CN109569520B - Modified metal organic framework composite material and preparation method and application thereof - Google Patents
Modified metal organic framework composite material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a modified metal organic framework composite material, a preparation method and application, belonging to the technical field of porous material preparation; the structural formula of the material is as follows:
(ii) a The invention uses metal organic framework composite material UiO-66-NH2Adding the mixture into N, N-dimethylformamide, adding ethylene glycol diglycidyl ether for reflux reaction, and washing, separating and drying after the reaction is finished to prepare MOF-EGD; sequentially adding the MOF-EGD and 2-amino-5-mercapto-1, 3, 4-thiadiazole into an N, N-dimethylformamide solution for reflux reaction, and after the reaction is finished, washing, separating and drying to prepare a modified metal organic framework composite material MOF-EGD-TTA; the method is simple and easy to operate, and the prepared modified metal organic framework composite material can be used as an adsorbent, adsorbs gold ions in a solution, is simple and convenient to operate, is easy to synthesize, is easy to separate from an aqueous solution, has high adsorbability and can be recycled.
Description
Technical Field
The invention relates to a modified metal organic framework composite material, a preparation method and application, and belongs to the technical field of porous material preparation.
Background
In the fields of electronic materials, jewelry, catalysts, and the like, there is an increasing demand for gold. In addition, the available gold resources begin to decrease. Therefore, there is an increasing interest in the recovery and enrichment of gold. However, due to the complex chemistry and overlapping nature, separation of gold ions has always been a challenge, and many methods have been developed to recover gold from aqueous solutions, such as electrolysis, precipitation, solvent extraction and adsorption.
Among all the above methods, the electrolytic method is only suitable for solutions with high ionic solubility, and is difficult to treat solutions with low concentration; the precipitation method has complex process, wastes time and labor, and is not suitable for industrialization; the extraction method mainly aims at the solution with higher ion concentration. However, adsorption is efficient and economical, and is particularly suitable for low concentrations of gold because of its low cost, ease of handling, and ease of handling. The adsorption separation enrichment method is generally regarded as important due to the characteristics of good selectivity, simple operation and the like. The adsorbents which are widely applied at present comprise nano silicon dioxide, active carbon, polyurethane foam plastics, chelating resin, metal organic framework composite materials and the like; in response to various objectives and requirements, efforts to develop new adsorbents have never been interrupted.
The same technical solution as the present invention is not disclosed at present.
Disclosure of Invention
Aiming at the problems and the defects in the prior art, the invention provides a modified metal organic framework composite material, a preparation method and application; the modified metal organic framework composite material can be used as an adsorbent, adsorbs gold ions in a solution, is simple and convenient to operate, easy to synthesize, easy to separate from an aqueous solution, has high adsorbability and can be recycled.
The structural formula of the modified metal organic framework composite material is as follows:
the preparation method of the modified metal organic framework composite material comprises the following steps:
(1) the metal organic framework composite material UiO-66-NH is added2Adding the mixture into N, N-dimethylformamide, then adding ethylene glycol diglycidyl ether, carrying out reflux reaction for 15-24 h at 70-90 ℃, taking out solid substances after the reaction is finished, washing the solid substances with N, N-dimethylformamide solution, then carrying out centrifugal separation, and carrying out vacuum drying, wherein the obtained product is marked as MOF-EGD;
the metal organic framework composite material UiO-66-NH2Adding the mixture into N, N-dimethylformamide to obtain a mixture with a liquid-solid ratio mL: g of 30: 1-50: 1, ethylene glycol diglycidyl ether and UiO-66-NH2The liquid-solid ratio of (mL) to (g) is 3: 2-5: 2;
(2) sequentially adding the MOF-EGD and 2-amino-5-mercapto-1, 3, 4-thiadiazole obtained in the step (1) into an N, N-dimethylformamide solution, carrying out reflux reaction for 15-24 h at 100-130 ℃, taking out solid substances after the reaction is finished, washing the solid substances with the N, N-dimethylformamide solution, carrying out centrifugal separation, and carrying out vacuum drying to obtain a modified metal organic framework composite material, wherein the label of the modified metal organic framework composite material is MOF-EGD-TTA;
the liquid-solid ratio mL/g of the MOF-EGD to the N, N-dimethylformamide is 30: 1-50: 1, and the mass ratio of the MOF-EGD to the 2-amino-5-mercapto-1, 3, 4-thiadiazole is 2: 3-2: 5.
