CN111992185A - Cu-MOF, modified adsorption material thereof and preparation method - Google Patents
Cu-MOF, modified adsorption material thereof and preparation method Download PDFInfo
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Abstract
The invention mainly relates to the technical field of metal organic framework materials, and particularly discloses a Cu-MOF (metal organic framework) and a modified adsorption material and a preparation method thereof. The preparation method of the modified Cu-MOF comprises the following steps: placing Cu-MOF in Fe-containing3+And Fe2+In the solution, modifying the Cu-MOF to prepare modified Cu-MOF; the specific surface area of the modified Cu-MOF is more than or equal to 150.85m2(ii)/g; the maximum adsorption amount of the modified Cu-MOF prepared by the method to As (III) is 66.12mg/g, and the modified Cu-MOF has excellent heavy metal ion adsorption performance.
Description
Technical Field
The invention mainly relates to the technical field of metal organic framework materials, and particularly relates to a Cu-MOF (metal organic framework) and a modified adsorption material and a preparation method thereof.
Background
Heavy metal pollution is an environmental problem which is difficult to avoid in the current industrial development process, heavy metal is not biodegradable and has bioaccumulation, and even if the concentration is low, the heavy metal has high toxicity and irreversible harm to the ecological environment. None of the Japanese Water ensures disease events, osteodynia events, and Shimen arsenic contamination events, etc., do not sound our alarm clock.
Metal organic framework Materials (MOFs) are a new emerging heavy metal ion adsorbing material, and since the first report on the adsorption properties of MOF materials by the Kitagawa research group in 1997, a large number of coordination polymers have been used as porous adsorbing materials. Due to the different surface structures of MOFs, their ability to remove heavy metal ions is also different. Thus, MOFs are typically modified to increase specific surface area, to add effective functional groups, to enhance hydrophobic/hydrophilic properties and surface charge, thereby increasing their adsorption capacity for heavy metal ions.
The pollution situation of As (III) in heavy metal ions is particularly severe, related papers report in the prior art, but the adsorption effect of the MOF adsorption material for As (III) is limited at present, for example, ZHEN adopts GUT-3 to adsorb the maximum adsorption amount of As being 33.91mg/g, Li Z-Q adopts MOF-808 to adsorb the maximum adsorption amount of As being 24.83mg/g, Vu T adopts MIL-53(Fe) to adsorb the maximum adsorption amount of As being 21.3mg/g, so that the preparation of the MOF material with excellent adsorption performance for heavy metal ions is an urgent need; for example, patent (CN111004398A) discloses a microporous Cu-MOF material, and a preparation method and application thereof, wherein a Cu-MOF material is disclosed, which has a chemical formula of CuTIPA N (DMF) (N ═ 1-3), wherein TIPA 2-is 5- (triazol-1-yl) isophthalic acid anion, and DMF is N, N-dimethylformamide, but the microporous Cu-MOF material has a limited adsorption capacity for heavy metals in a liquid.
Disclosure of Invention
1. Problems to be solved
The invention aims to solve the technical problems of small specific surface area and poor heavy metal ion adsorption effect of MOF materials in the prior art, and provides a Cu-MOF, a modified adsorption material and a preparation method thereof. The maximum adsorption amount of the modified Cu-MOF of the invention to As (III) is 66.12mg/g, which is higher than the adsorption amount of MOF materials developed at present to arsenic, such As GUT-3 maximum adsorption amount of 33.91mg/g, MOF-808 maximum adsorption amount of 24.83mg/g, and MIL-53(Fe) maximum adsorption amount of 21.3 mg/g.
2. Technical scheme
The invention provides a preparation method of a modified Cu-MOF adsorption material, and particularly relates to a method for placing Cu-MOF in a Fe-containing material3+And Fe2+In the solution, modifying the Cu-MOF to prepare modified Cu-MOF; the specific surface area of the modified Cu-MOF is more than or equal to 150.85m2(ii) in terms of/g. Using Fe3+And Fe2+The modification of Cu-MOF materials is mainly to convert Fe3+And Fe2+And S is simultaneously loaded on the Cu-MOF material, so that the specific surface area and the adsorption performance of the material are greatly improved.
Preferably, the ligand of the Cu-MOF is 5-bromosalicylaldehyde 4-amino-1, 2, 4-triazole.
Preferably, the method comprises the following specific steps:
step one, preparing Fe-containing3+And Fe2+Adding Cu-MOF into the solution, stirring, and loading two ions on the material;
step two, adding an alkaline reagent into the system obtained in the step one, and adjusting the pH of the solution to 10-11 to ensure that two iron ions form Fe (OH)2And Fe (OH)3Loaded on the material;
step three, adding NH into the system obtained in the step two4A Cl solution; stirring the system;
and step four, sequentially filtering, washing and drying the system obtained in the step three to obtain the modified Cu-MOF adsorbing material.
