CN108948368B - Method for rapidly preparing nickel-based metal organic framework material - Google Patents
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- CN108948368B CN108948368B CN201810818736.8A CN201810818736A CN108948368B CN 108948368 B CN108948368 B CN 108948368B CN 201810818736 A CN201810818736 A CN 201810818736A CN 108948368 B CN108948368 B CN 108948368B
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Abstract
The invention discloses a method for rapidly preparing a nickel-based metal organic framework material, which comprises the steps of adding nickel acetate tetrahydrate and trimesic acid into a reaction container, adding a ball milling ball and water, sealing the reaction container, carrying out ball milling at 25 Hz-50 Hz, cleaning and drying an obtained product, and thus obtaining the nickel-based metal organic framework material. The method is green, environment-friendly and efficient, the required product can be obtained within 1 minute at the fastest speed, the obtained product has better capacitance performance, and the high capacitance of 640F/g can be shown under the current density of 1A/g.
Description
Technical Field
The invention belongs to the field of metal organic framework material preparation, relates to a method for rapidly preparing a nickel-based metal organic framework material, and particularly relates to Ni3(BTC)212H2And (3) rapidly preparing O.
Background
Metal organic framework Materials (MOFs) have attracted considerable attention due to their attractive structural properties and have potential applications in gas storage, separation, catalysis and sensing. Recently, MOFs have been demonstrated due to their significant surface area, tunable pore size, controllable microporous structure and special structure with potential pseudocapacitive redox centersUseful electrochemical energy storage and is considered to be one of the most promising candidates for electrode materials. Among them, nickel-based MOFs, especially Ni3(BTC)2·12H2O (BTC ═ 1,3, 5-benzenetricarboxylic acid) has gained increasing attention, not only proving to have strong application prospects for supercapacitors, but also having templates/precursors for unique metal oxides and carbon materials of specific structures. For example, Kong's panel demonstrated hydrothermally synthesized Ni3(BTC)2·12H2O has a high specific capacitance of 726F/g. Wang et al prepared mesoporous metal oxides by calcining precursors in air using Ni-MOF as precursors, the prepared NiO had high capacitance retention at high scan rates and had special mesoporous characteristics of bimodal size distribution due to its excellent cycle life stability. Ni for Chen et al3(BTC)2·12H2And O is used as a precursor to synthesize the large-scale multi-wall carbon nano-tube. However, the synthesis of Ni-MOFs usually requires volume of solvent, high temperature and long reaction time. For example, Wang et al synthesized Ni in a Teflon lined stainless steel autoclave3(BTC)2·12H2O and heated at 200 ℃ for 24h, Du et al synthesized Ni-BTC MOF, lined in a polytetrafluoroethylene autoclave and heated to 150 ℃ in DMF for 12 h, Kong's group prepared Ni-MOF in DMF at a lower temperature of 105 ℃ but taking longer (up to 2 days). Although Jin et al describe the synthesis of Ni at room temperature in a short time3(BTC)2·12H2O, but the organic linker must be deprotonated beforehand and large amounts of organic solvents must also be used. Therefore, there is a great need for a simple, green, fast and energy-efficient process (neither requiring high temperatures nor large amounts of solvents) for the preparation of nickel-based MOFs.
Mechanochemistry, i.e., chemical synthesis achieved or maintained by mechanical forces, has been introduced as an alternative to conventional MOF synthesis. Although mechanochemical synthesis of MOFs avoids bulk solvents, high temperatures and/or corrosive reagents commonly used in solution synthesis, Pichon and James have investigated different nickel salts and H under mechanochemical solvent-free conditions3A reaction between BTCs, andno success was achieved.
