CN114479109B - Preparation and application of N, S-containing metal organic framework material - Google Patents
Preparation and application of N, S-containing metal organic framework material Download PDFInfo
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- CN114479109B CN114479109B CN202210121229.5A CN202210121229A CN114479109B CN 114479109 B CN114479109 B CN 114479109B CN 202210121229 A CN202210121229 A CN 202210121229A CN 114479109 B CN114479109 B CN 114479109B
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- 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
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- 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
Abstract
The patent discloses a preparation and application of N, S-containing metal organic framework material. A metal organic framework material (Zn-AMT) containing N, S functional atoms is prepared by utilizing zinc nitrate hexahydrate and 3-amino-5-mercapto-1, 2, 4-triazole through one-step reaction. The preparation method is simple, the prepared material is used as an adsorbent for treating trivalent gold ions in the aqueous solution, the adsorption capacity is high, the adsorption rate is high, the selective adsorption performance on gold is outstanding, the desorption and the recycling are easy, and a feasible new method is provided for the recycling of noble metals.
Description
Technical Field
The invention belongs to the technical field of material preparation, and particularly relates to a method for synthesizing an N, S-containing metal organic framework material Zn-AMT and adsorbing and separating Au (III) ions in an aqueous solution.
Background
Precious metals are extremely low in nature and are often co-located with other deposits. The traditional means for obtaining the noble metal has low efficiency and high energy consumption, so that the yield of the recovery of the noble metal is difficult to improve, and the demand of human beings for the noble metal is increasing. In order to cope with the contradiction between supply and demand of noble metal resources, the recovery of noble metal is a future development direction. The recovery of noble metal can not only reuse scarce resources, but also bring great economic benefit to society, and plays a promoting role in protecting biological environment. This measure is beneficial to the construction of ecological civilization society and promotes the national economic development and technological progress.
Gold is one of the most widely used noble metals, and has excellent physical and chemical properties, such as high-temperature oxidation resistance, corrosion resistance, electrical resistance, good conductivity, higher catalytic activity, stronger coordination ability and the like. In industrial applications, gold is called an industrial vitamin due to its wide use and indispensable functions. Currently, methods applied to gold ion separation include chemical precipitation, membrane filtration, ion exchange, adsorption, electrolysis, biological treatment, and the like. Among the above methods, the adsorption method is widely used for separation of noble metals because of advantages of low running cost, simple operation, small environmental impact, easy industrialization, etc.
The research prepares a novel metal organic framework material Zn-AMT by utilizing zinc nitrate hexahydrate and 3-amino-5-mercapto-1, 2, 4-triazole, and utilizes N and S with exposed surfaces as adsorption sites to show high-efficiency selective adsorption on Au (III) in an aqueous solution.
Disclosure of Invention
The invention aims to provide a preparation method of a N, S metal-containing organic framework material with excellent adsorption performance on Au (III) in an aqueous solution, and the material has high adsorption capacity, rapid adsorption rate, high selectivity and high recycling performance on the Au (III). The technical scheme adopted by the invention is as follows:
a certain amount of Zn (NO 3 ) 2 ·6H 2 O and 3-amino-5-mercapto-1, 2, 4-triazole are added into a mixed solvent of DMF and water, the mixture is heated in a closed way at a certain temperature for reaction for a period of time, the reaction solution is cooled to room temperature, and then suction filtration, washing and drying are carried out to obtain Zn-AMT. Adopting Zn-AMT as adsorbent to adsorb and separate Au (III) in water solution, preparing Au (III) solution with certain concentration with 98% gold trichloride, and using 0.1mol/L sodium hydroxide or HNO 3 And after the pH value of the aqueous solution is regulated, a certain volume of solution is taken and added into a centrifuge tube, a certain amount of Zn-AMT is added as an adsorbent, the mixture is placed into a constant-temperature water bath oscillator at a certain temperature and is fully stirred for a certain time, a certain amount of sample is taken after the adsorption is completed, the concentration of the original solution and the residual liquid after the adsorption is measured by an atomic absorption spectrometer, and the adsorption quantity and the adsorption rate are calculated. Adding a certain volume of thiourea solution into a 50mL centrifuge tube as a desorbing agent, adding 5mg of the Zn-AMT material after adsorption, placing the mixture into a constant-temperature water bath oscillator at 15-55 ℃ to carry out oscillation desorption for 0-45h, taking out the centrifuge tube for centrifugal separation, and adsorbing the Zn-AMT material after desorption again;
preferably, the volume ratio of the mixed solvent DMF and water for preparing the material is 1:3-3:1;
preferably, zn (NO 3 ) 2 ·6H 2 The mol ratio of O to 3-amino-5-mercapto-1, 2, 4-triazole is 1:2-1:5;
preferably, the molar concentration of 3-amino-5-mercapto-1, 2, 4-triazole is 0.03-0.1mol/L;
preferably, the reaction temperature is 110-180 ℃ and the synthesis time is 12-72 h;
preferably, the concentration of the prepared Au (III) solution is 0-2000mg/L;
preferably, the pH of the solution is set to 1-6;
preferably, the adsorption temperature is 15-80 ℃;
preferably, the adsorption time is 0-2880min;
preferably, the thiourea solution has a concentration of more than 0.2mol/L.
