CN107511134B - Mesoporous Zr-based coordination polymer and preparation and application thereof - Google Patents

Mesoporous Zr-based coordination polymer and preparation and application thereof Download PDF

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CN107511134B
CN107511134B CN201710515862.1A CN201710515862A CN107511134B CN 107511134 B CN107511134 B CN 107511134B CN 201710515862 A CN201710515862 A CN 201710515862A CN 107511134 B CN107511134 B CN 107511134B
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coordination polymer
mesoporous
based coordination
aqueous solution
terephthalic acid
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CN107511134A (en
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霍甲
金硼
李兴月
王双印
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Shanxi Li Pt long new materials Co.,Ltd.
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Shenzhen Research Institute Of Hunan University
Hunan University
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    • 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
    • B01J20/264—Synthetic macromolecular compounds derived from different types of monomers, e.g. linear or branched copolymers, block copolymers, graft copolymers
    • 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
    • C02F2101/30—Organic compounds
    • C02F2101/308—Dyes; Colorants; Fluorescent agents

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Abstract

A mesoporous Zr-based coordination polymer is a mesoporous material, the average pore diameter is-3.8 nm, and the specific surface area is 125-157 m2The preparation method comprises the following steps: separately preparing ZrCl4The aqueous solution of the mesoporous Zr-based coordination polymer and the aqueous solution of terephthalic acid and alkali (or organic amine) are mixed to obtain a sample system, the sample system reacts for 1-24 hours, and then is centrifuged, washed repeatedly for 2-3 times by triethylamine and acetone in sequence, and dried in vacuum at 60 ℃ for 12 hours to obtain the mesoporous Zr-based coordination polymer. The Zr-based coordination polymer has the characteristics of high specific surface area and mesopores, and the preparation method is simple, pollution-free, high in yield and suitable for large-scale production. The mesoporous Zr-based coordination polymer is used for dye (methylene blue and methyl orange) and heavy metal ions (Fe)3+、Co2+、Ni2+And Cu2+) Has higher adsorption capacity and can be repeatedly used, and the adsorption capacity reaches 93.4 percent of the initial adsorption capacity after being repeated five times.

Description

Mesoporous Zr-based coordination polymer and preparation and application thereof
(I) technical field
The invention relates to a mesoporous Zr-based coordination polymer, a preparation method thereof and application thereof as an adsorbent.
(II) background of the invention
The sewage treatment, especially the treatment of organic dyes and heavy metal examples in the sewage treatment, is a problem which needs to be solved urgently in the field of environmental protection. The adsorption method is widely used because of its simple operation, small sample amount and low cost. Commonly used adsorbents include activated carbon and porous coordination polymers, which have characteristics of high surface area, adjustable components and pore size, and the like, and have received much attention at home and abroad in recent years. The porous coordination polymer generally refers to a coordination polymer having a cavity of a single size and shape obtained from transition metal ions or metal clusters and organic ligands by means of molecular assembly and crystal engineering. Among them, Zr-based porous coordination polymers are attracting much attention because they exhibit high stability against acid and alkali. Therefore, the preparation of Zr-based porous coordination polymers and their application in the adsorption of dye molecules or heavy metal ions have been the focus and hot spot of research. However, most of the existing Zr-based porous coordination polymers are synthesized in organic solvents such as DMF, the preparation process is complex, the cost is high, further pollution to the environment is caused, and the obtained material is a microporous material, so that the adsorption amount of the adsorbent is difficult to increase.
Disclosure of the invention
The invention aims to provide a mesoporous Zr-based coordination polymer, a preparation method thereof and application thereof as an adsorbent.
