Anti-interference silver vanadium metal-organic framework derived material, preparation method and application thereof

Abstract

The present application relates to the technical field of wastewater pollutant treatment, and particularly relates to an anti-interference type silver vanadium metal-organic framework derived material and a preparation method and application thereof; the preparation method is as follows: first, an AgV-MOF material with a two-dimensional twisted wave layer structure is prepared, and then an Ag / V-MOF derived material is prepared through alkaline etching; the Ag / V-MOF derived material has a two-dimensional twisted wave layer structure with wrinkles, a large number of -OH groups are attached to the surface, and the material has a double-metal characteristic: silver ions and vanadium ions can be bridged by organic ligands to form an electron transfer path, which is conducive to the internal electron transmission of the material, and thus improves the adsorption performance of the active sites of the material; therefore, the Ag / V-MOF derived material, through the combined action of the material surface charge, the conjugated structure of the ligand, the electron transfer of the metal center and the two-dimensional twisted wave layer structure with wrinkles, can present the characteristics of high efficiency, short time and strong anti-interference performance when adsorbing creatinine.

Description

TECHNICAL FIELD

[0001] The application relates to the technical field of pollutant treatment in wastewater, in particular to an anti-interference type silver-vanadium metal-organic framework derived material and a preparation method and application thereof. BACKGROUND

[0002] Hemodialysis can remove uremic toxins such as creatinine (CA), uric acid and urea in the blood of patients. Creatinine is a nitrogen-containing five-membered ring, and its nitrogen content is as high as 40%. If it is not treated and is discharged in large quantities into the water environment with dialysis water, it will cause environmental pollution such as eutrophication.

[0003] A bimetal-organic framework material (MOFs) is a kind of crystal structure composed of two different metal ions and organic ligands, and has the following characteristics: synergistic catalysis is realized through metal synergistic effect; the structure and properties of the bimetal MOFs can be adjusted by selecting different metals and organic ligands; the size and shape of the micro-pore channel can be regulated by changing the combination of metal ions and organic ligands; the metal ions in the bimetal MOFs can form an electron transport channel.

[0004] It can be seen that the bimetal-organic framework material has a variety of metal centers and modifiability, and therefore has a wide application in the fields of catalysis, adsorption, gas separation, energy storage and the like; but there is no report on the adsorption treatment of creatinine.

[0005] Therefore, the applicant designs a new structure of Ag / V-MOF derived material under the category of bimetal-organic framework material to solve the problem of adsorption treatment of creatinine. SUMMARY

[0006] In order to achieve the above purpose, the application designs an anti-interference type silver-vanadium bimetal-organic framework derived material, which can present the characteristics of high efficiency, short time and strong anti-interference performance in adsorbing creatinine through the joint action of the surface charge of the material, the conjugated structure of the ligand, the electron transfer of the metal center and the two-dimensional twisted wave layer structure with wrinkles on the surface.

[0007] For the convenience of description, the anti-interference type silver-vanadium bimetal-organic framework derived material designed by the application is referred to as Ag / V-MOF derived material hereinafter, which is prepared based on AgV-MOF material by alkaline treatment, and the structure of the unit cell of the AgV-MOF material is as follows:

[0008]

[0009] The unit cell is an asymmetric structural unit, which contains one silver atom, three vanadium atoms, one tris(4-(1H-1,2,4-triazole)phenyl)amine and eight oxygen atoms.

[0010] The silver atom has a coordination number of 2 and exhibits a linear structure, coordinating with two N atoms from tris(4-(1H-1,2,4-triimidazole)phenyl)amine;

[0011] One vanadium atom adjacent to tris(4-(1H-1,2,4-triimidazole)phenyl)amine forms a {VNO4} tetragonal pyramidal vanadium-oxygen cluster, while the two vanadium atoms furthest from tris(4-(1H-1,2,4-triimidazole)phenyl)amine coordinate with oxygen atoms to form a {VO4} tetrahedral vanadium-oxygen cluster.

[0012] Furthermore, AgV-MOF materials belong to the triclinic crystal system, space group P-1, and their unit cell volume is... The length of the unit cell is: The angles of the unit cell are: α = 73.2775°, β = 79.4578°, γ = 78.4595°.

[0013] Furthermore, the Ag / V-MOF-derived material exhibits a two-dimensional twisted wavy layered structure with wrinkles on its surface and possesses bimetallic complex characteristics: silver ions and vanadium ions can be bridged through tris(4-(1H-1,2,4-triimidazole)phenyl)amine as an organic ligand, forming an electron transfer pathway based on the single-electron characteristics of the vanadium-oxygen cluster.