Compared with the prior art, the invention has the following advantages:
(1) The metal organic framework material containing functional atoms N and S is prepared by adopting a one-step method, the reaction solvent is green, the reaction temperature is moderate, and the raw material cost is low. (2) Zn-AMT can effectively adsorb Au (III) ions in aqueous solution, the adsorption quantity reaches 2878mg/g, and the adsorption quantity of the material can be continuously increased by increasing the temperature. (3) The Zn-AMT material is easy to elute, can be recycled after being desorbed, is an economical material and brings higher economic benefit. (4) The Zn-AMT material has better selectivity to Au (III), and is favorable for being applied to the selective adsorption of trivalent gold ions in complex practical solution.
[ detailed description ] A method for producing a composite article
Example 1
600mg of zinc nitrate hexahydrate (2 mmol) and 700mg of 3-amino-5-mercapto-1, 2, 4-triazole (6 mmol) are added into a 250mL beaker, a mixed solvent containing 100mL of DMF and 50mL of water is added, and the mixture is stirred until the mixture is completely dissolved; the solution was transferred to a reaction vessel which had been preheated to 140℃and reacted for 12-72 hours at 140 ℃. After the reaction is completed, cooling to room temperature, carrying out suction filtration to obtain solid powder, washing for a plurality of times by using DMF, deionized water and anhydrous methanol solvent, and carrying out suction filtration; the solid was dried overnight in a vacuum oven at 80℃and ground to give Zn-AMT as a white powder.
Example 2
Au (III) solution with the concentration of 10.9mg/L is prepared by gold trichloride with the purity of 98 percent, 20mL of the solution is added into a 50mL centrifuge tube, the pH value is regulated to 3.19 by 0.1mol/L NaOH, 5mg of Zn-AMT material obtained in the example 1 is added as an adsorbent, the mixture is placed into a constant-temperature water bath oscillator for oscillation adsorption, the temperature is set to be 25 ℃, the fixed-point sampling detection is carried out, the concentration of an original solution and residual liquid after adsorption is measured by an atomic absorption spectrometer, the adsorption quantity is 43.6mg/g after 20min, and the adsorption rate is 100 percent.
Example 3
Au (III) solution with the concentration of 10.9mg/L is prepared by gold trichloride with the purity of 98 percent, 20mL of the solution is added into a 50mL centrifuge tube, the pH value is regulated to 3.19 by 0.1mol/L NaOH, 5mg of Zn-AMT material obtained in the example 1 is added as an adsorbent, the mixture is placed into a constant-temperature water bath oscillator for oscillation adsorption, the temperature is set to 25 ℃, after 8 minutes, a certain amount of sample is taken, the concentration of an original solution and residual liquid after adsorption is measured by an atomic absorption spectrometer, the adsorption amount is 41.1mg/g, and the adsorption rate is 94.2%.