The technical scheme adopted by the invention is as follows:
a mesoporous Zr-based coordination polymer is a mesoporous material, the average pore diameter is 3.8-6 nm, and the specific surface area is 125-157 m2The preparation method comprises the following steps: separately preparing ZrCl4The aqueous solution of the mesoporous Zr-based coordination polymer and the aqueous solution of terephthalic acid and alkali are mixed to obtain a sample system, the sample system is centrifuged after reacting for 1-24 h, and is repeatedly washed for 2-3 times by triethylamine and acetone in sequence, and is dried for 24h in vacuum at 60 ℃ to obtain the mesoporous Zr-based coordination polymer.
Micropores, defined by the international association of pure and applied chemistry (IUPAC), having a pore size of less than 2 nm; macropores with a pore diameter of more than 50 nm; the coordination polymer is called mesopore (or called mesopore) with the pore diameter of 2-50 nanometers, and the adsorption quantity is greatly improved compared with the micropore structure.
Said ZrCl4And the molar ratio of the terephthalic acid to the alkali is 1: 1-2: 2 to 3.
The invention also relates to a method for preparing the mesoporous Zr-based coordination polymer, which comprises the following steps:
(1) separately preparing ZrCl4Mixing the aqueous solution of (A) and the aqueous solution of terephthalic acid and alkali to obtain a sample system; ZrCl4The molar ratio of the terephthalic acid to the alkali (organic alkali or inorganic alkali) is 1: 1-2: 2-3;
(2) stirring the sample system at room temperature for reaction for 1-24 h, or reacting in a stainless steel reaction kettle containing a polytetrafluoroethylene lining at 100-120 ℃ for 1-12 h;
(3) and centrifuging after the reaction is finished, sequentially washing the precipitate with triethylamine and acetone for 2-3 times, and drying in vacuum at 50-60 ℃ for 24 hours to obtain the mesoporous Zr-based coordination polymer.
Preferably, ZrCl4And the molar ratio of the terephthalic acid to the alkali is 1: 1: 2.
specifically, the alkali is one of triethylamine, ammonia water or NaOH.
The invention also relates to the application of the coordination polymer as an adsorbent.
In particular, the adsorbent is used for adsorbing dye or heavy metal ions.
The dye is preferably a methylene blue or methyl orange dye. The mesoporous Zr-based coordination polymer has higher adsorption capacity to dye molecules in aqueous solutions with different pH values, and the detection steps are as follows:
(1) preparing an aqueous solution with the pH of 2-11 and the dye molecule concentration of 20-400 mg/L;
(2) adding the mesoporous Zr-based coordination polymer into the aqueous solution prepared in the step (1), and oscillating for 0.5-24 h at room temperature;
(3) centrifuging the system obtained in the step (2), absorbing supernatant, and measuring the adsorption capacity and the decolorization rate of the sample by adopting an ultraviolet-visible spectrophotometer;
(4) the adsorbent is repeatedly washed by NaOH solution and ethanol for three times and can be repeatedly used.
The heavy metal ion is preferably Fe3+、Co2+、Ni2+Or Cu2+One or more of (a). The mesoporous Zr-based coordination polymer has higher adsorption capacity to different heavy metal ions in an aqueous solution, and the detection steps are as follows:
(1) preparing an aqueous solution containing heavy metals with the concentration of 1.2-5 g/L; the corresponding anion is selected from SO4 2-、NO3 -Or Cl-One of (1);
(2) adding the mesoporous Zr-based coordination polymer into the aqueous solution prepared in the step (1), and oscillating for 0.5-24 h at room temperature;
(3) and (3) centrifugally separating the system obtained in the step (2), absorbing supernatant liquor, and measuring the adsorption capacity and the decolorization rate of the sample by adopting an ultraviolet-visible spectrophotometer.
After the adsorbent is adsorbed and saturated, NaOH solution and ethanol can be adopted for repeated washing, and the adsorbent can be repeatedly used.
The invention has the following beneficial effects:
(1) the Zr-based coordination polymer has the characteristics of mesoporous structure and large specific surface area;
(2) the preparation method of the Zr-based coordination polymer is simple, can directly react at room temperature, has higher yield and obviously reduced cost, and is suitable for large-scale production;
(3) the Zr-based coordination polymer can be applied to adsorbing dyes in acid or alkaline aqueous solution (the removal rate can reach 98 percent or more);
(4) the Zr-based coordination polymer can be applied to adsorbing heavy metal ions (the adsorption capacity can reach 180mg/g and above) in aqueous solution.