Preferably, the Fe is contained in the first step3+And Fe2+The solution of (A) comprises one or more of sulfate, nitrate, chloride and perchlorate;
and/or the alkaline reagent in the step two is one or more of an alkaline solution and a strong base weak acid salt solution.
Preferably, the stirring temperature in the first step is 45-65 ℃, and the stirring time is 20-40 min;
and/or the stirring temperature in the third step is 70-90 ℃, and the stirring time is 1.5-2.5 h;
and/or the drying temperature in the fourth step is 50-60 ℃.
Preferably, the detailed steps are as follows:
adding 25.00-50.00mL of 0.3-0.5mol/L ferric sulfate solution and 100-200mL of 0.04-0.08mol/L ferrous sulfate solution into a beaker containing 10.00-20.00g of the Cu-MOF, stirring for 20-40min at 45-65 ℃, adding 8-12mol/L sodium hydroxide solution, adjusting the pH value of the solution to 10-11, then adding 400mL of 0.04-0.06mol/L ammonium chloride solution, stirring for 1.5-2.5h at 70-90 ℃, filtering and washing precipitates to be neutral, and drying at 50-60 ℃ to obtain the modified Cu-MOF adsorbing material.
The invention also provides the modified Cu-MOF adsorbing material prepared by any one of the preparation methods.
The invention also provides a preparation method of the modified Cu-MOF, which comprises the following steps: dissolving the 5-bromosalicylaldehyde condensed 4-amino-1, 2, 4-triazole ligand and copper ion salt in a solvent, and heating to prepare the Cu-MOF.
Preferably, the detailed steps are as follows:
weighing 0.15-0.30g of 5-bromosalicylaldehyde 4-amino-1, 2, 4-triazole ligand and 0.121-0.242g of copper nitrate trihydrate, placing the mixture in a reaction bottle, adding 3-6mL of DMF and 3-6mL of secondary distilled water, stirring for 10-20min, screwing the reaction bottle cap, placing the reaction bottle in an oven at 80-100 ℃ for standing for 24-48h to obtain dark green needle crystals, filtering the dark green needle crystals, washing the filtered dark green needle crystals with distilled water, and drying to obtain the Cu-MOF.
The invention also provides the Cu-MOF prepared by any one of the preparation methods, and the main coordination modes are as follows:
the Cu-MOF consists of seven Cu atoms, four deprotonated 5-bromosalicylaldehyde 4-amino-1, 2, 4-triazole ligands and six water molecules. Cu1 coordinates with N3, N4, N7 from three ligands and O2, O3 from two water molecules, forming a four coordinate plane configuration. The coordination environment of Cu3 and Cu3a is the same as Cu 1. Cu2 coordinates with O1, O1a, N1, N1a from two ligands, forming a penta-coordinate tetragonal pyramid configuration. The coordination environment of Cu2a, Cu4, and Cu4a is the same as Cu 2.
3. Advantageous effects
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention relates to a modified Cu-MOF adsorption material, which adopts Fe3+And Fe2+Doping of the Cu-MOF material may be to Fe3+And Fe2+The modified Cu-MOF is loaded on the surface of the material in an ion form, so that the specific surface area of the Cu-MOF material is favorably enlarged, and a complex is more easily formed with heavy metal ions to achieve the effect of removing the heavy metal ions, compared with the existing material, the maximum adsorption amount of the modified Cu-MOF to As (III) is 66.12mg/g, which is higher than the adsorption amount of the MOF material developed at present to arsenic, such As GUT-3 maximum adsorption amount of 33.91mg/g, MOF-808 maximum adsorption amount of 24.83mg/g, and MIL-53(Fe) maximum adsorption amount of 21.3 mg/g.
(2) The modified Cu-MOF adsorption material provided by the invention adopts 5-bromosalicylaldehyde 4-amino-1, 2, 4-triazole as a ligand, so that on one hand, a spatial network structure with the pore diameter of about 11.93nm can be formed for subsequent Fe loading3+And Fe2+Provides a certain structural foundation, thereby realizing the preparation of the modified Cu-MOF adsorbing material with high specific surface area, and the specific surface area of the modified Cu-MOF adsorbing material is from 7.16m2Increase in g to 150.85m2(ii)/g; on the other hand, the bromine contained in the catalyst can replace heavy metal ions As (III) in the presence of Fe3+And Fe2+The substitution rate of the modified metal ion can reach 71.3 percent, and the modified metal ion has excellent heavy metal ion adsorption performance.