Example 4
Au (III) solution with the concentration of 10.9mg/L is prepared by gold trichloride with the purity of 98 percent, 20mL of the solution is added into a 50mL centrifuge tube, the pH value is regulated to 3.19 by 0.1mol/L NaOH, 5mg of Zn-AMT material obtained in the example 1 is added as an adsorbent, the mixture is placed into a constant-temperature water bath oscillator for oscillation adsorption, the temperature is set to 25 ℃, after 2min, a certain amount of sample is taken, the concentration of the original solution and residual liquid after adsorption is measured by an atomic absorption spectrometer, the adsorption amount is 30.4mg/g, and the adsorption rate is 49.7 percent.
Example 5
Preparing an Au (III) solution with the concentration of 93mg/L by using gold trichloride with the purity of 98%, adding 20mL of the solution into a 50mL centrifuge tube, adjusting the pH to 3.19 by using 0.1mol/L NaOH, adding 5mg of the Zn-AMT material obtained in the example 1 as an adsorbent, placing the adsorbent in a constant-temperature water bath oscillator for oscillation adsorption, setting the temperature to 25 ℃, taking a certain amount of samples after 30min, and measuring the concentration of an original solution and residual liquid after adsorption by using an atomic absorption spectrometer, wherein the adsorption amount is 372.6mg/g and the adsorption rate is 100%.
Example 6
Au (III) solution with the concentration of 243.7mg/L is prepared by gold trichloride with the purity of 98 percent, 20mL of the solution is added into a 50mL centrifuge tube, the pH value is regulated to 3.19 by 0.1mol/L NaOH, 5mg of Zn-AMT material obtained in the example 1 is added as an adsorbent, the mixture is placed into a constant-temperature water bath oscillator for oscillation adsorption, the temperature is set to be 25 ℃, after 4.5 hours, a certain amount of samples are taken, the concentration of an original solution and residual liquid after adsorption is measured by an atomic absorption spectrometer, the adsorption amount is 939mg/g, and the adsorption rate is 96.3 percent.
Example 7
Preparing an Au (III) solution with the concentration of 89mg/L by using gold trichloride with the purity of 98%, adding 20mL of the solution into a 50mL centrifuge tube, adjusting the pH to 5.22 by using 0.1mol/L NaOH, adding 5mg of the Zn-AMT material obtained in the example 1 as an adsorbent, placing the adsorbent in a constant-temperature water bath oscillator for oscillation adsorption, setting the temperature to 25 ℃, taking a certain amount of samples after 18 hours, and measuring the concentration of an original solution and residual liquid after adsorption by using an atomic absorption spectrometer, wherein the adsorption amount is 343mg/g, and the adsorption rate is 96%.
Example 8
Preparing an Au (III) solution with the concentration of 89mg/L by using gold trichloride with the purity of 98%, adding 20mL of the solution into a 50mL centrifuge tube, adjusting the pH to 7.57 by using 0.1mol/L NaOH, adding 5mg of the Zn-AMT material obtained in the example 1 as an adsorbent, placing the adsorbent in a constant-temperature water bath oscillator for oscillation adsorption, setting the temperature to 25 ℃, taking a certain amount of samples after 18 hours, and measuring the concentration of an original solution and residual liquid after adsorption by using an atomic absorption spectrometer, wherein the adsorption amount is 193.4mg/g, and the adsorption rate is 54.2%.
Example 9
Au (III) solution with the concentration of 5 mg/L is prepared by gold trichloride with the purity of 98%, 20mL of the solution is added into a 50mL centrifuge tube, the pH value is regulated to 3.19 by 0.1mol/L NaOH, 5mg of Zn-AMT material obtained in example 1 is added as an adsorbent, the mixture is placed into a constant-temperature water bath oscillator for oscillation adsorption, the temperature is set to 25 ℃, after 48 hours, a certain amount of sample is taken, the concentration of an original solution and residual liquid after adsorption is measured by an atomic absorption spectrometer, the adsorption amount is 20mg/g, and the adsorption rate is 100%.
Example 10
Preparing an Au (III) solution with the concentration of 58mg/L by using gold trichloride with the purity of 98%, adding 20mL of the solution into a 50mL centrifuge tube, adjusting the pH to 3.19 by using 0.1mol/L NaOH, adding 5mg of the Zn-AMT material obtained in the example 1 as an adsorbent, placing the adsorbent in a constant-temperature water bath oscillator for oscillation adsorption, setting the temperature to 25 ℃, taking a certain amount of samples after 48 hours, measuring the concentration of an original solution and residual liquid after adsorption by using an atomic absorption spectrometer, wherein the adsorption amount is 232mg/g, and the adsorption rate is 100%.