(IV) description of the drawings
FIG. 1 is a scanning electron microscope photograph of a Zr-based coordination polymer of the present invention.
FIG. 2 is an infrared spectrum (A) and a powder X-ray diffraction pattern (B) of the Zr-based coordination polymer of the present invention.
FIG. 3 is a thermogravimetric plot of the Zr-based coordination polymer of the present invention.
FIG. 4 shows N of a Zr-based coordination polymer of the present invention2Adsorption and desorption isotherms (A) and a pore size distribution diagram (B).
FIG. 5 is a graph showing the relationship between the adsorption amounts of the Zr-based coordination polymer according to the present invention to methylene blue solutions having different initial concentrations and the change with adsorption time.
FIG. 6 is a graph showing the relationship between the adsorption amounts of the Zr-based coordination polymer of the present invention to cobalt ion solutions having different initial concentrations and the adsorption time.
FIG. 7 shows the recycling efficiency of methylene blue adsorbed by the Zr-based coordination polymer of the present invention.
(V) detailed description of the preferred embodiments
The invention will be further described with reference to specific examples, but the scope of the invention is not limited thereto:
example 1:
0.114 g of terephthalic acid and 0.16 g of ZrCl were mixed4Dispersed in a polytetrafluoroethylene lining of 50ml containing 20 ml of ultrapure water and then put into a reaction kettle to react for 24 hours in an oven with the reaction temperature of 120 ℃. After the reaction is finished, naturally cooling to room temperature, respectively and repeatedly washing for 3 times by using saturated triethylamine aqueous solution and absolute ethyl alcohol, and carrying out vacuum drying for 24 hours in a vacuum oven at the temperature of 60 ℃ to obtain the Zr-based coordination polymer, wherein the average pore diameter is 3.8nm, and the specific surface area is 157m2/g。
Example 2:
0.114 g of terephthalic acid and 0.055 g of sodium hydroxide, and 0.16 g of ZrCl were added respectively4Respectively dissolving the two solutions in 10mL of ultrapure water, mixing the two solutions, fully and uniformly stirring, then putting the mixture into a 50mL polytetrafluoroethylene lining, putting the mixture into a reaction kettle, and reacting for 12 hours in an oven with the reaction temperature of 120 ℃. After the reaction is finished, naturally cooling to room temperature, respectively and repeatedly washing with saturated triethylamine aqueous solution and ethanol for multiple times, and carrying out vacuum drying in a vacuum oven at 60 ℃ for 24 hours to obtain the Zr-based coordination polymer, wherein the average pore diameter is 3.7nm, and the specific surface area is 135m2/g。
Example 3:
0.114 g of terephthalic acid and 0.055 g of sodium hydroxide, and 0.16 g of ZrCl were added respectively4Each was dissolved in 10mL of ultrapure water, and the two solutions were mixed and reacted at room temperature with stirring thoroughly for 24 hours. After the reaction is finished, naturally cooling to room temperature, respectively washing with saturated triethylamine aqueous solution and ethanol for multiple times, and vacuum-drying in a vacuum oven at 60 ℃ for 24 hours to obtain the Zr-based coordination polymer, wherein a scanning electron microscope picture of the Zr-based coordination polymer shows that the obtained product is an aggregate consisting of 500nm particles (see figure 1), an infrared spectrogram (figure 2A) shows that the obtained product is the coordination polymer formed by coordination of terephthalic acid and ZrCl4, a powder X-ray diffraction pattern (figure 2B) shows that the obtained product is amorphous, and a thermal weight loss curve chart (figure 3) shows that the proportion between the terephthalic acid and the Zr is about 1: 1; n is a radical of2The absorption and desorption isotherms and the pore size distribution are shown in FIG. 4, which shows an average pore size of 3.8nm and a specific surface area of 125m2/g。
