CN114307878A - Zirconium-containing organic framework material composite aerogel and preparation method and application thereof - Google Patents
Zirconium-containing organic framework material composite aerogel and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a zirconium-containing organic framework material composite aerogel and a preparation method and application thereof, wherein the zirconium-containing organic framework material composite aerogel comprises a zirconium-containing organic framework material and agarose aerogel, and the zirconium-containing organic framework material is attached to a pore structure of the agarose aerogel; the preparation method comprises the steps of preparing a zirconium-containing organic framework material by a solvothermal method, and mixing the zirconium-containing organic framework material with agarose by a direct mixing method to obtain the zirconium-containing organic framework material composite aerogel; the zirconium-containing organic framework material composite aerogel is excellent in mechanical property, good in stability and rich in pore structure, and can effectively adsorb and remove oxyanions in wastewater; the separation is easy, the recovery and the reuse can be realized, and the recovery rate of the adsorption performance after regeneration is high; and the preparation method is simple and safe to operate, low in cost and wide in applicability.
Description
Technical Field
The invention belongs to the technical field of water treatment, and particularly relates to a zirconium-containing organic framework material composite aerogel as well as a preparation method and application thereof.
Background
With the rapid development of industry, oxoanions as pollutants are widely present in wastewater, contaminated drinking water sources and ground water, and pose a threat to the environment and human health to some extent. Compared with organic pollutants, oxoanions have the problems of high fluidity, difficult degradation and the like, and can generate carcinogenic effect after long-term accumulation in organisms. The oxygen-containing anion pollution in water environment has received global attention, and the method for removing toxic oxygen-containing anions in sewage mainly comprises electrochemical treatment, biological treatment, membrane filtration and the like, wherein the adsorption method is widely applied to the removal process of oxygen-containing anions due to the advantages of high efficiency, easiness in implementation, relatively low cost and the like.
The metal organic framework material is a novel material synthesized by metal nodes and organic connectors, wherein the metal organic framework material synthesized by zirconium metal nodes has rich pore structures and good chemical and thermal stability, can be used as an adsorbent to be applied to a water treatment process, but has limited application performance due to the problems of powder crystallization state, complex recovery process and the like in the application process. The aerogel is a light porous material with low density, high porosity and high specific surface area, and the composite nano material aerogel prepared by the aerogel and the metal organic framework material can enhance the mechanical property of the metal organic framework material, increase the specific surface area and is easy to recover.
CN110483831A discloses a MOF aerogel and a preparation method thereof. The main steps of the method comprise 1) taking inorganic Co salt as a raw material; 2) polyacrylic acid (PAA) is used as an additive;
3) preparing precursor gel containing Co by using propylene oxide as a gel accelerator; 4) aging the precursor gel in a methanol solution containing 2-methylimidazole, and converting the precursor gel into MOF gel; 5) and (3) obtaining the MOF aerogel by adopting supercritical drying. The prepared aerogel is characterized by 1) the crystal structure is ZIF-67 structure; 2) the specific surface area is 500-1000 m2Between/g; 3) the microstructure of the aerogel is MOF particles with the size of 10-200 nm. However, the method adopts a two-step method to prepare the MOF aerogel, the operation is complicated, and meanwhile, the treatment effect of the MOF aerogel on oxyanion-containing wastewater or organic arsenic wastewater is not verified.
Therefore, it is necessary to provide a porous adsorbent with large specific surface area, strong stability, simple preparation operation and easy recovery for efficiently removing oxyanion wastewater and organic arsenic wastewater.
Disclosure of Invention
The invention aims to provide a zirconium-containing organic framework material composite aerogel, a preparation method and application thereof, wherein the zirconium-containing organic framework material composite aerogel comprises a zirconium-containing organic framework material and an agarose aerogel, and the zirconium-containing organic framework material is attached to a pore structure of the agarose aerogel; the zirconium-containing organic framework material composite aerogel is excellent in mechanical property, good in stability and rich in pore structure, and can effectively adsorb and remove oxyanions in wastewater; the separation is easy, the recovery and the reuse can be realized, and the recovery rate of the adsorption performance after regeneration is high; and the preparation method is simple and safe to operate, low in cost and wide in applicability.
In order to achieve the purpose, the invention adopts the following technical scheme:
one of the objectives of the present invention is to provide a zirconium-containing organic framework material composite aerogel, which comprises a zirconium-containing organic framework material and an agarose aerogel, wherein the zirconium-containing organic framework material is attached in a pore structure of the agarose aerogel.
According to the invention, the zirconium-containing organic framework material has a larger specific surface area and good water stability, zirconium has stronger affinity to various oxyanions, and can efficiently remove the oxyanions in water, the zirconium-containing organic framework material/agarose aerogel is based on agarose, is light in weight, has a porous structure, is low in density, and is excellent in mechanical property and stability, and after being added into water, the solid-liquid separation process can be simplified, so that the purpose of removing the oxyanions in water is achieved.
The invention also aims to provide a preparation method of the zirconium-containing organic framework material composite aerogel, which comprises the following steps:
(1) dissolving a zirconium-containing compound and a first regulator in a first solvent, and heating for the first time to obtain a mixed solution;
(2) adding an organic ligand into the mixed solution obtained in the step (1), and heating for the second time to obtain a zirconium-containing organic framework material;
(3) and (3) dissolving agarose and the zirconium-containing organic framework material obtained in the step (2) in a second solvent, and sequentially heating, cooling and drying for the third time to obtain the zirconium-containing organic framework material composite aerogel.
The method is simple and safe to operate, low in cost and wide in applicability, and can be used for removing the oxyanions in drinking water, industrial wastewater and natural water.