Example 11
Au (III) solution with the concentration of 105 mg/L is prepared by gold trichloride with the purity of 98%, 20mL of the solution is added into a 50mL centrifuge tube, the pH value is regulated to 3.19 by 0.1mol/L NaOH, 5mg of Zn-AMT material obtained in example 1 is added as an adsorbent, the mixture is placed into a constant-temperature water bath oscillator for oscillation adsorption, the temperature is set to 25 ℃, after 48 hours, a certain amount of sample is taken, the concentration of an original solution and residual liquid after adsorption is measured by an atomic absorption spectrometer, the adsorption amount is 419.2mg/g, and the adsorption rate is 99.6%.
Example 12
Au (III) solution with the concentration of 292.7mg/L is prepared by gold trichloride with the purity of 98%, 20mL of the solution is added into a 50mL centrifuge tube, the pH value is regulated to 3.19 by 0.1mol/L NaOH, 5mg of Zn-AMT material obtained in example 1 is added as an adsorbent, the mixture is placed into a constant-temperature water bath oscillator for oscillation adsorption, the temperature is set to 25 ℃, after 48 hours, a certain amount of sample is taken, the concentration of an original solution and residual liquid after adsorption is measured by an atomic absorption spectrometer, the adsorption amount is 1154.6mg/g, and the adsorption rate is 98.6%.
Example 13
Au (III) solution with the concentration of 965.1mg/L is prepared by gold trichloride with the purity of 98%, 20mL of the solution is added into a 50mL centrifuge tube, the pH value is regulated to 3.19 by 0.1mol/L NaOH, 5mg of Zn-AMT material obtained in example 1 is added as an adsorbent, the mixture is placed into a constant-temperature water bath oscillator for oscillation adsorption, the temperature is set to 25 ℃, after 48 hours, a certain amount of sample is taken, the concentration of an original solution and residual liquid after adsorption is measured by an atomic absorption spectrometer, the adsorption amount is 2040.2mg/g, and the adsorption rate is 52.8%.
Example 14
Au (III) solution with the concentration of 1021mg/L is prepared by gold trichloride with the purity of 98 percent, 20mL of the solution is added into a 50mL centrifuge tube, the pH value is regulated to 3.19 by 0.1mol/L NaOH, 5mg of Zn-AMT material obtained in the example 1 is added as an adsorbent, the mixture is placed into a constant-temperature water bath oscillator for oscillation adsorption, the temperature is set to be 15 ℃, a certain amount of samples are taken after 48 hours, the concentration of the original solution and the residual solution after adsorption is measured by an atomic absorption spectrometer, the adsorption amount is 1317mg/g, and the adsorption rate is 32.2 percent.
Example 15
Au (III) solution with the concentration of 1021mg/L is prepared by gold trichloride with the purity of 98 percent, 20mL of the solution is added into a 50mL centrifuge tube, the pH value is regulated to 3.19 by 0.1mol/L NaOH, 5mg of Zn-AMT material obtained in the example 1 is added as an adsorbent, the mixture is placed into a constant-temperature water bath oscillator for oscillation adsorption, the temperature is set to 35 ℃, a certain amount of samples are taken after 48 hours, the concentration of the original solution and the residual solution after adsorption is measured by an atomic absorption spectrometer, the adsorption amount is 2605mg/g, and the adsorption rate is 63.8 percent.
Example 16
Au (III) solution with the concentration of 1021mg/L is prepared by gold trichloride with the purity of 98 percent, 20mL of the solution is added into a 50mL centrifuge tube, the pH value is regulated to 3.19 by 0.1mol/L NaOH, 5mg of Zn-AMT material obtained in the example 1 is added as an adsorbent, the mixture is placed into a constant-temperature water bath oscillator for oscillation adsorption, the temperature is set to be 42 ℃, a certain amount of samples are taken after 48 hours, the concentration of an original solution and residual liquid after adsorption is measured by an atomic absorption spectrometer, the adsorption amount is 2878mg/g, and the adsorption rate is 70.4 percent.