Example 4:
0.114 g of terephthalic acid, 0.19 ml of triethylamine and 0.16 g of ZrCl were added4Respectively dissolving the two solutions in 10mL of ultrapure water, combining the two solutions, fully and uniformly stirring, then putting the two solutions into a 50mL polytetrafluoroethylene lining, putting the lining into a reaction kettle, and reacting for 24 hours in an oven with the reaction temperature of 120 ℃. After the reaction is finished, naturally cooling to room temperature, respectively and repeatedly washing with saturated triethylamine aqueous solution and ethanol for multiple times, and carrying out vacuum drying in a vacuum oven at 60 ℃ for 24 hours to obtain the Zr-based coordination polymer, wherein the average pore diameter is 3.7nm, and the specific surface area is 131m2/g。
Example 5:
0.114 g of terephthalic acid, 0.21 ml of concentrated ammonia water and 0.16 g of ZrCl are added4Respectively dissolving the two solutions in 10mL of ultrapure water, combining the two solutions, fully and uniformly stirring, then putting the two solutions into a 50mL polytetrafluoroethylene lining, putting the lining into a reaction kettle, and reacting for 24 hours in an oven with the reaction temperature of 120 ℃. After the reaction is finished, naturally cooling to room temperature, respectively and repeatedly washing with saturated triethylamine water solution and ethanol for multiple times, and carrying out vacuum drying in a vacuum oven at 60 ℃ for 24 hours to obtain the Zr-based coordination polymer, wherein the average pore diameter is 3.8nm, and the specific surface area is 127m2/g。
Example 6: adsorption of organic dyes
Taking an aqueous solution containing methylene blue as an example, adjusting the pH value, the adsorption time or the concentration of the methylene blue of the solution, and testing the capability of the porous adsorbent to adsorb the dye in the solution, wherein the specific steps are as follows:
i) 7 sets of 10ml of methylene blue solutions of 100mg/l were prepared, the pH of the solutions was adjusted to 1, 3, 5, 7, 9, 11 and 14, 50mg of the coordination polymer prepared in example 3 was added thereto, the mixture was shaken at room temperature and 250rpm for 24 hours, and after sampling and centrifugal separation for 10 minutes, the amount of methylene blue that was not adsorbed in the solution was measured using an ultraviolet-visible spectrophotometer. Experimental results show that the adsorbent has excellent adsorption capacity in acid-base solutions, and the optimal pH value is 7.
ii) 7 sets of 10ml of a methylene blue solution of 100mg/l were prepared, the pH of the solution was adjusted to 7, 50mg of the coordination polymer prepared in example 1 was added thereto, respectively, and shaken at room temperature and 250rpm for various times of 0.5h, 1h, 2h, 3h, 6h, 10h and 24h, respectively, and after sampling and centrifugal separation for 10min, the amount of methylene blue that was not adsorbed in the solution was measured using an ultraviolet-visible spectrophotometer. Experimental results show that the adsorption equilibrium time of the adsorbent is short, and saturated adsorption can be achieved within 2 hours.
iii) preparing 7 sets of 10ml methylene blue solutions with pH 7, changing initial concentration of methylene blue in the solutions to 20mg/L, 40mg/L, 60mg/L, 80mg/L, 100mg/L, 150mg/L, 200mg/L and 400mg/L, respectively, adding 50mg of the coordination polymer prepared in example 3 thereto, shaking at room temperature and 250rpm for 2h, sampling and centrifuging for 10min, and then measuring the amount of non-adsorbed methylene blue in the solution using a UV-visible spectrophotometer. The experimental result is shown in fig. 5, and it can be seen that the adsorption capacity of the adsorbent increases with the increase of the initial concentration of methylene blue in the solution, the maximum adsorption capacity can reach 38mg/g, and the decolorization rate can reach 98%.