[0014] Note: After alkaline etching, a large number of -OH groups are introduced and attached to the material surface, changing the surface charge and increasing the isoelectric point from 5.35 to 10.70; secondly, see... Figure 2 , 3 The SEM images show that the processed material surface becomes wrinkled, further increasing the specific surface area of ​​the derived material by approximately 300%. Based on these structural characteristics, the isoelectric point of the Ag / V-MOF derived material ranges from 10.6 to 10.7, and the specific surface area ranges from 1.7766 to 3.6027 m². 2 / g.

[0015] This invention also provides a method for preparing Ag / V-MOF-derived materials, comprising the following steps:

[0016] S1. Preparation of AgV-MOF materials;

[0017] S1-1. First, add tris(4-(1H-1,2,4-triimidazole)phenyl)amine, ammonium metavanadate and silver nitrate to pure water and mix well to obtain the first mixture. Then adjust the pH of the first mixture to 3.5.

[0018] Let n be the multiplier and n∈R +When the amount of tris(4-(1H-1,2,4-triimidazole)phenyl)amine added to S1-1 is 1 nmol, the amount of ammonium metavanadate added is [4.5n,6n] mol, the amount of silver nitrate added is [3n,5n] mol, and the amount of pure water added is [9n,10n] L.

[0019] S1-2. The mixture in S1-1 is reacted at 150℃ for 48-96h. After the reaction is completed, the temperature is lowered to room temperature at a rate of -10℃ / h to obtain a two-dimensional twisted wave layered AgV-MOF material.

[0020] S2. Preparation of Ag / V-MOF derivative materials;

[0021] S2-1: First, grind and crush the AgV-MOF material in S1-1, then disperse it evenly in pure water and ultrasonically vibrate it for 10-20 minutes. Then, add 3M NaOH solution and stir continuously for 1-1.5 hours to obtain the second mixture.

[0022] Let n be the multiplier and n∈R + When the amount of AgV-MOF material added in S2-1 is 1n g, the amount of pure water added is [100n, 110n] mL, and the amount of 3M NaOH solution added is [100n, 110n] mL.

[0023] S2-2. First, filter the second mixture to obtain filter residue. Wash the filter residue with pure water until the washing liquid is neutral. Then, dry the washed filter residue at 60°C for 1.5 to 2 hours to obtain Ag / V-MOF derivative material.

[0024] The present invention also designed an application of Ag / V-MOF derivative material to adsorb creatine anhydride in wastewater. Under the following reaction conditions, when the dosage of Ag / V-MOF derivative material is 0.2 g / L, the maximum adsorption capacity of creatine anhydride in wastewater is 140 mg / g.

[0025] The reaction conditions are: temperature range of 15–45℃; adsorption time of 180 min; pH range of 5–11; and interfering substances in the wastewater include… And one or more of humic acids.

[0026] Compared with existing creatine adsorbents, the advantages of this invention are:

[0027] (1) The Ag / V-MOF derivative material prepared by this invention has bimetallic properties. Silver ions and vanadium ions can form an electron transfer pathway through organic ligand bridging, which is beneficial to the internal electron transport and transfer of the material, thereby improving the adsorption performance of the active sites of the material.

[0028] (2) The Ag / V-MOF derivative material prepared in this invention has high efficiency, short time and strong anti-interference performance when used to adsorb creatine. It can still maintain high adsorption efficiency in an environment with many interfering substances, and the adsorption amount of creatine can reach 140 mg / g within 180 min.

[0029] (3) The synthesis process designed in this invention maximizes the utilization rate of the reaction substrate, reduces the generation of waste and by-products, and has atom economy; moreover, the waste generated during the synthesis process should be controllable and have no negative environmental impact, which meets the advocacy concept of green process. Attached Figure Description

[0030] Figure 1 This is a coordination environment diagram of the AgV-MOF material in Embodiment 1 of the present invention;

[0031] Figure 2 This is a SEM image of the morphology of the AgV-MOF material in Example 1 of this invention;

[0032] Figure 3 This is a SEM image of the Ag / V-MOF-derived material in Example 1 of this invention;

[0033] Figure 4 This is a graph showing the adsorption amount of Ag / V-MOF-derived material when removing creatine in the experimental examples of this invention.

[0034] Figure 5 This is an anti-interference test diagram of Ag / V-MOF-derived material adsorbing and removing creatinine under independent interfering conditions in the experimental examples of this invention;

[0035] Figure 6 This is an anti-interference test diagram of Ag / V-MOF derivative material adsorbing and removing creatine anhydride under mixed interfering conditions in the experimental examples of this invention;

[0036] Figure 7 This is a graph showing the adsorption capacity of Ag / V-MOF-derived materials for creatinine in different pH ranges in the experimental examples of this invention.