Example 17
5mg of Zn-AMT material is added into a mixed solution containing 20mL of Au (III), ni (II), zn (II), cu (II), cd (II) and Co (II) ions with the pH value of 3.19 and the concentration of 100mg/L, a constant-temperature water bath shaking table at 25 ℃ is used for shaking for 24 hours, and after the filtration of a microporous filter membrane, the absorbance of each ion solution before and after the absorption is measured by an atomic absorption spectrophotometer. In this example, the adsorption amount of Au (III) by the material was 400mg/g, and there was little adsorption effect on other coexisting metal ions.
Example 18
20mL of 0.5mol/L thiourea aqueous solution is taken and added into a 50mL centrifuge tube to be used as a desorbing agent, 5mg of the Zn-AMT material after adsorption is added, the mixture is placed into a constant-temperature water bath oscillator to be subjected to oscillation desorption, the temperature is set at 25 ℃, and after 24 hours, the mixture is filtered and dried, and the Zn-AMT material after desorption is subjected to adsorption again. After 3 times of repeated use, the adsorption performance is only reduced by 4 percent.
The above examples merely represent several embodiments of the present invention, and the description thereof is more specific and detailed, but the technical scope thereof is not limited to the above embodiments. Various modifications and implementations of the invention will be apparent to those skilled in the art without departing from the spirit of the invention, and these modifications and implementations are intended to be within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (7)
1. A method for preparing a N, S metal organic framework material Zn-AMT is characterized in that Zn (NO 3 ) 2 ·6H 2 Adding O and 3-amino-5-mercapto-1, 2, 4-triazole into a mixed solvent of DMF and water, wherein the volume ratio of the mixed solvent of DMF to water is 2:1; after the reaction is carried out for 12-72 hours under the airtight heating condition at 140 ℃, the reaction liquid is cooled to the room temperature, and then the Zn-AMT is obtained after suction filtration, washing and drying; adopting Zn-AMT as adsorbent to adsorb and separate Au (III) in water solution, preparing Au (III) solution with certain concentration with 98% gold trichloride, and using 0.1mol/L sodium hydroxide or HNO 3 After regulating the pH value of the aqueous solution, adding a certain volume of solution into a centrifuge tube, adding a certain amount of Zn-AMT as an adsorbent, placing the centrifuge tube in a constant-temperature water bath oscillator at a certain temperature, fully stirring for a certain time, taking a certain amount of sample after the adsorption is finished, measuring the concentrations of the original solution and residual liquid after the adsorption by using an atomic absorption spectrometer, and calculating the adsorption quantity and the adsorption rate; adding a certain volume of thiourea solution into a 50mL centrifuge tube as a desorbing agent, adding 5mg of the Zn-AMT material after adsorption, placing the mixture into a constant-temperature water bath oscillator at 15-55 ℃ for oscillation desorption for 0-45h, taking out the centrifuge tube for centrifugal separation, and adsorbing the Zn-AMT material after desorption again.
2. The method for preparing a metal-organic framework material Zn-AMT comprising N, S according to claim 1, wherein the molar concentration of 3-amino-5-mercapto-1, 2, 4-triazole is 0.03-0.1mol/L.
3. The method for preparing the organic framework material Zn-AMT containing N, S as claimed in claim 1, wherein the concentration of the prepared Au (III) solution is more than 0mg/L and less than or equal to 2000 mg/L.
4. A method for preparing a Zn-AMT containing N, S metal organic framework material according to claim 1, characterized in that the pH of the solution is set to 1-6.
5. The method for preparing the organic framework material Zn-AMT containing N, S as claimed in claim 1, wherein the adsorption temperature is 15-80 ℃.
6. The method for preparing the organic framework material Zn-AMT containing N, S according to claim 1, wherein the adsorption time is more than 0min and less than or equal to 2880 min.
7. The method for preparing the organic framework material Zn-AMT containing N, S as claimed in claim 1, wherein the concentration of the thiourea solution is more than 0.2mol/L.
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