In a preferred embodiment of the present invention, the molar ratio of the zirconium-containing compound in step (1) to the first modifier is 1 (50 to 80), and may be, for example, 1:50, 1:52, 1:55, 1:58, 1:60, 1:63, 1:65, 1:67, 1:70, 1:72, 1:74, 1:76, 1:78, 1:80, or the like, but is not limited to the above-mentioned values, and other values not listed in the above-mentioned numerical range are also applicable.
The preferred molar ratio of the zirconium-containing compound to the first regulator in the step (1) is 1 (50-80), and if the ratio is more than 1:50, namely the content of the first regulator is too low, the growth of MOF crystals cannot be promoted, and the formation of disordered or amorphous precipitated materials cannot be prevented, because in the solution added with the regulator, zirconium is mainly combined with the regulator, and then the regulator molecules are replaced by organic ligands to synthesize MOF; below 1:80, i.e., too much first modifier content, would result in too many metal cluster nodes being capped with first modifier, the organic ligand would not be able to replace the excess first modifier, interrupting the formation of MOF crystals.
Preferably, the zirconium-containing compound of step (1) comprises zirconium oxychloride and/or zirconium chloride.
Preferably, the first conditioning agent of step (1) comprises benzoic acid.
Preferably, the first solvent of step (1) comprises N, N-dimethylformamide and/or N, N-diethylformamide.
Preferably, the mass ratio of the zirconium-containing compound to the first solvent in step (1) is 1 (90-100), and examples thereof include 1:90, 1:91, 1:92, 1:93, 1:94, 1:95, 1:96, 1:97, 1:98, 1:99, and 1:100, but are not limited to the above-mentioned values, and other values not listed in the above-mentioned range of values are also applicable.
Preferably, the dissolving of step (1) is a first ultrasonic dissolving.
Preferably, the temperature of the first ultrasonic dissolution is 20 to 30 ℃, for example, 20 ℃, 21 ℃, 22 ℃, 23 ℃, 24 ℃, 25 ℃, 26 ℃, 27 ℃, 28 ℃, 29 ℃, 30 ℃ and the like, but not limited to the recited values, and other values not recited in the above numerical range are also applicable.
Preferably, the time for the first ultrasonic dissolution is 8-15 min, such as 8min, 9min, 10min, 11min, 12min, 13min, 14min, 15min, etc., but not limited to the recited values, and other values not recited in the above range of values are also applicable.
Preferably, the temperature of the first heating in step (1) is 80-100 ℃, for example, 80 ℃, 82 ℃, 84 ℃, 86 ℃, 88 ℃, 90 ℃, 92 ℃, 94 ℃, 96 ℃, 98 ℃, 100 ℃ and the like, but not limited to the recited values, and other values not recited in the above range are also applicable.
In the invention, the first heating in the step (1) is used for promoting the reaction of the first regulator and the zirconium metal cluster, the preferable first heating temperature is 80-100 ℃, and if the temperature is higher than 100 ℃, a plurality of topological structures can be formed; below 80 c this results in the first modifier not reacting to the maximum extent with the zirconium metal clusters, affecting the synthesis of subsequent MOF crystals.
Preferably, the time for the first heating in step (1) is 0.6 to 1.2 hours, such as 0.6 hour, 0.7 hour, 0.8 hour, 0.9 hour, 1.0 hour, 1.1 hour, 1.2 hours, but not limited to the recited values, and other values not recited in the above-mentioned range of values are also applicable.
As a preferable technical scheme of the invention, the organic ligand in the step (2) comprises 1,3,6, 8-tetra (4-carboxyphenyl) pyrene.
Preferably, the mass ratio of the organic ligand in the step (2) to the zirconium-containing compound in the step (1) is 1 (5-6), and examples thereof include 1:5, 1:5.1, 1:5.2, 1:5.3, 1:5.4, 1:5.5, 1:5.6, 1:5.7, 1:5.8, 1:5.9, and 1:6, but the present invention is not limited to the above-mentioned values, and other values not listed in the above-mentioned range of values are also applicable.
The preferred mass ratio of the organic ligand in the step (2) to the zirconium-containing compound in the step (1) is 1 (5-6), and if the mass ratio is more than 1:5, namely, the addition amount of the organic ligand is too much, the excessive ligand is doped in the synthesized MOF crystal, so that the purity of the MOF crystal is influenced; below 1:6, i.e., too little organic ligand is added, this may result in incomplete substitution of the first modifier and formation of pure phase MOF crystals.
Preferably, before the second heating in step (2), after adding the organic ligand to the mixed solution in step (1), performing second ultrasound to obtain a homogeneous suspension.
Preferably, the temperature of the second ultrasonic treatment is 20 to 30 ℃, for example, 20 ℃, 21 ℃, 22 ℃, 23 ℃, 24 ℃, 25 ℃, 26 ℃, 27 ℃, 28 ℃, 29 ℃, 30 ℃ and the like, but the temperature is not limited to the recited values, and other values not recited in the above numerical range are also applicable.
Preferably, the time of the second ultrasonic treatment is 25-35 min, such as 25min, 26min, 27min, 28min, 29min, 30min, 31min, 32min, 33min, 34min, 35min, etc., but not limited to the values listed, and other values not listed in the above range are also applicable.
As a preferable technical scheme of the invention, before the second heating in the step (2), a second regulator is added into the mixed solution in the step (1).
Preferably, the second modulator comprises trifluoroacetic acid.
Preferably, the mass ratio of the organic ligand to the second modifier in step (2) is 1 (1.0-2.0), and may be, for example, 1:1.0, 1:1.2, 1:1.3, 1:1.4, 1:1.5, 1:1.6, 1:1.7, 1:1.8, 1:2.0, but not limited to the enumerated values, and other unrecited values within the above-mentioned range of values are also applicable.
