the covalent organic framework material with the sulfonic acid group under the condition is shown in figure 21, and the kinetic fitting result is shown in figures 22-25.
As can be seen from figure 21, the sulfonic acid covalent organic framework adsorption material prepared by the invention has a high ammonia nitrogen adsorption rate, and the ammonia nitrogen adsorption amount can reach about 70% of the equilibrium adsorption amount within 10 s. From fig. 22 to 25, it can be seen that the process of adsorbing ammonia nitrogen by the sulfonic acid covalent organic framework satisfies second order kinetics, and the results of ammonia nitrogen adsorption kinetic constants and equilibrium adsorption amounts of 4 sulfonic acid covalent organic frameworks shown in the examples of the present invention are shown in the table.
TABLE 1 summary of kinetic results
| K obs (g·mg -1 ·min -1 ) | q e (mg/g) | |
| TpBSA-1 | 0.2 | 9.06 |
| TpBSA-2 | 0.87 | 4.98 |
| TpBDSA-1 | 0.3 | 6.04 |
| TpBDSA-2 | 0.05 | 2.26 |
The TpBSA-1 material, in which the adsorption performed the best, was also subjected to an adsorption isotherm and an experiment for calculating the maximum adsorption amount. The specific results are shown in FIG. 26.
It can be seen that in the adsorption isothermal experiment, the equilibrium ammonia nitrogen adsorption capacity of the TpBSA-1 is increased along with the increase of the ammonia nitrogen concentration, and when the initial ammonia nitrogen concentration is 80mg/L, the ammonia nitrogen equilibrium adsorption capacity of the TpBSA-1 gradually increases and approaches to the maximum value. To estimate the maximum theoretical adsorption amount, a Langmuir model was fitted to the adsorption isotherm, and the fitting result is shown in fig. 27.
The adsorption isotherm of TpBSA-1 has better fitting degree with the Langmuir model, and the fitting result shows that the maximum ammonia nitrogen adsorption quantity q of TpBSA-1 max 23.58mg/g can be achieved with a Langmuir adsorption equilibrium constant K of 254.3L/g.
According to the specific explanation, it is obvious that the sulfonic acid covalent organic framework provided by the invention has good adsorption performance on ammonia nitrogen, which is represented by extremely fast adsorption rate and considerable equilibrium adsorption quantity.
Regenerating the adsorbed TJU-COFs-SO3H material by using NaCl solution. The method comprises the following specific steps: TJU-COFs-SO3H powder (taking TpBSA-1 powder obtained in example 1 as an example) after adsorption balance is collected and filtered, the powder is dispersed in 0.1-1 mol/L NaCl solution, the solution is shaken for 1-2 hours under the condition of 200-300 rpm by using a constant temperature shaking table, TJU-COFs-SO3H after full desorption is separated by filtration, and finally vacuum drying is carried out for 12-24 hours under the condition of 80-120 ℃, and finally, the regenerated TJU-COFs-SO3H can be used for a new round of adsorption. The results of the laboratory test for 5 cycles are shown in FIG. 28, from which it can be seen that TJU-COFs-SO3H exhibited good recycling performance.
The TJU-COFs-SO3H material obtained in the above examples 1-4 also has a good effect of removing some metal ions in water. The adsorption experiments of metal ions were tested according to the following conditions: (taking TpBSA-1 prepared in example 1 as an example) TJU-COFs-SO3H is added in an amount of 0.5g/L, the stirring speed is 200-300 rpm, the stirring time is 1-2 hours, the temperature is room temperature (20-25 ℃), the pH is 5-6, and Ca is added 2+ 、Na + 、Pb 2+ The initial concentration of the ions is about 30-35 mg/L, 15-20 mg/L, 25-30 mg/L. The experimental result is shown in FIG. 29, from which it can be seen that the removal rates of TJU-COFs-SO3H for the three metal ions are 98.9% (Ca) respectively 2+ )、86.4％(Na + )、Pb 2+ (99.75%). Therefore, the TJU-COFs-SO3H material prepared by the invention has wide application scenes, has excellent adsorption effect on ammonia nitrogen, heavy metal and related metal ions, and is a novel adsorption material with great application prospect.
Example 5
A preparation method of a covalent organic framework material containing sulfonic acid groups comprises the following steps:
(1) 1,3, 5-trialdehyde phloroglucinol and 2, 5-diaminobenzene sulfonic acid are mixed according to a molar ratio of 1: 1.5 into the reactor, then adding the reaction solvent: mesitylene, 1, 4-dioxane and acetic acid, wherein the dosage of the mesitylene and the 1, 4-dioxane is as follows: 10mL of reactants is added per gram, the concentration of the acetic acid is 3mol/L, and the dosage is as follows: adding 1mL of reactant per gram; fully mixing the reactants and the solvent by ultrasonic treatment for 5 minutes;
(2) freezing, exhausting and unfreezing the mixture in the reactor by adopting liquid nitrogen for circular degassing until no bubbles are generated;
(3) carrying out vacuum sealing on the mixture subjected to circular degassing, placing the mixture in a vacuum condition at 80 ℃ for reaction for 3 days, and filtering to obtain a sulfonic acid covalent organic framework coarse body;
(4) cleaning the obtained sulfonic acid covalent organic framework crude body with an organic solvent, wherein the organic solvent is any two of dimethylformamide, acetone and dichloromethane which are matched with tetrahydrofuran, and the using amount of the organic solvent is as follows: adding 5mL of product per gram, and activating for 12 hours at the vacuum temperature of 80 ℃ to finally obtain the covalent organic framework material containing the sulfonic acid group.