The metal organic framework composite material UiO-66-NH2Adding zirconium chloride particles and 2-aminoterephthalic acid into an N, N-dimethylformamide solution, carrying out reflux reaction for 15-24 h at 125-140 ℃, taking out solid substances, washing the solid substances with N, N-dimethylformamide, carrying out centrifugal separation, carrying out vacuum drying, and marking the obtained product as UiO-66-NH2(ii) a Wherein the mass ratio of the zirconium chloride particles to the 2-amino terephthalic acid is 1.5: 1-2: 1, and the liquid-solid ratio mL/g of the N, N-dimethylformamide solution to the zirconium chloride particles is 20: 1-30: 1.
The invention also aims to apply the modified metal organic framework composite material to a gold adsorption process to be used as a gold adsorbent.
The above reagents are all analytical pure reagents.
The invention has the beneficial effects that:
(1) the modified metal organic framework composite material can be used as an adsorbent, has high adsorption rate on gold ions and good selectivity on ions in a solution;
(2) the modified metal organic framework composite material is non-toxic and harmless, has stable performance, is easy to separate and can be repeatedly used, and does not cause secondary pollution to the environment;
(3) the modified metal organic framework composite material has great potential in the aspect of adsorption and separation of gold ions, and has good application and economic value.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to limit the scope of the invention.
Example 1: the structural formula of the modified metal organic framework composite material is as follows:
the preparation method of the modified metal organic framework composite material comprises the following steps:
step 1, adding 2g of zirconium chloride particles and 2-aminoterephthalic acid into N, N-dimethylformamide solution, carrying out reflux reaction for 15h at 140 ℃, taking out solid substances, washing the solid substances with N, N-dimethylformamide, carrying out centrifugal separation, carrying out vacuum drying, and marking the obtained product as UiO-66-NH2(ii) a Wherein the mass ratio of the zirconium chloride particles to the 2-amino terephthalic acid is 2:1, and the liquid-solid ratio mL of the N, N-dimethylformamide solution to the zirconium chloride particles is 30: 1;
step 2, 2g of the metal organic framework composite material UiO-66-NH obtained in the step 12Adding the mixture into N, N-dimethylformamide, then adding ethylene glycol diglycidyl ether, carrying out reflux reaction for 24 hours at 70 ℃, taking out solid substances after the reaction is finished, washing the solid substances with N, N-dimethylformamide solution, carrying out centrifugal separation, and then carrying out vacuum drying to obtain a composite material, wherein the label of the composite material is MOF-EGD; wherein the metal organic framework composite material UiO-66-NH2Adding the mixture into N, N-dimethylformamide to obtain a mixture with a liquid-solid ratio of mL to g of 30:1, ethylene glycol diglycidyl ether and UiO-66-NH2The liquid-solid ratio of (mL: g) is 3: 2;
step 3, adding 2g of MOF-EGD obtained in the step 2 into N, N-dimethylformamide, then adding 2-amino-5-mercapto-1, 3, 4-thiadiazole, carrying out reflux reaction for 24h at 100 ℃, taking out solid substances after the reaction is finished, washing the solid substances with N, N-dimethylformamide solution, carrying out centrifugal separation, and carrying out vacuum drying to obtain a modified metal framework composite material, wherein the modified metal framework composite material is marked as MOF-EGD-TTA; wherein the liquid-solid ratio of the MOF-EGD added into the N, N-dimethylformamide is mL: g30:1, and the mass ratio of the MOF-EGD to the 2-amino-5-mercapto-1, 3, 4-thiadiazole is 2: 3;
and (3) testing the performance of adsorbing gold ions:
10mg of the MOF-EGD-TTA adsorbent prepared in the embodiment is put into a gold ion solution with the initial concentration of 100mg/L for shaking adsorption for 10 hours, the adsorbent is centrifugally separated, the concentration of the residual gold ions in the filtrate is determined to be 21mg/L by ICP-OES, and the adsorption rate is 79%; stirring and washing the adsorbent adsorbing the gold ions in a thiourea solution (0.5M) for 8 hours, then washing the adsorbent with distilled water for 3 times, and finally drying the adsorbent at 80 ℃ in vacuum for 8 hours; adding 10mg of the adsorbent into a gold ion solution with the initial concentration of 100mg/L, performing vibration adsorption for 10 hours, performing centrifugal separation on the adsorbent, and measuring the concentration of the residual gold ions in the filtrate to be 26mg/L by using ICP-OES, wherein the adsorption rate is 74%; the MOF-EGD-TTA composite material of the modified metal organic framework can be recycled.