Preferably, the temperature of the second heating in step (2) is 85-110 ℃, and may be, for example, 85 ℃, 86 ℃, 87 ℃, 88 ℃, 89 ℃, 90 ℃, 91 ℃, 92 ℃, 93 ℃, 94 ℃, 95 ℃, 96 ℃, 97 ℃, 98 ℃, 99 ℃, 100 ℃, 101 ℃, 102 ℃, 103 ℃, 104 ℃, 105 ℃, 106 ℃, 107 ℃, 108 ℃, 109 ℃, 110 ℃, etc., but is not limited to the recited values, and other values not recited in the above range of values are also applicable.
In the invention, the second heating in the step (2) is used for completing the synthesis of the MOF material by a solvothermal method. The preferable temperature of the second heating is 85-110 ℃, and if the temperature is higher than 110 ℃, various topological structures can be formed; if the temperature is lower than 85 ℃, the organic ligand can not replace the first regulator to the maximum extent, the crystal structure is influenced, and the heterogeneous crystal is generated.
Preferably, the time for the second heating in step (2) is 15.5 to 24 hours, such as 15.5 hours, 16 hours, 17 hours, 18 hours, 19 hours, 20 hours, 21 hours, 22 hours, 23 hours, 24 hours, etc., but not limited to the recited values, and other values not recited in the above range of values are also applicable.
As a preferable technical scheme of the invention, before the step (3), the zirconium-containing organic framework material in the step (2) is washed and dried in vacuum in sequence.
Preferably, the washing temperature is 20 to 30 ℃, for example, 20 ℃, 21 ℃, 22 ℃, 23 ℃, 24 ℃, 25 ℃, 26 ℃, 27 ℃, 28 ℃, 29 ℃, 30 ℃ and the like, but not limited to the recited values, and other values not recited in the above numerical range are also applicable.
Preferably, the washing comprises soaking the zirconium-containing organic framework material obtained in the step (2) in a washing solution and then performing centrifugal separation.
Preferably, the wash solution comprises N, N-dimethylformamide.
Preferably, the temperature of the vacuum drying is 110-130 ℃, for example, 110 ℃, 112 ℃, 114 ℃, 116 ℃, 118 ℃, 120 ℃, 122 ℃, 124 ℃, 126 ℃, 128 ℃, 130 ℃ and the like, but not limited to the recited values, and other values not recited in the above numerical range are also applicable.
Preferably, the vacuum drying time is 6 to 12 hours, for example, 6 hours, 6.5 hours, 7 hours, 7.5 hours, 8 hours, 8.5 hours, 9 hours, 9.5 hours, 10 hours, 10.5 hours, 11 hours, 11.5 hours, 12 hours, etc., but the vacuum drying time is not limited to the recited values, and other values not recited in the above numerical range are also applicable.
In a preferred embodiment of the present invention, the mass ratio of the agarose to the organic framework material containing zirconium in step (3) is (0.5 to 5: 1), and may be, for example, 0.5:1, 0.8:1, 1:1:1, 1.2:1, 1.5:1, 1.8:1, 2:1, 2.3:1, 2.5:1, 2.8:1, 3:1, 3.3:1, 3.5:1, 3.8:1, 4:1, 4.2:1, 4.5:1, 4.8:1, 5:1, etc., but the present invention is not limited to the above-mentioned values, and other values not listed in the above-mentioned range are also applicable.
The mass ratio of the agarose to the organic framework material containing zirconium in the step (3) is preferably (0.5-5): 1, and if the mass ratio is less than 0.5:1, namely, the organic framework material containing zirconium is too much, and the agarose is too little, the loading rate is too high, so that the material falls off; above 5:1, i.e., too little organic framework material containing zirconium and too much agarose, the agarose cannot be utilized to the maximum extent and the subsequent practical treatment effect is affected.
Preferably, the second solvent of step (3) comprises ultrapure water.
Preferably, the mass ratio of the second solvent to the agarose in step (3) is (20-200):1, and may be, for example, 20:1, 30:1, 40:1, 50:1, 60:1, 70:1, 80:1, 90:1, 100:1, 120:1, 140:1, 150:1, 160:1, 180:1, 200:1, etc., but is not limited to the enumerated values, and other unrecited values within the above numerical range are also applicable.
Preferably, the dissolving in step (3) is a third ultrasonic dissolving.
Preferably, the temperature of the third ultrasonic dissolution is 20 to 30 ℃, for example, 20 ℃, 21 ℃, 22 ℃, 23 ℃, 24 ℃, 25 ℃, 26 ℃, 27 ℃, 28 ℃, 29 ℃, 30 ℃ and the like, but not limited to the recited values, and other values not recited in the above numerical range are also applicable.
Preferably, the time for the third ultrasonic dissolution is 8-15 min, such as 8min, 9min, 10min, 11min, 12min, 13min, 14min, 15min, etc., but not limited to the recited values, and other values not recited in the above range of values are also applicable.
Preferably, the temperature of the third heating in step (3) is 62-68 ℃, for example, 62 ℃, 63 ℃, 64 ℃, 65 ℃, 66 ℃, 67 ℃, 68 ℃ and the like, but not limited to the recited values, and other values not recited in the above-mentioned value range are also applicable.
In the invention, the third heating in the step (3) is used for melting the agarose to form gel, the preferable temperature for the third heating is 62-68 ℃, and if the temperature is higher than 68 ℃, the agarose cannot form gel, because the internal structure is damaged by high temperature; if the temperature is lower than 62 ℃, the agarose will not reach the melting point and will not melt to form a gel.