The adsorbent is used for adsorbing wastewater containing low-concentration ammonia nitrogen, wherein the initial concentration of the ammonia nitrogen is 10mg/L, the temperature is 25 ℃ (room temperature), the pH value is 5-6, and the adding ratio of the adsorbent is 0.5 g/L. The adsorption capacity of the material to low-concentration ammonia nitrogen within 10s is 62 percent of the equilibrium adsorption capacity, and the theoretical maximum adsorption capacity q max ＝23.58mg/L。
Example 6
A preparation method of a covalent organic framework material containing sulfonic acid groups comprises the following steps:
(1) 1,3, 5-trialdehyde phloroglucinol and 4,4 '-diamino [1,1' -biphenyl ] -3-sulfonic acid are mixed according to a molar ratio of 1: 2 into the reactor, then adding the reaction solvent: mesitylene, 1, 4-dioxane and acetic acid, wherein the dosage of the mesitylene and the 1, 4-dioxane is as follows: adding 30mL of reactants per gram, wherein the concentration of the acetic acid is 6mol/L, and the dosage is as follows: adding 6mL of reactants per gram; fully mixing the reactants and the solvent by ultrasonic treatment for 10 minutes;
(2) freezing, exhausting and unfreezing the mixture in the reactor by adopting liquid nitrogen for circular degassing until no bubbles are generated;
(3) carrying out vacuum sealing on the mixture subjected to circular degassing, placing the mixture in a vacuum environment at 120 ℃ for reaction for 3 days, and filtering to obtain a sulfonic acid covalent organic framework coarse body;
(4) cleaning the obtained sulfonic acid covalent organic framework crude body with an organic solvent, wherein the organic solvent is any two of dimethylformamide, acetone and dichloromethane which are matched with tetrahydrofuran, and the using amount of the organic solvent is as follows: adding 20mL of product per gram, and activating for 24 hours at the temperature of 180 ℃ in vacuum to finally obtain the covalent organic framework material containing the sulfonic acid group.
The adsorbent is used for adsorbing wastewater containing low-concentration ammonia nitrogen, wherein the initial concentration of the ammonia nitrogen is 10mg/L, the temperature is 25 ℃ (room temperature), the pH value is 5-6, and the adding ratio of the adsorbent is 0.5 g/L. The adsorption capacity of the material to low-concentration ammonia nitrogen within 10s is 72 percent of the equilibrium adsorption capacity, and the theoretical maximum adsorption capacity q max ＝17.99mg/g。
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (6)
1. The application of a covalent organic framework material containing sulfonic acid groups to rapid adsorption of ammonia nitrogen ions in water is characterized in that the covalent organic framework material is TJU-COFs-SO 3 H；
The covalent organic framework material is prepared by taking 1,3, 5-trialdehyde phloroglucinol and sulfonic acid phenylenediamine monomer as reactants and mesitylene, 1, 4-dioxane and acetic acid as reaction solvents through Schiff base reaction, and the preparation method specifically comprises the following steps:
(1) adding 1,3, 5-trialdehyde phloroglucinol and a sulfonic acid phenylenediamine monomer into a reactor, then adding a reaction solvent, and carrying out ultrasonic treatment for 5-10 minutes to fully mix a reactant and the solvent;
(2) circularly degassing the mixture in the reactor by adopting liquid nitrogen until no bubbles are generated;
(3) carrying out vacuum sealing on the mixture subjected to circular degassing, placing the mixture in a vacuum condition of 80-120 ℃ for reaction for 3 days, and filtering to obtain a coarse sulfonic acid covalent organic framework;
(4) cleaning the obtained sulfonic acid covalent organic framework crude body with an organic solvent, and activating for 12-24 hours at the temperature of 80-180 ℃ in vacuum to finally obtain the sulfonic acid group-containing covalent organic framework material;
the molar ratio of the 1,3, 5-trialdehyde phloroglucinol to the sulfonic acid phenylenediamine monomer is 1: 1.5-2;
the dosage of mesitylene and 1, 4-dioxane in the reaction solvent is as follows: 10-30 mL of reactant per gram, wherein the concentration of the acetic acid is 3-6 mol/L, and the dosage is as follows: the usage amount of the reactant per gram is 1-6 mL;
the sulfoacid phenylenediamine monomer comprises any one of 2, 5-diaminobenzene sulfonic acid, 2, 5-diaminobenzene-1, 4-disulfonic acid, 4,4 '-diamino [1,1' -biphenyl ] -3-sulfonic acid and 4,4 '-diamino-3, 3' -biphenyl disulfonic acid.
2. The use of claim 1, wherein the covalent organic framework material is of formula I or formula II:
formula I:
wherein R and R1 represent HSO 3 Or H;
formula II:
wherein R and R1 represent HSO 3 Or H.
3. The use according to claim 1, wherein the TJU-COFs-SO3H is a nanowire-shaped structure having a length of 10 to 100 μm and a width of 10 to 100 nm.
4. The use according to claim 1, wherein the TJU-COFs-SO3H has a microporous structure with a pore size of 0.8 to 10 nm.
5. The use according to claim 1, wherein the step (2) of cyclic degassing is performed by cyclically freezing, evacuating and thawing the mixture.
6. The use according to claim 1, wherein the organic solvent for cleaning in step (4) is selected from two of dimethylformamide, acetone and dichloromethane, and the organic solvent is selected from tetrahydrofuran, and the amount of the organic solvent is as follows: 5-20 mL of the product per gram is added.
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