Recently, there have been some reports on rapid synthesis methods of MOFs. For example, Duan et al rapidly synthesized a hierarchical porous ZIF-8 material at room temperature within 1 minute by using an organic amine as a hyper-molecular template (organic amine template), but still required a large amount of organic solvent (methanol) and additives (organic amine). Jin et al synthesized Ni by a simple solution phase method at room temperature for a short time (5min)3(BTC)2·12H2O, but the organic linker must be deprotonated in advance and an organic solvent is used. Huang et al reported the synthesis of F within 100s using water-assisted milling4-UiO-66, however, the metal source must be a pre-prepared zirconium-oxygen pre-assembled cluster. Despite these developments, it should be noted that no method exists for the rapid synthesis of Ni-MOF without the use of large amounts of solvents or any prior preparation techniques.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and particularly aims at the problems of long time consumption, large solvent consumption, pre-reaction and the like in the conventional nickel-based MOFs (metal organic framework) method, and provides a method for quickly preparing a nickel-based metal organic framework material (Ni-MOF) by a water-assisted grinding method, wherein the method is green, environment-friendly and efficient, the required product can be obtained within 1 minute at the fastest speed, the obtained product has better capacitance performance, and the high capacitance of 640F/g is shown under the current density of 1A/g.
In order to solve the technical problems, the invention adopts the following technical scheme.
A method for rapidly preparing a nickel-based metal organic framework material comprises the following steps:
adding nickel acetate tetrahydrate and trimesic acid into a reaction container as reactants, adding ball milling balls and water, sealing the reaction container, carrying out ball milling at 25 Hz-50 Hz, cleaning and drying the obtained product to obtain the nickel-based metal organic framework material, namely Ni3(BTC)2·12H2O。
In the method for rapidly preparing the nickel-based metal organic framework material, the mass ratio of the water to the reactant is preferably 0.01-0.8: 1.
In the method for rapidly preparing the nickel-based metal organic framework material, preferably, the mass ratio of the nickel acetate tetrahydrate to the trimesic acid is 0.2-5: 1, namely 1: 5-5: 1.
In the method for rapidly preparing the nickel-based metal organic framework material, the mass ratio of the ball grinding balls to the reactants is preferably 10-20: 1.
In the above method for rapidly preparing the nickel-based metal organic framework material, preferably, the diameter of the ball grinding ball is 3mm to 15mm, and the number of the particles of the ball grinding ball is 2 to 8.
In the above method for rapidly preparing a nickel-based metal organic framework material, preferably, the reaction vessel comprises an agate tank or a zirconia tank; the ball grinding balls comprise agate balls or zirconium balls.
In the method for rapidly preparing the nickel-based metal organic framework material, the ball milling time is preferably 1min to 180 min.
In the above method for rapidly preparing the nickel-based metal organic framework material, preferably, the cleaning is performed by respectively cleaning with ethanol and water for 2 to 4 times.
In the method for rapidly preparing the nickel-based metal organic framework material, preferably, the drying temperature is 30-120 ℃, and the drying time is 2-24 hours.
Compared with the prior art, the invention has the advantages that:
(1) the method is very quick, can obtain the product in 1 minute at the fastest speed, and is very efficient.
(2) The method does not need to use an organic solvent, can complete the reaction by only using a very small amount of water, and is green and environment-friendly.
(3) The method provided by the invention can be carried out after mixing the raw materials without carrying out any preliminary reaction.
Drawings
FIG. 1 shows Ni in example 13(BTC)2·12H2Infrared spectrum of O.
FIG. 2 isNi in example 13(BTC)2·12H2XRD pattern of O.
FIG. 3 shows Ni in example 13(BTC)2·12H2SEM photograph of O (2 ten thousand magnification on the left, 6 ten thousand magnification on the right).
FIG. 4 shows Ni in example 13(BTC)2·12H2Nitrogen adsorption desorption curve of O.
FIG. 5 shows Ni in example 13(BTC)2·12H2Constant current charge and discharge curve of O under the condition of 1A/g.
FIG. 6 shows Ni in example 23(BTC)2·12H2Infrared spectrum of O.
FIG. 7 shows Ni in example 23(BTC)2·12H2XRD pattern of O.
FIG. 8 shows Ni in example 23(BTC)2·12H2SEM photograph of O (2 ten thousand magnification on the left, 6 ten thousand magnification on the right).
FIG. 9 shows Ni in example 23(BTC)2·12H2Nitrogen adsorption desorption curve of O.
Detailed Description
The invention is further described below with reference to the drawings and specific preferred embodiments of the description, without thereby limiting the scope of protection of the invention.
The materials and equipment used in the following examples are commercially available.