Preferably, the time for the third heating in step (3) is 4 to 6 hours, such as 4 hours, 4.2 hours, 4.4 hours, 4.6 hours, 4.8 hours, 5 hours, 5.2 hours, 5.4 hours, 5.6 hours, 5.8 hours, 6 hours, etc., but not limited to the recited values, and other values in the above-mentioned range are also applicable.
Preferably, the final temperature of the cooling in step (3) is-85 to-75 deg.C, such as-85 deg.C, -84 deg.C, -83 deg.C, -82 deg.C, -81 deg.C, -80 deg.C, -79 deg.C, -78 deg.C, -77 deg.C, -76 deg.C, -75 deg.C, etc., but not limited to the recited values, and other values not recited in the above-mentioned range of values are also applicable.
Preferably, the drying of step (3) comprises freeze-drying.
Preferably, the freeze-drying time is 48 to 72 hours, for example, 48 hours, 50 hours, 52 hours, 54 hours, 56 hours, 58 hours, 60 hours, 62 hours, 64 hours, 66 hours, 68 hours, 70 hours, 72 hours, etc., but the freeze-drying time is not limited to the recited values, and other values not recited in the above numerical range are also applicable.
As a preferred technical scheme of the invention, the preparation method comprises the following steps:
(1) dissolving a zirconium-containing compound and a first regulator in a first solvent according to a molar ratio of 1 (50-80), controlling the temperature to be 80-100 ℃, and heating for 0.6-1.2 h for the first time to obtain a mixed solution;
wherein the mass ratio of the zirconium-containing compound to the first solvent is 1 (90-100), and the dissolving comprises carrying out first ultrasonic treatment at 20-30 ℃ for 8-15 min;
(2) adding an organic ligand and a second regulator into the mixed solution in the step (1) according to the mass ratio of 1 (1.0-2.0), controlling the mass ratio of the organic ligand to the zirconium-containing compound in the step (1) to be 1 (5-6), carrying out secondary ultrasonic treatment at 20-30 ℃ for 25-35 min, controlling the temperature to be 85-110 ℃ for carrying out secondary heating for 15.5-24 h to obtain a zirconium-containing organic framework material, and then sequentially washing and vacuum drying the zirconium-containing organic framework material;
the washing comprises the steps of soaking the zirconium-containing organic framework material in N, N-dimethylformamide at the temperature of 20-30 ℃ and then carrying out centrifugal separation, wherein the vacuum drying temperature is controlled to be 110-130 ℃, and the vacuum drying time is controlled to be 6-12 h;
(3) and (3) dissolving agarose and the zirconium-containing organic framework material in the step (2) in a second solvent according to a mass ratio of (0.5-5): 1, controlling the mass ratio of the second solvent to the agarose to be (20-200):1, carrying out third ultrasonic treatment at 20-30 ℃ for 8-15 min, controlling the temperature to be 62-68 ℃ for third heating for 4-6 h, cooling to-85-75 ℃, and carrying out freeze drying for 48-72 h to obtain the zirconium-containing organic framework material composite aerogel.
The invention also aims to provide application of the zirconium-containing organic framework material composite aerogel, and the zirconium-containing organic framework material composite aerogel is used for treating oxyanion wastewater and/or organic arsenic wastewater.
Preferably, the component of the oxyanion-containing wastewater comprises dichromate (Cr)2O7 2-) Chromate (CrO)4 2-) Arsenate (AsO)4 3-) Arsenite (AsO)2 -) Antimonate (SbO)3 -) Selenate (SeO)4 2-) Selenite (SeO)3 2-) Or perrhenates (ReO)4 -) Any one or a combination of at least two of, including but not limited to, CrO4 2-And AsO4 3-Combination of (A) AsO2 -And SeO4 2-Combinations of (A) and (B), ReO4 -And Cr2O7 2-Combination of (A) CrO4 2-And SbO3 -Combination of (A) AsO4 3-And SbO3 -Combination of (A) AsO2 -And SeO3 2-Combination of (A) AsO2 -And ReO4 -Combination of (5), SeO4 2-And ReO4 -Combinations of (a) and (b).
The recitation of numerical ranges herein includes not only the above-recited numerical values, but also any numerical values between non-recited numerical ranges, and is not intended to be exhaustive or to limit the invention to the precise numerical values encompassed within the range for brevity and clarity.
Compared with the prior art, the invention has the following beneficial effects:
(1) the zirconium-containing organic framework material composite aerogel disclosed by the invention is excellent in mechanical property, good in stability and rich in pore structure, and in addition, oxygen-containing anions in wastewater can be effectively adsorbed and removed;
(2) the zirconium-containing organic framework material composite aerogel is easy to separate and can be recycled, and the adsorption performance recovery rate after regeneration is high;
(3) the preparation method of the zirconium-containing organic framework material composite aerogel prepares the zirconium-containing organic framework material/agarose composite aerogel by a direct mixing method, and has the advantages of simple operation, safety, low cost and wide applicability.