[0037] Figure 8 This is a test diagram of the recyclability of Ag / V-MOF derived materials in the experimental examples of this invention. Detailed Implementation

[0038] To further illustrate the methods and effects of this invention, the technical solution of this invention will be clearly and completely described below in conjunction with experiments.

[0039] Example 1: This example describes the preparation method of an anti-interference silver-vanadium bimetallic-organic framework derived material.

[0040] S1. Preparation of AgV-MOF materials;

[0041] S1-1. First, add tris(4-(1H-1,2,4-triimidazole)phenyl)amine, ammonium metavanadate and silver nitrate to pure water and mix well to obtain the first mixture. Then adjust the pH of the first mixture to 3.5.

[0042] When the amount of tris(4-(1H-1,2,4-triimidazole)phenyl)amine added in S1-1 is 0.1 mol, the amount of ammonium metavanadate added is 0.4 mol, the amount of silver nitrate added is 0.3 mol, and the amount of pure water added is 9 L.

[0043] S1-2. The mixture in S1-1 was reacted at 150℃ for 96h. After the reaction was completed, the temperature was lowered to room temperature at a rate of -10℃ / h to obtain a two-dimensional twisted wave layered AgV-MOF material.

[0044] S2. Preparation of Ag / V-MOF derivative materials;

[0045] S2-1. First, grind and crush the AgV-MOF material in S1-1, then disperse it evenly in pure water and ultrasonically vibrate it for 20 minutes. Then, add 3M NaOH solution and stir continuously for 1.5 hours to obtain the second mixture.

[0046] When the amount of AgV-MOF material added in S2-1 is 10g, the amount of pure water added is 1.1L, and the amount of 3M NaOH solution added is 1.1L.

[0047] S2-2. First, filter the second mixture to obtain filter residue. Wash the filter residue with pure water until the washing liquid is neutral. Then, dry the washed filter residue at 60°C for 2 hours to obtain Ag / V-MOF derived material, namely, anti-interference silver-vanadium bimetallic-organic framework derived material.

[0048] Specifically, the cell structure of the AgV-MOF material prepared in S1 is as follows:

[0049]

[0050] The unit cell is an asymmetric structural unit containing one silver atom, three vanadium atoms, one tris(4-(1H-1,2,4-triimidazole)phenyl)amine and eight oxygen atoms;

[0051] The silver atom has a coordination number of 2 and exhibits a linear structure, coordinating with two N atoms from tris(4-(1H-1,2,4-triimidazole)phenyl)amine;

[0052] One vanadium atom adjacent to tris(4-(1H-1,2,4-triimidazole)phenyl)amine forms a {VNO4} tetragonal pyramidal vanadium-oxygen cluster, while the two vanadium atoms furthest from tris(4-(1H-1,2,4-triimidazole)phenyl)amine coordinate with oxygen atoms to form a {VO4} tetrahedral vanadium-oxygen cluster.

[0053] Specifically, the Ag / V-MOF-derived material prepared in S2 has a two-dimensional twisted wavy layered structure with wrinkled surface and possesses bimetallic complex characteristics: silver ions and vanadium ions can be bridged by tris(4-(1H-1,2,4-triimidazole)phenyl)amine as an organic ligand, forming an electron transfer pathway based on the single-electron characteristics of the vanadium-oxygen cluster.

[0054] In this embodiment, the isoelectric point of the Ag / V-MOF-derived material ranges from 10.7, and the specific surface area ranges from 3.6027 m². 2 / g.

[0055] Example 2: This example describes the preparation method of an anti-interference silver-vanadium bimetallic-organic framework derived material.

[0056] S1. Preparation of AgV-MOF materials;

[0057] S1-1. First, add tris(4-(1H-1,2,4-triimidazole)phenyl)amine, ammonium metavanadate and silver nitrate to pure water and mix well to obtain the first mixture. Then adjust the pH of the first mixture to 3.5.

[0058] When the amount of tris(4-(1H-1,2,4-triimidazole)phenyl)amine added in S1-1 is 0.1 mol, the amount of ammonium metavanadate added is 0.6 mol, the amount of silver nitrate added is 0.5 mol, and the amount of pure water added is 10 L.

[0059] S1-2. The mixture in S1-1 was reacted at 150℃ for 48h. After the reaction was completed, the temperature was lowered to room temperature at a rate of -10℃ / h to obtain a two-dimensional twisted wave layered AgV-MOF material.