(3) The preparation method of the modified Cu-MOF adsorption material has the advantages of simple process, low cost, easy control of chemical components, good repeatability, high yield and the like.
Drawings
FIG. 1 is a diagram of the application of modified Cu-MOF in the invention to remove As (III) by adsorption.
FIG. 2 is SEM scanning electron micrographs of Cu-MOF (left) and modified Cu-MOF (middle) of the invention and modified Cu-MOF (right) adsorbing As (III)
FIG. 3 is EDS energy spectra of Cu-MOF (left) and modified Cu-MOF (middle) of the present invention and modified Cu-MOF (right) adsorbing As (III).
FIG. 4 shows XPS survey spectra and As (III) fine spectra before and after adsorption of As (III) by the modified Cu-MOF of the present invention.
FIG. 5 shows the adsorption rates of As (III) by modified Cu-MOF, Cu-MOF and Cu-MOF-2 at different pH values.
Detailed Description
Example one
The embodiment provides a preparation method of a Cu-MOF material, which specifically comprises the following steps:
weighing 0.20g of 5-bromosalicylaldehyde 4-amino-1, 2, 4-triazole ligand and 0.16g of copper nitrate trihydrate, placing the mixture in a 20mL micro-reaction bottle, adding 5mL of DMF (dimethyl formamide) and 4mL of secondary distilled water, stirring for 10min, screwing a reaction bottle cover, placing the reaction bottle cover in an oven at 80 ℃, standing for 24h to obtain dark green needle crystals, filtering the dark green needle crystals, washing the filtered dark green needle crystals with distilled water, and drying to obtain the Cu-MOF.
This example also provides a Cu-MOF prepared by the preparation method described above, wherein the pore size of the Cu-MOF is about 11.93nm by detecting the XRD pattern and calculating.
The embodiment provides a preparation method of a modified Cu-MOF adsorption material, which specifically comprises the following steps:
adding 30.00mL of 0.4mol/L ferric sulfate solution and 150mL of 0.06mol/L ferrous sulfate solution into a beaker containing 15.00g of the Cu-MOF, stirring at 55 ℃ for 30min, adding 10mol/L sodium hydroxide solution, adjusting the pH value of the solution to be 11, then adding 300mL of 0.05mol/L ammonium chloride solution, stirring at 80 ℃ for 2h, filtering and washing the precipitate to be neutral, and drying at 60 ℃ to obtain the modified Cu-MOF adsorbing material.
The embodiment also provides the modified Cu-MOF adsorbing material prepared by the preparation method.
In order to explore the maximum adsorption capacity of the modified Cu-MOF on As (III), different initial arsenic ion concentrations are set in the embodiment, As shown in FIG. 1, researches show that the modified Cu-MOF has excellent adsorption performance on As (III), the maximum adsorption capacity is 66.12mg/g, and is higher than that of currently developed MOF materials, such As GUT-3 maximum adsorption capacity of 33.91mg/g, MOF-808 maximum adsorption capacity of 24.83mg/g, and MIL-53(Fe) maximum adsorption capacity of 21.3 mg/g.
Comparative example 1
The comparative example provides a preparation method of a Cu-MOF material, and the specific preparation method is the same as that of the first example.
The comparative example also provides the Cu-MOF prepared by the preparation method, which is different from the first example in that the Cu-MOF is not subjected to subsequent modification treatment, but is directly subjected to various performance tests.
The specific surface areas of Cu-MOF (comparative example I) and modified Cu-MOF (example I) are detected by using a BET method, the specific data are shown in Table 1, and the specific surface area of Cu-MOF before modification is 7.16m2G, and the specific surface area of the modified Cu-MOF material is 150.85m2The specific surface area of the modified Cu-MOF material is increased by 20 times compared with that of the Cu-MOF material, and the modified Cu-MOF material is more beneficial to adsorbing and removing heavy metal ions.