Example 2: the structural formula of the modified metal organic framework composite material is as follows:
the preparation method of the modified metal organic framework composite material comprises the following steps:
step 1, adding 2g of zirconium chloride particles and 2-aminoterephthalic acid into N, N-dimethylformamide solution, carrying out reflux reaction for 18h at 135 ℃, taking out solid substances, washing the solid substances with N, N-dimethylformamide, carrying out centrifugal separation, carrying out vacuum drying, and marking the obtained product as UiO-66-NH2(ii) a Wherein the mass ratio of the zirconium chloride particles to the 2-amino terephthalic acid is 1.5:1, and the liquid-solid ratio mL of the N, N-dimethylformamide solution to the zirconium chloride particles is 20: 1;
step 2, 2g of the metal organic framework composite material UiO-66-NH obtained in the step 12Adding the mixture into N, N-dimethylformamide, then adding ethylene glycol diglycidyl ether, carrying out reflux reaction for 20 hours at the temperature of 80 ℃, taking out solid substances after the reaction is finished, washing the solid substances with N, N-dimethylformamide solution, carrying out centrifugal separation, and then carrying out vacuum drying to obtain a composite material, wherein the label of the composite material is MOF-EGD; wherein the metal organic framework composite material UiO-66-NH2Adding the mixture into N, N-dimethylformamide to obtain a mixture with a liquid-solid ratio of mL to g of 40:1mL/g, ethylene glycol diglycidyl ether and UiO-66-NH2The liquid-solid ratio of (mL: g) is 2: 1;
step 3, adding 2g of MOF-EGD obtained in the step 2 into N, N-dimethylformamide, then adding 2-amino-5-mercapto-1, 3, 4-thiadiazole, carrying out reflux reaction for 19h at 110 ℃, taking out solid substances after the reaction is finished, washing the solid substances with N, N-dimethylformamide solution, carrying out centrifugal separation, and carrying out vacuum dryingDrying to obtain a modified metal framework composite material marked as MOF-EGD-TTA; wherein the liquid-solid ratio mL/g of the MOF-EGD added into the N, N-dimethylformamide is 40:1mL/g, and the ethylene glycol diglycidyl ether and UiO-66-NH are2The liquid-solid ratio of (mL) to (g) is 5: 2;
and (3) testing the performance of adsorbing gold ions:
10mg of the MOF-EGD-TTA adsorbent prepared in the embodiment is put into a gold ion solution with the initial concentration of 100mg/L for vibration adsorption for 10 hours, the adsorbent is centrifugally separated, the concentration of the residual gold ions in the filtrate is determined to be 18mg/L by ICP-OES, and the adsorption rate is 82%; stirring and washing the adsorbent adsorbing the gold ions in a thiourea solution (0.5M) for 8 hours, then washing the adsorbent with distilled water for 3 times, and finally drying the adsorbent at 80 ℃ in vacuum for 8 hours; 10mg of the adsorbent is put into a gold ion solution with the initial concentration of 100mg/L for shaking adsorption for 10 hours, the adsorbent is centrifugally separated, the concentration of the residual gold ions in the filtrate is measured by ICP-OES to be 22mg/L, and the adsorption rate is 78%. The MOF-EGD-TTA composite material of the modified metal organic framework can be recycled.
Example 3: the structural formula of the modified metal organic framework composite material is as follows:
the preparation method of the modified metal organic framework composite material comprises the following steps:
step 1, adding 2g of zirconium chloride particles and 2-aminoterephthalic acid into N, N-dimethylformamide solution, carrying out reflux reaction for 15h at 140 ℃, taking out solid substances, washing the solid substances with N, N-dimethylformamide, carrying out centrifugal separation, carrying out vacuum drying, and marking the obtained product as UiO-66-NH2(ii) a Wherein the mass ratio of the zirconium chloride particles to the 2-amino terephthalic acid is 1.8: 1, and the liquid-solid ratio mL of the N, N-dimethylformamide solution to the zirconium chloride particles is 25: 1;
step 2, 2g of the metal organic framework composite material UiO-66-NH obtained in the step 12Adding into N, N-dimethylformamide, adding ethylene glycol diglycidyl ether, and refluxing at 90 deg.CTaking out solid substances after the reaction is finished, washing the solid substances by using an N, N-dimethylformamide solution, then carrying out centrifugal separation and vacuum drying to obtain a composite material which is marked as MOF-EGD; wherein the metal organic framework composite material UiO-66-NH2Adding the mixture into N, N-dimethylformamide to obtain 50:1 parts of liquid-solid ratio mL: g, ethylene glycol diglycidyl ether and UiO-66-NH2The liquid-solid ratio mL to g is 5: 2;
step 3, adding 2g of MOF-EGD obtained in the step 2 into N, N-dimethylformamide, then adding 2-amino-5-mercapto-1, 3, 4-thiadiazole, carrying out reflux reaction for 15h at 130 ℃, taking out solid substances after the reaction is finished, washing the solid substances with N, N-dimethylformamide solution, carrying out centrifugal separation, and carrying out vacuum drying to obtain a modified metal framework composite material, wherein the modified metal framework composite material is marked as MOF-EGD-TTA; wherein the liquid-solid ratio mL of the MOF-EGD added into the N, N-dimethylformamide is 50:1, and the ratio of the MOF-EGD to the 2-amino-5-mercapto-1, 3, 4-thiadiazole is 2: 5;
and (3) testing the performance of adsorbing gold ions:
10mg of the MOF-EGD-TTA adsorbent prepared in the embodiment is put into a gold ion solution with the initial concentration of 100mg/L for shaking adsorption for 10 hours, the adsorbent is centrifugally separated, the concentration of the residual gold ions in the filtrate is determined to be 17mg/L by ICP-OES, and the adsorption rate is 83%; the adsorbent having adsorbed gold ions was washed in a thiourea solution (0.5M) for 8 hours with stirring, then washed 3 times with distilled water, and finally dried under vacuum at 80 ℃ for 8 hours. Adding 10mg of the adsorbent into a gold ion solution with the initial concentration of 100mg/L, performing vibration adsorption for 10 hours, performing centrifugal separation on the adsorbent, and measuring the concentration of the residual gold ions in the filtrate to be 22mg/L by using ICP-OES, wherein the adsorption rate is 78%; the MOF-EGD-TTA composite material of the modified metal organic framework can be recycled.