The invention relates to a method for rapidly preparing a nickel-based metal organic framework material, which comprises the following steps of:
adding nickel acetate tetrahydrate and trimesic acid into a reaction vessel according to the mass ratio of 0.2-5: 1 (1: 5-5: 1) as reactants, adding 2-8 ball milling balls with the diameter of 3-15 mm, ensuring the mass ratio of the ball milling balls to the added reactants to be 10-20: 1, and adding water. Sealing the reaction container, putting the sealed reaction container into a ball mill, carrying out ball milling for 1-180 min at 25-50 Hz, scraping the product, washing the product with ethanol and water for 2-4 times, and drying the product for 2-24 h at 30-120 ℃ to obtain the nickel-based metal organic framework material, wherein the green solid powder is Ni3(BTC)2·12H2O。
In the preparation method, the water can be preferably deionized water, and the mass ratio of the amount of the deionized water to the reactants is 0.01-0.8: 1.
In the preparation method, the reaction vessel can be preferably an agate tank or a zirconia tank, and the corresponding ball grinding balls are agate balls or zirconium balls.
Example 1:
the invention relates to a method for rapidly preparing a nickel-based metal organic framework material, which comprises the following steps of:
nickel acetate tetrahydrate and trimesic acid (0.45 g in total) are added into an 80mL agate tank according to the mass ratio of 2: 3, 310 mm agate balls (4.5g) are added to ensure that the mass ratio of the agate balls to the added reactants is 10: 1, and then 0.2mL deionized water is added. Sealing agate tank, placing into ball mill, ball milling at 40Hz for 180min, scraping product, washing with ethanol for 2 times, washing with water for 2 times, and drying at 60 deg.C for 8 hr to obtain green solid powder Ni3(BTC)2·12H2And O, obtaining the nickel-based metal organic framework material.
The characterization data are shown in FIGS. 1, 2, 3, and 4. The product in FIG. 1 is located at 1680-1700cm-1The characteristic peak of-COOH at the position is basically disappeared and is at 1040-1646cm-1The appearance of characteristic peaks in BTC marks the progress of the reaction and the formation of new species. The characteristic crystal peaks at 10.99, 14.63, 15.24, 17.66, 17.94, 18.92, 19.32, 22.11, 27.37, 28.88, 29.65 degrees and the like in the figure 2 correspond to Ni respectively3(BTC)2·12H2Peaks of crystal planes of O such as 200, 001, -111, 220, 310, -3-11(111), 400, 330, -202, -112, 002, etc. Comparative Ni3(BTC)2·12H2The sample peaks for O were found to be completely coincident in peak position. FIG. 3 shows that the product from the ball milling process exhibits a small, fragmentary mass with the largest mass being about 2 microns and the smallest being about 500 nm. FIG. 4 shows that the adsorption/desorption curve indicates a type II adsorption/desorption isothermal curve, P/P0<There are micropores in the material due to rise at 0.1, mesopores due to rise at 0.1-0.7, and rises at 0.7-1Therefore, it has large pores and a BET specific surface area of about 10m2(ii) in terms of/g. FIG. 5 shows Ni in this example3(BTC)2·12H2The constant current charge-discharge curve of O in 6M NaOH solution under the condition of 1A/g can be obtained by calculation according to the discharge curve, and the specific capacitance of the constant current charge-discharge curve is 640F/g.
Example 2
The invention relates to a method for rapidly preparing a nickel-based metal organic framework material, which comprises the following steps of:
nickel acetate tetrahydrate and trimesic acid (0.45 g in total) are added into an 80mL agate tank according to the mass ratio of 2: 3, 6 agate balls (9.0g) with the diameter of 10mm are added, the mass ratio of the agate balls to the added reactants is ensured to be 20: 1, and then 0.1mL deionized water is added. Sealing agate tank, placing into ball mill, ball milling at 50Hz for 1min, scraping product, washing with ethanol for 3 times, washing with water for 3 times, and drying at 60 deg.C for 8 hr to obtain green solid powder Ni3(BTC)2·12H2And O, obtaining the nickel-based metal organic framework material.