[0060] S2. Preparation of Ag / V-MOF derivative materials;

[0061] S2-1. First, grind and crush the AgV-MOF material in S1-1, then disperse it evenly in pure water and ultrasonically vibrate for 10 minutes. Then, add 3M NaOH solution and stir continuously for 1 hour to obtain the second mixture.

[0062] When the amount of AgV-MOF material added in S2-1 is 10g, the amount of pure water added is 1L, and the amount of 3M NaOH solution added is 1L.

[0063] S2-2. First, filter the second mixture to obtain filter residue. Wash the filter residue with pure water until the washing liquid is neutral. Then, dry the washed filter residue at 60°C for 1.5 hours to obtain Ag / V-MOF derived material, namely, anti-interference silver-vanadium bimetallic-organic framework derived material.

[0064] Specifically, the cell structure of the AgV-MOF material prepared in S1 is as follows:

[0065]

[0066] The unit cell is an asymmetric structural unit containing one silver atom, three vanadium atoms, one tris(4-(1H-1,2,4-triimidazole)phenyl)amine and eight oxygen atoms;

[0067] The silver atom has a coordination number of 2 and exhibits a linear structure, coordinating with two N atoms from tris(4-(1H-1,2,4-triimidazole)phenyl)amine;

[0068] One vanadium atom adjacent to tris(4-(1H-1,2,4-triimidazole)phenyl)amine forms a {VNO4} tetragonal pyramidal vanadium-oxygen cluster, while the two vanadium atoms furthest from tris(4-(1H-1,2,4-triimidazole)phenyl)amine coordinate with oxygen atoms to form a {VO4} tetrahedral vanadium-oxygen cluster.

[0069] Specifically, the Ag / V-MOF-derived material prepared in S2 has a two-dimensional twisted wavy layered structure with wrinkled surface and possesses bimetallic complex characteristics: silver ions and vanadium ions can be bridged by tris(4-(1H-1,2,4-triimidazole)phenyl)amine as an organic ligand, forming an electron transfer pathway based on the single-electron characteristics of the vanadium-oxygen cluster.

[0070] In this embodiment, the isoelectric point of the Ag / V-MOF-derived material ranges from 10.6 to 1.7766 m². 2 / g.

[0071] Experimental Example: The description of this experimental example is based on the scheme described in Example 1, and aims to illustrate the practical application effect of the present invention.

[0072] 1) Cell parameters

[0073] The AgV-MOF material prepared in Example 1 belongs to the triclinic crystal system, space group P-1, and its unit cell volume is... The length of the unit cell is: The angles of the unit cell are: α = 73.2775°, β = 79.4578°, γ = 78.4595°.

[0074] 2) Adsorption performance

[0075] The specific procedure for using the Ag / V-MOF derivative material prepared in Example 1 to directly adsorb and remove creatinine (CA) from water is as follows:

[0076] To compare the adsorption performance of Ag / V-MOF-derived materials at different dosages, the following experimental group was designed:

[0077] Group A: 25 mg / L, Group B: 50 mg / L, Group C: 75 mg / L, Group D: 100 mg / L, Group E: 125 mg / L, Group F: 150 mg / L.

[0078] According to the experimental design, Ag / V-MOF derivative material was weighed and placed in a reactor, and 50 mL of CA solution was added. The adsorption experiment was carried out in a constant temperature water bath shaker at 180 rpm / min and 45℃. Every once in a while, 2 mL of the reaction solution was taken and filtered through a 0.22 μm filter membrane. The experiment lasted for 180 min.

[0079] Its concentration change was determined using high-performance liquid chromatography (HPLC). The degradation rate is calculated using the formula, where c0 and ct are the mass concentrations of the solution before and after adsorption, respectively, in mg / L, and qt is the adsorption amount, in mg / g.

[0080] When the Ag / V-MOF-derived material prepared in Example 1 was used to adsorb CA, the adsorption capacity of group F reached 140 mg / g after 180 min (see Example 1). Figure 4 ).

[0081] 2) The applicable pH range for Ag / V-MOF derived materials

[0082] 1) When Ag / V-MOF derivatives adsorbed creatinine, the pH range of the reaction system solution was adjusted to 3–11, verifying that the Ag / V bimetallic MOF derivatives could still exhibit good adsorption and removal effects within the range of 5–11 (see [link to relevant documentation]). Figure 7 ).

[0083] 3) Material anti-interference performance

[0084] 1) Add 10 mmol / L interfering ions during the adsorption of CA by the Ag / V-MOF-derived material: And 10 mg / L humic acid (HA); the material still maintains good adsorption performance when interfering substances are present alone or in mixtures, proving that the material has strong anti-interference ability (see...). Figures 5-6 ).