While the present invention has been described in detail with reference to the specific embodiments thereof, the present invention is not limited to the embodiments described above, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art.
Claims (5)
1. A modified metal organic framework composite material is characterized in that the structural formula is as follows:
the preparation method of the modified metal organic framework composite material comprises the following steps:
(1) the metal organic framework composite material UiO-66-NH is added2Adding the mixture into N, N-dimethylformamide, then adding ethylene glycol diglycidyl ether, carrying out reflux reaction for 15-24 h at 70-90 ℃, taking out solid substances after the reaction is finished, washing the solid substances with N, N-dimethylformamide solution, then carrying out centrifugal separation, and carrying out vacuum drying, wherein the obtained product is marked as MOF-EGD;
(2) sequentially adding the MOF-EGD and 2-amino-5-mercapto-1, 3, 4-thiadiazole obtained in the step (1) into N, N-dimethylformamide solution, carrying out reflux reaction for 15-24 h at 100-130 ℃, taking out solid substances after the reaction is finished, washing the solid substances with the N, N-dimethylformamide solution, carrying out centrifugal separation, and carrying out vacuum drying to obtain the modified metal organic framework composite material, wherein the label of the modified metal organic framework composite material is MOF-EGD-TTA.
2. The method of preparing a modified metal organic framework composite material according to claim 1, wherein: metal organic framework composite material UiO-66-NH2Adding the mixture into N, N-dimethylformamide to obtain a mixture with a liquid-solid ratio mL: g of 30: 1-50: 1, ethylene glycol diglycidyl ether and UiO-66-NH2The ratio of liquid to solid (mL: g) is 3: 2-5: 2.
3. The method of preparing a modified metal organic framework composite material according to claim 1, wherein: in the step (2), the liquid-solid ratio mL/g of the MOF-EGD to the N, N-dimethylformamide is 30: 1-50: 1, and the mass ratio of the MOF-EGD to the 2-amino-5-mercapto-1, 3, 4-thiadiazole is 2: 3-2: 5.
4. The method of preparing a modified metal organic framework composite material according to claim 1, wherein: metal organic framework composite material UiO-66-NH2Is prepared by mixing zirconium chloride particles withAdding 2-aminoterephthalic acid into an N, N-dimethylformamide solution, carrying out reflux reaction for 15-24 h at 125-140 ℃, taking out solid substances, washing the solid substances with N, N-dimethylformamide, carrying out centrifugal separation, carrying out vacuum drying, and marking the obtained product as UiO-66-NH2(ii) a Wherein the mass ratio of the zirconium chloride particles to the 2-amino terephthalic acid is 1.5: 1-2: 1, and the liquid-solid ratio mL/g of the N, N-dimethylformamide solution to the zirconium chloride particles is 20: 1-30: 1.
5. Use of the modified metal organic framework composite material of claim 1 as gold adsorbent.
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| US11124530B1 (en) | 2019-10-22 | 2021-09-21 | King Fahd University Of Petroleum And Minerals | Zirconium metal-organic framework and a method of detecting copper and chromate ions |
| CN111001392A (en) * | 2019-12-30 | 2020-04-14 | 中山大学 | Preparation method and application of modified zirconium-based metal organic framework adsorbent for gold ion adsorption |
| CN113045767B (en) * | 2021-03-24 | 2023-03-31 | 肇庆市武大环境技术研究院 | Nitrogen heterocyclic ring molecule modified UiO-66-NH with stable structure 2 Material and method for the production thereof |
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