Example 7: adsorption of heavy metal ions
50mg of coordination polymer prepared in example 1 is accurately weighed and placed into a 50ml centrifuge tube, 10ml of cobalt nitrate solution with a certain mass concentration (1.2, 1.6, 2.0, 3.0, 4.0 and 5.0 g/L) is added, a conical flask is sealed by a preservative film in the adsorption process, then the conical flask is placed into an oscillator, the conical flask is oscillated for a period of time (0.5, 1, 2, 3, 5, 10 and 24 hours) at room temperature, the conditions are kept consistent, and then the adsorption experiment is carried out. Centrifuging turbid liquid of the experimental sample after adsorption is finished by using a centrifugal machine, carefully absorbing supernatant by using a dropper, measuring the absorbance of the supernatant by using an ultraviolet-visible spectrophotometer, and finally calculating the adsorption amount of the sample, wherein the result is shown in figure 62+The maximum adsorption capacity can be up to 180 mg/g.
Example 8: recovery of adsorbent
The dried porous coordination polymer having an initial concentration of 400mg/L of methylene blue solution adsorbed in example 6 was put into a 50-ml centrifuge tube, and then repeatedly washed three times with 20 ml of 0.1mol/L NaOH solution and ethanol, respectively, and vacuum-dried in a vacuum oven at 60 ℃ for 24 hours. Adding a methylene blue aqueous solution with the initial concentration of 400mg/L into a centrifugal tube loaded with the porous coordination polymer, oscillating for 2h at the room temperature and the rotating speed of 250rpm, sampling, centrifuging for 10min, and then measuring the amount of non-adsorbed methylene blue in the solution by using an ultraviolet-visible spectrophotometer. The recovery rate (this/first adsorption) still reached 93.4% after five times of repeated use, and the experimental results are shown in fig. 7.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes performed by the present specification and drawings, or directly or indirectly applied to other related technical fields, are included in the scope of the present invention.

Claims (6)

1. A mesoporous Zr-based coordination polymer formed by coordination of Zr oxide clusters and terephthalic acid is a mesoporous material, the average pore diameter is 3.8-6 nm, and the specific surface area is 125-157 m2The preparation method comprises the following steps: separately preparing ZrCl4Mixing the aqueous solution of (A) and aqueous solution of terephthalic acid and alkali to obtain a sample system, reacting the sample system for 1-24 h, centrifuging, repeatedly washing with triethylamine and acetone for 2-3 times in sequence, and vacuum drying at 50-60 ℃ for 12-24 h to obtain the mesoporous Zr-based coordination polymer; said ZrCl4And the molar ratio of the terephthalic acid to the alkali is 1: 1: 2.
2. a method of preparing the mesoporous Zr-based coordination polymer of claim 1, said method comprising:
(1) separately preparing ZrCl4Mixing the aqueous solution of (A) and the aqueous solution of terephthalic acid and alkali to obtain a sample system;ZrCl4and the molar ratio of the terephthalic acid to the alkali is 1: 1: 2; the alkali is one of triethylamine, ammonia water or NaOH;
(2) stirring the sample system at room temperature for reaction for 1-24 h, or reacting in a stainless steel reaction kettle containing a polytetrafluoroethylene lining at 100-120 ℃ for 1-24 h;
(3) and centrifuging after the reaction is finished, sequentially washing the precipitate with triethylamine and acetone for 2-3 times, and drying in vacuum at 50-60 ℃ for 12-24 h to obtain the mesoporous Zr-based coordination polymer.
3. Use of the coordination polymer of claim 1 as an adsorbent.
4. Use according to claim 3, characterized in that the adsorbent is used for adsorbing dyes or heavy metal ions.
5. Use according to claim 4, characterized in that the dye is a methylene blue or methyl orange dye.
6. Use according to claim 4, characterized in that the heavy metal ion is Fe3+、Co2+、Ni2+Or Cu2+One or more of (a).
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