Drawings
FIG. 1 is a diagram of a composite aerogel containing organic framework material obtained in example 1, which is placed on a pistil;
fig. 2 is an XRD pattern of the composite aerogel of the organic framework material containing zirconium and the organic framework material containing zirconium in example 1.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides a zirconium-containing organic framework material composite aerogel and a preparation method thereof, wherein the preparation method comprises the following steps:
(1) dissolving zirconium oxychloride and benzoic acid in a molar ratio of 1:73.45 in N, N-dimethylformamide, and heating for the first time for 1h at a temperature of 80 ℃ to obtain a mixed solution;
wherein the mass ratio of the zirconium oxychloride to the N, N-dimethylformamide is 1:95, and the dissolving comprises carrying out first ultrasonic treatment at 25 ℃ for 10 min;
(2) adding 1,3,6, 8-tetra (4-carboxyphenyl) pyrene and trifluoroacetic acid into the mixed solution in the step (1) according to the mass ratio of 1:1.5, controlling the mass ratio of 1,3,6, 8-tetra (4-carboxyphenyl) pyrene to the zirconium oxychloride in the step (1) to be 1:5.14, carrying out secondary ultrasonic treatment at 25 ℃ for 30min, controlling the temperature to be 100 ℃, carrying out secondary heating for 24h to obtain a zirconium-containing organic framework material, and then sequentially washing and vacuum-drying the zirconium-containing organic framework material;
wherein, the washing comprises the steps of soaking the zirconium-containing organic framework material in N, N-dimethylformamide at the temperature of 25 ℃ and then carrying out centrifugal separation, wherein the vacuum drying temperature is controlled at 120 ℃, and the vacuum drying time is controlled at 12 h;
(3) and (3) dissolving agarose and the zirconium-containing organic framework material in the step (2) in ultrapure water according to the mass ratio of 2:1, controlling the mass ratio of the ultrapure water to the agarose to be 50:1, performing third ultrasonic treatment at 25 ℃ for 10min, controlling the temperature to be 65 ℃ for third heating for 4h, cooling to-80 ℃, and freeze-drying for 72h to obtain the zirconium-containing organic framework material composite aerogel.
FIG. 1 is a diagram of a zirconium-containing organic framework material composite aerogel obtained in this example, which is placed on a pistil, and it can be seen from FIG. 1 that the composite aerogel is light and can be placed on the pistil; fig. 2 is an XRD chart of the composite aerogel of the organic framework material containing zirconium and the organic framework material containing zirconium in this example, and it can be seen from fig. 2 that the organic framework material containing zirconium has been successfully loaded on the agarose gel by the preparation method described in this example.
Example 2
The embodiment provides a zirconium-containing organic framework material composite aerogel and a preparation method thereof, wherein the preparation method comprises the following steps:
(1) dissolving zirconium chloride and benzoic acid in a molar ratio of 1:50 in N, N-diethylformamide, controlling the temperature at 90 ℃ and heating for the first time for 1.2 hours to obtain a mixed solution;
wherein the mass ratio of zirconium chloride to N, N-diethylformamide is 1:100, and the dissolving step comprises carrying out first ultrasonic treatment at 20 ℃ for 15 min;
(2) adding 1,3,6, 8-tetra (4-carboxyphenyl) pyrene and trifluoroacetic acid into the mixed solution in the step (1) according to the mass ratio of 1:1.0, controlling the mass ratio of 1,3,6, 8-tetra (4-carboxyphenyl) pyrene to the zirconium chloride in the step (1) to be 1:5, carrying out secondary ultrasonic treatment at 20 ℃ for 35min, controlling the temperature to be 110 ℃ for secondary heating for 15.5h to obtain a zirconium-containing organic framework material, and then sequentially washing and vacuum drying the zirconium-containing organic framework material;
wherein, the washing comprises the steps of soaking the zirconium-containing organic framework material in N, N-dimethylformamide at the temperature of 20 ℃ and then carrying out centrifugal separation, wherein the vacuum drying temperature is controlled at 110 ℃, and the vacuum drying time is controlled at 9 h;
(3) and (3) dissolving agarose and the zirconium-containing organic framework material in the step (2) in ultrapure water according to the mass ratio of 0.3:1, controlling the mass ratio of the ultrapure water to the agarose to be 20:1, carrying out third ultrasonic treatment at 20 ℃ for 15min, controlling the temperature to be 62 ℃, carrying out third heating for 6h, cooling to-85 ℃, and carrying out freeze drying for 48h to obtain the zirconium-containing organic framework material composite aerogel.
Example 3
The embodiment provides a zirconium-containing organic framework material composite aerogel and a preparation method thereof, wherein the preparation method comprises the following steps:
(1) dissolving zirconium oxychloride and benzoic acid in a molar ratio of 1:80 in N, N-dimethylformamide, and heating for 0.6h for the first time at 100 ℃ to obtain a mixed solution;
wherein the mass ratio of the zirconium oxychloride to the N, N-dimethylformamide is 1:90, and the dissolving comprises carrying out first ultrasonic treatment at 30 ℃ for 8 min;
(2) adding 1,3,6, 8-tetra (4-carboxyphenyl) pyrene and trifluoroacetic acid into the mixed solution in the step (1) according to the mass ratio of 1:2.0, controlling the mass ratio of 1,3,6, 8-tetra (4-carboxyphenyl) pyrene to the zirconium oxychloride in the step (1) to be 1:6, carrying out secondary ultrasonic treatment at 30 ℃ for 25min, controlling the temperature to be 85 ℃, carrying out secondary heating for 20h to obtain a zirconium-containing organic framework material, and then sequentially washing and vacuum-drying the zirconium-containing organic framework material;
wherein, the washing comprises the steps of soaking the zirconium-containing organic framework material in N, N-dimethylformamide at the temperature of 30 ℃ and then carrying out centrifugal separation, wherein the vacuum drying temperature is controlled at 130 ℃, and the vacuum drying time is controlled at 6 h;
(3) and (3) dissolving agarose and the zirconium-containing organic framework material in the step (2) in ultrapure water according to the mass ratio of 5:1, controlling the mass ratio of the ultrapure water to the agarose to be 150:1, performing third ultrasonic treatment at 30 ℃ for 8min, controlling the temperature to be 68 ℃ for third heating for 5h, cooling to-75 ℃, and freeze-drying for 60h to obtain the zirconium-containing organic framework material composite aerogel.