The characterization data are shown in fig. 6, 7, 8, 9. The product in FIG. 6 is located at 1680-1700cm-1The characteristic peak of-COOH at the position is basically disappeared and is at 1040-1646cm-1The appearance of characteristic peaks in BTC marks the progress of the reaction and the formation of new species. The characteristic crystal peaks at 10.99, 14.63, 15.24, 17.66, 17.94, 18.92, 19.32, 22.11, 27.37, 28.88, 29.65 degrees and the like in the figure 7 correspond to Ni respectively3(BTC)2·12H2Peaks of crystal planes of O such as 200, 001, -111, 220, 310, -3-11(111), 400, 330, -202, -112, 002, etc. FIG. 8 shows that the product from the ball milling process exhibited a small, fragmented mass with the largest mass being about 2 microns and the smallest being about 500 nm. FIG. 9 shows that the adsorption/desorption curve indicates a type II adsorption/desorption isothermal curve, P/P0<0.1 rise time, so that micropores exist in the material, 0.1-0.7 rise time, so that mesopores exist, 0.7-1 rise time, so that macropores exist, and the BET specific surface area is about 4.85m2/g。
Comparative example 1:
a method for preparing a nickel-based metal organic framework material, which is substantially the same as that of example 1 except that: no deionized water is added into the agate tank, no product is generated even if the ball milling time is as long as 90min, and after the three times of washing with ethanol and water, all the products after reaction are washed away.
Comparative example 2:
a method for preparing a nickel-based metal organic framework material, which is substantially the same as that of example 1 except that: the power of the ball milling is 20Hz, and the result shows that: even if the ball milling time is as long as 90min, no product is generated, and after the reaction product is washed by water and ethanol for three times respectively, all the products after the reaction are washed away.
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner. Although the present invention has been described with reference to the preferred embodiments, it is not intended to be limited thereto. Those skilled in the art can make many possible variations and modifications to the disclosed embodiments, or equivalent modifications, without departing from the spirit and scope of the invention, using the methods and techniques disclosed above. Therefore, any simple modification, equivalent replacement, equivalent change and modification made to the above embodiments according to the technical essence of the present invention are still within the scope of the protection of the technical solution of the present invention.
Claims (7)
1. A method for rapidly preparing a nickel-based metal organic framework material comprises the following steps:
adding nickel acetate tetrahydrate and trimesic acid into a reaction container as reactants, adding ball milling balls and water, sealing the reaction container, carrying out ball milling at 40 Hz-50 Hz, cleaning and drying the obtained product to obtain the nickel-based metal organic framework material, namely Ni3(BTC)2•12H2O；
The mass ratio of the water to the reactant is 0.01-0.8: 1;
the ball milling time is 1-180 min.
2. The method for rapidly preparing the nickel-based metal organic framework material as claimed in claim 1, wherein the mass ratio of the nickel acetate tetrahydrate to the trimesic acid is 0.2-5: 1.
3. The method for rapidly preparing the nickel-based metal organic framework material according to claim 1, wherein the mass ratio of the ball grinding balls to the reactants is 10-20: 1.
4. The method for rapidly preparing the nickel-based metal organic framework material according to claim 3, wherein the diameter of the ball grinding ball is 3mm to 15mm, and the number of the particles of the ball grinding ball is 2 to 8.
5. The method for rapidly preparing the nickel-based metal organic framework material according to any one of claims 1 to 4, wherein the reaction vessel comprises an agate tank or a zirconia tank; the ball grinding balls comprise agate balls or zirconium balls.
6. The method for rapidly preparing the nickel-based metal organic framework material according to any one of claims 1 to 4, wherein the cleaning is 2 to 4 times by respectively using ethanol and water.
7. The method for rapidly preparing the nickel-based metal organic framework material according to any one of claims 1 to 4, wherein the drying temperature is 30 ℃ to 120 ℃, and the drying time is 2h to 24 h.
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| CN110372877A (en) * | 2019-07-29 | 2019-10-25 | 南京工业大学 | A kind of method that green prepares metal-organic framework materials |
| CN110790944B (en) * | 2019-11-14 | 2021-06-25 | 中国人民解放军国防科技大学 | Method for preparing zirconium metal organic framework nanotube |
| CN114230806B (en) * | 2022-01-05 | 2023-04-14 | 太原理工大学 | Large-scale preparation method of nickel-based MOF material and application of nickel-based MOF material in separation of ethylene from multi-component gas |
| CN115304779A (en) * | 2022-07-07 | 2022-11-08 | 中国人民解放军国防科技大学 | MIL-101 (Cr) and preparation method thereof |
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