In order to compare the change of the surface morphology of the Cu-MOF before and after modification and the adsorption of the modified Cu-MOF to As (III), the analysis of SEM, EDS and XPS is carried out on the Cu-MOF before modification (comparative example I), the modified Cu-MOF (example I) and the modified Cu-MOF material after adsorption of As (III) by adopting a JMS-7900 type scanning electron microscope, and the results are shown in FIGS. 2, 3 and 4:
from the SEM image in FIG. 2, it can be seen that the morphology of the material surface before and after modification is obviously changed, after the Cu-MOF before modification is modified, the smooth surface becomes wrinkled, rough and porous, such a porous structure provides a certain structural basis for the adsorption of As (III), and the modified Cu-MOF material surface after the adsorption of As (III) becomes smoother, which is probably because As (III) is adsorbed onto the pores and the rough surface, thereby reducing the roughness of the material;
from the EDS analysis in fig. 3, it can be seen that the modified Cu-MOF has significantly more Fe, S and Cl elements than the Cu-MOF, which proves that the modified Cu-MOF successfully loads the Fe, S and Cl elements on the surface of the Cu-MOF material, and the modified Cu-MOF material after adsorbing As (iii) has significantly more As elements than before modification, which proves that As (iii) is successfully adsorbed into the modified Cu-MOF material;
from the XPS analysis of fig. 4, it can be seen that similar results to EDS occurred with the appearance of Cu 2p, C1 s, N1 s, O1 s, Br 3d in XPS wide scan spectra of Cu-MOF before modification; the XPS broad scanning spectrum of the modified Cu-MOF increases the peaks of Fe 2p, Cl 2p and S2 p; as3d peak is added in the wide scanning spectrum of the modified Cu-MOFXPS after the adsorption of As (III), which confirms that the As (III) is adsorbed to the modified Cu-MOF.
Comparative example No. two
The comparative example provides a preparation method of a Cu-MOF material, which is basically the same as the first example, and is different from the first example in that:
immersing the synthesized prepared Cu-MOF into an ammonium ferrous sulfate solution with the concentration of 0.14mol/L, wherein the ratio of the Cu-MOF to the ammonium ferrous sulfate is 5: and 4, performing ultrasonic treatment at normal temperature for 20min, then taking out, filtering and washing the precipitate to be neutral, and drying at 60 ℃ to obtain the sample Cu-MOF-2.
The comparative example also provides a Cu-MOF prepared by the preparation method.
In order to verify that the two ferric ion modified Cu-MOFs of the invention have excellent adsorption performance, the adsorption rates of the modified Cu-MOF (example I) prepared by modifying two ferric ions, the unmodified Cu-MOF (comparative example I) and the Cu-MOF-2 (comparative example II) prepared by modifying ferrous ions on As (III) at different pH values are respectively compared, and the specific test method comprises the following steps: the initial concentration of the As (iii) -containing solution was set at 10mg/L, the amount of adsorbent added was selected to be 0.1g/25mL, the adsorption temperature T was 25 ℃, the adsorption time T was 24h, the rotational speed of the shaker was 180r/min, and the pH of the solution was adjusted with HCl and NaOH solutions, the results of which are shown in fig. 5.
As can be seen from FIG. 5, the modified two types of iron ions at a pH value in the range of 3 to 11The adsorption rate of the modified Cu-MOF to As (III) is basically maintained to be more than 95 percent, which is much higher than the adsorption rate of the Cu-MOF-2 prepared by the unmodified Cu-MOF and ferrous ion modification to As (III), and the result shows that the adsorption effect of the Cu-MOF material modified by two ferric ions is better than that of the Cu-MOF material before modification, and simultaneously better than that of single Fe2+A modified Cu-MOF-2 material;
meanwhile, the adsorption rate of the modified Cu-MOF material to As (III) is obviously improved within the pH range of 3-10, the modified Cu-MOF material is the highest value when the pH value reaches 11, and the adsorption capacity of the modified Cu-MOF material is gradually reduced after the pH value exceeds 11, so that the effective adsorption pH range of the modified Cu-MOF material to As (III) is 3-11, and the adsorption performance is optimal when the pH value is 11.
In addition, EDS analysis shows that the percentage of Br after adsorption is obviously reduced, probably due to the fact that Br is replaced by As (III), the data of the specific substitution rate of As to Br are shown in table 1, and the substitution rate of As to Br of the modified Cu-MOF is As high As 71.3 percent and is far higher than that of Cu-MOF and Cu-MOF-2 before modification, so that the modified Cu-MOF shows excellent As (III) adsorption performance.
Table 1 comparison of effects
| Example one | Comparative example 1 | Comparative example No. two | |
| Kind of adsorbent | Modified Cu-MOF | Cu-MOF | Cu-MOF-2 |
| Specific surface area (m)2/g) | 150.85 | 7.16 | — |
| Substitution rate of As for Br | 71.3％ | 23.0％ | 39.8％ |
The invention has been described in detail hereinabove with reference to specific exemplary embodiments thereof. It will, however, be understood that various modifications and changes may be made without departing from the scope of the invention as defined in the appended claims. The detailed description and drawings are to be regarded as illustrative rather than restrictive, and any such modifications and variations are intended to be included within the scope of the present invention as described herein. Furthermore, the background is intended to be illustrative of the state of the art as developed and the meaning of the present technology and is not intended to limit the scope of the invention or the application and field of application of the invention.