Example 4
This example provides a zirconium-containing organic framework composite aerogel and a method for preparing the same, except that the molar ratio of zirconium oxychloride to benzoic acid in step (1) is changed from 1:73.45 to 1:45, and the other conditions are exactly the same as in example 1.
Example 5
This example provides a zirconium-containing organic framework composite aerogel and a method for preparing the same, except that the molar ratio of zirconium oxychloride to benzoic acid in step (1) is changed from 1:73.45 to 1:85, and the other conditions are exactly the same as in example 1.
Example 6
The embodiment provides a zirconium-containing organic framework material composite aerogel and a preparation method thereof, and except that the mass ratio of 1,3,6, 8-tetra (4-carboxyphenyl) pyrene in the step (2) to zirconium oxychloride in the step (1) is replaced by 1:4.5 from 1:5.14, the other conditions are completely the same as those in the example 1.
Example 7
The embodiment provides a zirconium-containing organic framework material composite aerogel and a preparation method thereof, and except that the mass ratio of 1,3,6, 8-tetra (4-carboxyphenyl) pyrene in the step (2) to zirconium oxychloride in the step (1) is replaced by 1:6.5 from 1:5.14, the other conditions are completely the same as those in the example 1.
Example 8
This example provides a zirconium-containing organic framework composite aerogel and a method for preparing the same, except that the temperature of the second heating in step (2) is changed from 100 ℃ to 80 ℃, and the other conditions are exactly the same as in example 1.
Example 9
This example provides a zirconium-containing organic framework composite aerogel and a method for preparing the same, except that the temperature of the second heating in step (2) is changed from 100 ℃ to 115 ℃, and the other conditions are exactly the same as those in example 1.
Example 10
The embodiment provides a zirconium-containing organic framework material composite aerogel and a preparation method thereof, and except that the mass ratio of the agarose to the zirconium-containing organic framework material in the step (3) is replaced by 0.2:1 from 2:1, the other conditions are completely the same as those in the embodiment 1.
Example 11
The embodiment provides a zirconium-containing organic framework material composite aerogel and a preparation method thereof, and the other conditions are completely the same as those in the embodiment 1 except that the mass ratio of the agarose to the zirconium-containing organic framework material in the step (3) is replaced by 6:1 from 2: 1.
Example 12
This example provides a zirconium-containing organic framework composite aerogel and a method for preparing the same, except that the temperature of the third heating in step (3) is changed from 65 ℃ to 55 ℃, and the other conditions are exactly the same as in example 1.
Example 13
This example provides a zirconium-containing organic framework composite aerogel and a method for preparing the same, except that the temperature of the third heating in step (3) is changed from 65 ℃ to 75 ℃, and the other conditions are exactly the same as in example 1.
Comparative example 1
The comparative example provides an agarose aerogel and a preparation method thereof, the preparation method comprising the steps of:
mixing agarose and ultrapure water according to the mass ratio of 1:50, performing third ultrasonic treatment at 25 ℃ for 10min, controlling the temperature at 65 ℃ for third heating for 4h, cooling to-80 ℃, and freeze-drying for 72h to obtain the agarose aerogel.
(I) the zirconium-containing organic framework material composite aerogel obtained in the example and the agarose aerogel obtained in the comparative example are applied to the treatment of oxyanion-containing wastewater, and the application method comprises the following steps:
adding 30mg of zirconium-containing organic framework material composite aerogel into a wastewater solution with the concentration of oxoanion being 100mg/L, and placing the wastewater solution in a constant-temperature shaking incubator for shaking adsorption for 24 hours.
The removal rate of oxoanions was tested by the following method: sampling the adsorbed oxyanion-containing wastewater solution by inductively coupled plasma emission spectrometry (ICP-OES) test for the concentration of oxoanions, denoted as C; then, the removal rate of the oxoanion, that is, the removal rate of the oxoanion ═ 1-C/C, can be obtained by calculation0) X 100% where C0＝100mg/L。
The above examples and comparative examples are for ReO4 -The removal results are shown in Table 1.
TABLE 1
The following points can be derived from table 1:
(1) as can be seen from examples 1 to 3, the zirconium-containing organic framework material composite aerogel can effectively adsorb and remove oxyanions in wastewater;
(2) comparing example 1 with examples 4 and 5, it can be seen that, since the molar ratio of the zirconium oxychloride to the benzoic acid in step (1) of example 4 is 1:45, which is more than the preferred molar ratio of 1 (50-80) in the present invention, too little benzoic acid content may not promote the growth of MOF crystals, may not prevent the formation of disordered or amorphous precipitate material, and may further result in ReO4 -The removal rate is reduced; since the molar ratio of the zirconium oxychloride to the benzoic acid in the step (1) in the example 5 is 1:85, which is lower than the preferable molar ratio of the zirconium oxychloride to the benzoic acid in the step 1 (50-80), too much benzoic acid content can cause too many metal cluster nodes to be capped by the benzoic acid, too much benzoic acid cannot be replaced by subsequent organic ligands, and the formation of MOF crystals is interrupted, thereby causing ReO4 -The removal rate is reduced;
(3) comparing example 1 with examples 6 and 7, it can be seen that, since the mass ratio of the 1,3,6, 8-tetra (4-carboxyphenyl) pyrene in step (2) in example 6 to the zirconium oxychloride in step (1) is 1:4.5, which is higher than 1 (5-6) preferred in the present invention, too much organic ligand 1,3,6, 8-tetra (4-carboxyphenyl) pyrene is added, which may result in too much organic ligand 1,3,6, 8-tetra (4-carboxyphenyl) pyreneThe excess ligand is doped into the synthesized MOF crystal, affecting the purity thereof, and further leading to ReO4 -The removal rate is reduced; since the mass ratio of the 1,3,6, 8-tetra (4-carboxyphenyl) pyrene in the step (2) to the zirconium oxychloride in the step (1) in the embodiment 7 is 1:6.5, which is more preferable than the preferable mass ratio of the 1:5 to 6 in the invention, if the addition amount of the organic ligand 1,3,6, 8-tetra (4-carboxyphenyl) pyrene is too small, benzoic acid cannot be completely substituted, a pure phase MOF crystal is formed, and ReO is caused4 -The removal rate is reduced;