[0085] 4) Material recyclability

[0086] After each experimental run, the Ag / V-MOF-derived material was separated from the reaction solution for reusability testing. The material was recycled five times, and its adsorption capacity for CA still reached 90 mg / g (see [reference]). Figure 8 ).

Claims

1. An anti-interference silver-vanadium bimetallic-organic framework derived material, characterized in that, The aforementioned anti-interference silver-vanadium bimetallic-organic framework derived material is referred to as an Ag / V-MOF derived material. This Ag / V-MOF derived material is prepared based on AgV-MOF material through alkaline treatment. The cell structure of the AgV-MOF material is as follows: The unit cell is an asymmetric structural unit containing one silver atom, three vanadium atoms, one tris(4-(1H-1,2,4-triimidazole)phenyl)amine and eight oxygen atoms; The silver atoms have a coordination number of 2 and exhibit a linear structure, coordinated with two N atoms from tris(4-(1H-1,2,4-triimidazole)phenyl)amine; One vanadium atom of the three vanadium atoms adjacent to tris(4-(1H-1,2,4-triimidazole)phenyl)amine forms a {VNO4} tetragonal pyramidal vanadium-oxygen cluster, while the two vanadium atoms far from tris(4-(1H-1,2,4-triimidazole)phenyl)amine coordinate with oxygen atoms to form a {VO4} tetrahedral vanadium-oxygen cluster.

2. The anti-interference silver-vanadium bimetallic-organic framework derived material as described in claim 1, characterized in that, The AgV-MOF material belongs to the triclinic crystal system, space group P-1, and its unit cell volume is... The length of the unit cell is: The angles of the unit cell are: α = 73.2775°, β = 79.4578°, γ = 78.4595°.

3. The anti-interference silver-vanadium bimetallic-organic framework derived material as described in claim 1, characterized in that, The Ag / V-MOF-derived material has a two-dimensional twisted wave-like layered structure with wrinkles on its surface and possesses bimetallic complex characteristics: silver ions and vanadium ions can be bridged by tris(4-(1H-1,2,4-triimidazole)phenyl)amine as an organic ligand, forming an electron transfer pathway based on the single-electron characteristics of the vanadium-oxygen cluster.

4. A method for preparing anti-interference silver-vanadium bimetallic-organic framework derived materials, characterized in that, The preparation method for preparing the Ag / V-MOF derivative material as described in claim 1 includes the following steps: S1. Preparation of AgV-MOF materials; S1-1. First, add tris(4-(1H-1,2,4-triimidazole)phenyl)amine, ammonium metavanadate and silver nitrate to pure water and mix evenly to obtain the first mixture. Then adjust the pH of the first mixture to 3.

5. Let n be the multiplier and n∈R + When the amount of tris(4-(1H-1,2,4-triimidazole)phenyl)amine added to S1-1 is 1 nmol, the amount of ammonium metavanadate added is [4.5n,6n] mol, the amount of silver nitrate added is [3n,5n] mol, and the amount of pure water added is [9n,10n] L. S1-2. The mixture in S1-1 is reacted at 150℃ for 48-96h. After the reaction is completed, the temperature is lowered to room temperature at a rate of -10℃ / h to obtain a two-dimensional twisted wave layered AgV-MOF material. S2. Preparation of Ag / V-MOF derivative materials; S2-1: First, grind and crush the AgV-MOF material in S1-1, then disperse it evenly in pure water and ultrasonically vibrate it for 10-20 minutes. Then, add 3M NaOH solution and stir continuously for 1-1.5 hours to obtain the second mixture. Let n be the multiplier and n∈R + When the amount of AgV-MOF material added in S2-1 is 1n g, the amount of pure water added is [100n, 110n] mL, and the amount of 3M NaOH solution added is [100n, 110n] mL. S2-2. First, filter the second mixture to obtain filter residue. Wash the filter residue with pure water until the washing liquid is neutral. Then, dry the washed filter residue at 60°C for 1.5 to 2 hours to obtain Ag / V-MOF derivative material.

5. Application of anti-interference silver-vanadium bimetallic-organic framework derived materials, based on the Ag / V-MOF derived material of claim 1, characterized in that, The Ag / V-MOF derivative material is used to adsorb creatine anhydride in wastewater.

6. The application of the anti-interference silver-vanadium bimetallic-organic framework derived material as described in claim 5, characterized in that, In an interfering environment, the Ag / V-MOF-derived material is used to adsorb creatine anhydride from wastewater, wherein the interfering environment includes... And one or more interfering substances in humic acid.

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