More specifically, although exemplary embodiments of the invention have been described herein, the invention is not limited to these embodiments, but includes any and all embodiments modified, omitted, combined (e.g., between various embodiments), adapted and/or substituted as would be recognized by those skilled in the art from the foregoing detailed description, and which may be combined as desired. The limitations in the claims are to be interpreted broadly based the language employed in the claims and not limited to examples described in the foregoing detailed description or during the prosecution of the application, which examples are to be construed as non-exclusive. Any steps recited in any method or process claims may be executed in any order and are not limited to the order presented in the claims. The scope of the invention should, therefore, be determined only by the appended claims and their legal equivalents, rather than by the descriptions and examples given above.
Claims (10)
1. A preparation method of a modified Cu-MOF adsorption material is characterized in that Cu-MOF is placed in a Fe-containing state3+And Fe2+In the solution, modifying the Cu-MOF to prepare modified Cu-MOF; the specific surface area of the modified Cu-MOF is more than or equal to 150.85m2/g。
2. The preparation method of the modified Cu-MOF adsorption material according to claim 1, wherein a ligand of the Cu-MOF is 5-bromosalicylaldehyde 4-amino-1, 2, 4-triazole.
3. The preparation method of the modified Cu-MOF adsorption material according to claim 1, characterized by comprising the following specific steps:
step one, preparing Fe-containing3+And Fe2+Adding Cu-MOF into the solution, stirring, and loading two ions on the material;
step two, adding an alkaline reagent into the system obtained in the step one, and adjusting the pH of the solution to 10-11 to ensure that two iron ions form Fe (OH)2And Fe (OH)3Loaded on the material;
step three, adding NH into the system obtained in the step two4A Cl solution; stirring the system;
and step four, sequentially filtering, washing and drying the system obtained in the step three to obtain the modified Cu-MOF adsorbing material.
4. The method for preparing the modified Cu-MOF adsorbing material according to claim 3, wherein the Fe content in the first step3+And Fe2+The solution of (A) comprises one or more of sulfate, nitrate, chloride and perchlorate;
and/or the alkaline reagent in the step two is one or more of an alkaline solution and a strong base weak acid salt solution.
5. The preparation method of the modified Cu-MOF adsorption material according to claim 3, characterized in that in the first step, the stirring temperature is 45-65 ℃, and the stirring time is 20-40 min;
and/or the stirring temperature in the third step is 70-90 ℃, and the stirring time is 1.5-2.5 h;
and/or the drying temperature in the fourth step is 50-60 ℃.
6. The method as claimed in any one of claims 1 to 5, wherein 25.00 to 50.00mL of 0.3 to 0.5mol/L ferric sulfate solution and 100 mL of 0.04 to 0.08mol/L ferrous sulfate solution are added into a beaker containing 10.00 to 20.00g of the Cu-MOF, and after stirring for 20 to 40min at 45 to 65 ℃, 8 to 12mol/L of sodium hydroxide solution is added to adjust the pH of the solution to 10 to 11, and then 200mL of 0.04 to 0.06mol/L ammonium chloride solution is added and stirred for 1.5 to 2.5h at 70 to 90 ℃, and the precipitate is filtered, washed to be neutral and dried at 50 to 60 ℃ to obtain the modified Cu-MOF adsorbing material.
7. A modified Cu-MOF adsorption material, which is characterized in that the modified Cu-MOF adsorption material is prepared by the preparation method of any one of claims 1 to 6.
8. The preparation method of the modified Cu-MOF adsorption material according to claim 1, wherein the preparation method of the pre-modified Cu-MOF is as follows: dissolving the 5-bromosalicylaldehyde condensed 4-amino-1, 2, 4-triazole ligand and copper ion salt in a solvent, and heating to prepare the Cu-MOF.
9. The preparation method of the modified Cu-MOF adsorption material according to claim 8, wherein 0.15-0.30g of 5-bromosalicylaldehyde 4-amino-1, 2, 4-triazole ligand and 0.121-0.242g of copper nitrate trihydrate are weighed and placed in a reaction bottle, 3-6mL of DMF and 3-6mL of secondary distilled water are added and stirred for 10-20min, the reaction bottle cap is screwed and placed in an oven with the temperature of 80-100 ℃ for standing for 24-48h to obtain dark green needle crystals, and the dark green needle crystals are filtered, washed with distilled water and dried to obtain the Cu-MOF.
10. A Cu-MOF, characterized in that it is produced by the process of any one of claims 8 to 9.
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