(4) comparing example 1 with examples 8 and 9, it can be seen that, since the temperature of the second heating in step (2) in example 8 is 80 ℃ which is lower than the preferred temperature of 85-110 ℃ in the present invention, the organic ligand 1,3,6, 8-tetra (4-carboxyphenyl) pyrene cannot substitute benzoic acid to the maximum extent, the crystal structure is affected, a hetero-phase crystal is generated, and ReO is caused4-The removal rate is reduced; since the temperature of the second heating in the step (2) in example 9 is 115 ℃, which exceeds the preferred temperature of 85-110 ℃ in the invention, the formation of various topological structures can be caused, and ReO is further caused4 -The removal rate is reduced, which in turn leads to ReO4 -The removal rate is reduced;
(5) comparing example 1 with examples 10 and 11, it can be seen that, since the mass ratio of the agarose and the zirconium-containing organic framework material in step (3) in example 10 is 0.2:1, which is lower than that (0.5-5) 1 preferred in the present invention, too much zirconium-containing organic framework material and too little agarose result in too high loading rate, and the material is easy to fall off; since the mass ratio of the agarose to the organic framework material containing zirconium in the step (3) in the example 11 is 6:1, which is more than (0.5-5): 1 preferred in the invention, agarose cannot be utilized to the maximum extent, and the subsequent actual treatment effect, ReO, is affected4 -The removal rate is reduced;
(6) comparing example 1 with examples 12 and 13, it can be seen that, since the temperature of the third heating in step (3) of example 12 is 55 ℃ and is lower than the preferred temperature of 62-68 ℃ in the present invention, agarose cannot reach the melting point and cannot be melted to form gel; since the temperature of the third heating in step (3) of example 13 was 75 ℃, the temperature was exceededThe optimal temperature of the agarose gel is 62-68 ℃, and the internal structure can be damaged at high temperature, so that the agarose cannot form gel; when the temperature of the third heating is out of the preferable range, stable aerogel cannot be formed against ReO4 -The removal rate of (a) is 0%;
(7) comparing example 1 with comparative example 1, it can be seen that the agarose aerogel modified without the zirconium-containing organic framework material was used for ReO4 -No adsorption effect and 0 percent of removal rate.
(II) the zirconium-containing organic framework material composite aerogel obtained in the example 1 and the agarose aerogel obtained in the comparative example 1 are used for removing CrO4 2-、SeO3 2-、AsO2 -、ReO4 -And rocarsone waste water, the results for the removal of five contaminants are shown in table 2.
TABLE 2
As can be seen from table 2:
the zirconium-containing organic framework material composite aerogel obtained by the invention has different adsorption performances on different oxygen-containing acid radicals, the removal effect on organic acid roxarsone is superior to that of other inorganic acid radicals, the agarose aerogel which is not modified by the zirconium-containing organic framework material has no adsorption effect on the oxygen-containing acid radicals, and the removal rate is 0%.
(III) the zirconium-containing organic framework material composite aerogel obtained in the example 1 is used for adsorbing the roxarsone-containing wastewater, and the zirconium-containing organic framework material composite aerogel after adsorption is regenerated, wherein the regeneration method comprises the following steps:
soaking the adsorbed zirconium-containing organic framework material composite aerogel in 30% methanol water solution for 24 hours, washing with ultrapure water, freezing at-80 ℃ overnight, and freeze-drying for 72 hours to obtain regenerated zirconium-containing organic framework material composite aerogel, and testing the removal rate of the zirconium-containing organic framework material composite aerogel on rocarsone after N times of regeneration by the test method for the removal rate of oxyanions; the ratio of the removal rate of the regenerated zirconium-containing organic framework material composite aerogel to the wastewater to be treated to the removal rate of the regenerated zirconium-containing organic framework material composite aerogel for the first time in wastewater treatment is called as the regeneration rate.
The removal rate of roxarsone from the zirconium-containing organic framework material composite aerogel obtained in example 1 and the removal rate of roxarsone after regeneration are shown in table 3.
TABLE 3
From table 3 it can be derived:
the regenerated aerogel can still retain the capacity of removing target pollutants, which shows that the regenerated aerogel has good cyclic regeneration performance, and the regeneration rate of the regenerated zirconium-containing organic framework material composite aerogel after three times of regeneration can still reach 85 percent compared with the removal rate of the zirconium-containing organic framework material composite aerogel for the initial removal of roxarsone.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (10)
1. The zirconium-containing organic framework material composite aerogel is characterized by comprising a zirconium-containing organic framework material and agarose aerogel, wherein the zirconium-containing organic framework material is attached in a pore structure of the agarose aerogel.
2. A method for preparing the zirconium-containing organic framework material composite aerogel according to claim 1, wherein the method comprises the following steps:
(1) dissolving a zirconium-containing compound and a first regulator in a first solvent, and heating for the first time to obtain a mixed solution;
(2) adding an organic ligand into the mixed solution obtained in the step (1), and heating for the second time to obtain a zirconium-containing organic framework material;
(3) and (3) dissolving agarose and the zirconium-containing organic framework material obtained in the step (2) in a second solvent, and sequentially heating, cooling and drying for the third time to obtain the zirconium-containing organic framework material composite aerogel.
3. The preparation method according to claim 2, wherein the molar ratio of the zirconium-containing compound to the first modifier in step (1) is 1 (50-80);
preferably, the zirconium-containing compound of step (1) comprises zirconium oxychloride and/or zirconium chloride;
preferably, the first conditioning agent of step (1) comprises benzoic acid;
preferably, the first solvent of step (1) comprises N, N-dimethylformamide and/or N, N-diethylformamide;
preferably, the mass ratio of the zirconium-containing compound to the first solvent in the step (1) is 1 (90-100);
preferably, the dissolving of step (1) is a first ultrasonic dissolving;
preferably, the temperature of the first ultrasonic dissolution is 20-30 ℃;
preferably, the time for the first ultrasonic dissolution is 8-15 min;
preferably, the temperature of the first heating in the step (1) is 80-100 ℃;
preferably, the time for the first heating in the step (1) is 0.6-1.2 h.
4. The method according to claim 2 or 3, wherein the organic ligand in the step (2) comprises 1,3,6, 8-tetrakis (4-carboxyphenyl) pyrene;
preferably, the mass ratio of the organic ligand in the step (2) to the zirconium-containing compound in the step (1) is 1 (5-6);
preferably, before the second heating in step (2), after adding an organic ligand into the mixed solution in step (1), performing second ultrasound to obtain a homogeneous suspension;
preferably, the temperature of the second ultrasonic is 20-30 ℃;
preferably, the time of the second ultrasonic treatment is 25-35 min.
5. The method according to any one of claims 2 to 4, wherein a second conditioning agent is added to the mixed solution of step (1) before the second heating of step (2);
preferably, the second modulator comprises trifluoroacetic acid;
preferably, the mass ratio of the organic ligand to the second regulator in the step (2) is 1 (1.0-2.0);
preferably, the temperature of the second heating in the step (2) is 85-110 ℃;
preferably, the time for the second heating in the step (2) is 15.5-24 h.
6. The method according to any one of claims 2 to 5, wherein, prior to step (3), the zirconium-containing organic framework material of step (2) is subjected to washing and vacuum drying in this order;
preferably, the washing temperature is 20-30 ℃;
preferably, the washing comprises the step of soaking the zirconium-containing organic framework material obtained in the step (2) in a washing solution and then performing centrifugal separation;
preferably, the wash solution comprises N, N-dimethylformamide;
preferably, the temperature of the vacuum drying is 110-130 ℃;
preferably, the vacuum drying time is 6-12 h.
7. The method according to any one of claims 2 to 6, wherein the mass ratio of the agarose to the organic framework material containing zirconium in the step (3) is (0.5-5: 1;
preferably, the second solvent of step (3) comprises ultrapure water;
preferably, the mass ratio of the second solvent to the agarose in the step (3) is (20-200): 1;
preferably, the dissolving in the step (3) is a third ultrasonic dissolving;
preferably, the temperature of the third ultrasonic dissolution is 20-30 ℃;
preferably, the time of the third ultrasonic dissolution is 8-15 min;
preferably, the temperature of the third heating in the step (3) is 62-68 ℃;
preferably, the time for the third heating in the step (3) is 4-6 h;
preferably, the final temperature of the cooling in the step (3) is-85 to-75 ℃;
preferably, the drying of step (3) comprises freeze-drying;
preferably, the freeze drying time is 48-72 h.
8. The method of any one of claims 2 to 7, comprising the steps of:
(1) dissolving a zirconium-containing compound and a first regulator in a first solvent according to a molar ratio of 1 (50-80), controlling the temperature to be 80-100 ℃, and heating for 0.6-1.2 h for the first time to obtain a mixed solution;
wherein the mass ratio of the zirconium-containing compound to the first solvent is 1 (90-100), and the dissolving comprises carrying out first ultrasonic treatment at 20-30 ℃ for 8-15 min;
(2) adding an organic ligand and a second regulator into the mixed solution in the step (1) according to the mass ratio of 1 (1.0-2.0), controlling the mass ratio of the organic ligand to the zirconium-containing compound in the step (1) to be 1 (5-6), carrying out secondary ultrasonic treatment at 20-30 ℃ for 25-35 min, controlling the temperature to be 85-110 ℃ for carrying out secondary heating for 15.5-24 h to obtain a zirconium-containing organic framework material, and then sequentially washing and vacuum drying the zirconium-containing organic framework material;
the washing comprises the steps of soaking the zirconium-containing organic framework material in N, N-dimethylformamide at the temperature of 20-30 ℃ and then carrying out centrifugal separation, wherein the vacuum drying temperature is controlled to be 110-130 ℃, and the vacuum drying time is controlled to be 6-12 hours;
(3) and (3) dissolving agarose and the zirconium-containing organic framework material in the step (2) in a second solvent according to a mass ratio of (0.5-5): 1, controlling the mass ratio of the second solvent to the agarose to be (20-200):1, carrying out third ultrasonic treatment at 20-30 ℃ for 8-15 min, controlling the temperature to be 62-68 ℃ for third heating for 4-6 h, cooling to-85-75 ℃, and carrying out freeze drying for 48-72 h to obtain the zirconium-containing organic framework material composite aerogel.
9. Use of the zirconium containing organic framework material composite aerogel as claimed in claim 1, wherein said zirconium containing organic framework material composite aerogel is used for treating oxyanion waste water and/or organic arsenic waste water.
10. The use of the zirconium-containing organic framework material composite aerogel as claimed in claim 9, wherein the component of the oxyanion waste water comprises any one or a combination of at least two of dichromate, chromate, arsenate, arsenite, antimonate, selenate, selenite, or perrhenate.
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