CN115490868B - Preparation method of HKUST-1 crystal - Google Patents
Preparation method of HKUST-1 crystal Download PDFInfo
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- CN115490868B CN115490868B CN202110672509.0A CN202110672509A CN115490868B CN 115490868 B CN115490868 B CN 115490868B CN 202110672509 A CN202110672509 A CN 202110672509A CN 115490868 B CN115490868 B CN 115490868B
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- 239000013148 Cu-BTC MOF Substances 0.000 title claims abstract description 88
- 239000013078 crystal Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000002245 particle Substances 0.000 claims abstract description 52
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 239000003960 organic solvent Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- 239000003513 alkali Substances 0.000 claims description 27
- 230000001105 regulatory effect Effects 0.000 claims description 18
- 239000002585 base Substances 0.000 claims description 17
- 230000001276 controlling effect Effects 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000001878 scanning electron micrograph Methods 0.000 description 20
- 239000010949 copper Substances 0.000 description 17
- 239000000243 solution Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000012621 metal-organic framework Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 229910000431 copper oxide Inorganic materials 0.000 description 2
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 150000005837 radical ions Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 239000002520 smart material Substances 0.000 description 1
- HOWHQWFXSLOJEF-MGZLOUMQSA-N systemin Chemical compound NCCCC[C@H](N)C(=O)N[C@@H](CCSC)C(=O)N[C@@H](CCC(N)=O)C(=O)N[C@@H]([C@@H](C)O)C(=O)N[C@@H](CC(O)=O)C(=O)OC(=O)[C@@H]1CCCN1C(=O)[C@H]1N(C(=O)[C@H](CC(O)=O)NC(=O)[C@H](CCCN=C(N)N)NC(=O)[C@H](CCCCN)NC(=O)[C@H](CO)NC(=O)[C@H]2N(CCC2)C(=O)[C@H]2N(CCC2)C(=O)[C@H](CCCCN)NC(=O)[C@H](CO)NC(=O)[C@H](CCC(N)=O)NC(=O)[C@@H](NC(=O)[C@H](C)N)C(C)C)CCC1 HOWHQWFXSLOJEF-MGZLOUMQSA-N 0.000 description 1
- 108010050014 systemin Proteins 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 150000003639 trimesic acids Chemical class 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- 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
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
Abstract
The application provides a preparation method of HKUST-1 crystals, which comprises the following steps: cu (NO) 3 ) 2 ·3H 2 O and PVP are mixed in an organic solvent, an organic solution of trimesic acid is added, and the HKUST-1 crystal is obtained through reaction. The method is simple to operate, can effectively control the particle size of HKUST-1, and can synthesize the HKUST-1 with the required size on a large scale. The HKUST-1 with the particle size of 50 nm-850 nm, uniform particle size and good crystal form can be synthesized on a large scale by the technical method.
Description
Technical Field
The application relates to a metal organic frame material, in particular to a preparation method of the metal organic frame material.
Background
Crystal size is an important controlling factor, beyond chemical composition, affecting the physicochemical properties of a substance in the material science. For example, the crystal size and morphology of zeolites are closely related to the effectiveness of industrial catalysis. In addition to the important effects on adsorption, catalysis, photoelectric properties, etc., for Metal Organic Frameworks (MOFs), crystal size effects remain one of the most challenging issues in smart materials to control framework flexibility, and its understanding is still in its infancy.
HKUST-1, a metal organic framework material that is readily available and relatively stable in raw materials, has found application in a variety of fields. For example, it can be used as a nanofiller to prepare efficient ultrafiltration membranes with high water repellency while maintaining high water permeability. The nano-scale copper oxide particle can be used as a coating material to wrap nano-scale copper oxide particles therein, and hydrogen and methylene blue can be degraded under the catalysis of visible light. In addition, HKUST-1 itself has many excellent properties, and it has a certain hydrogen storage capacity at low temperatures. At room temperature, HKUST-1's high pressure methane storage is capable of meeting U.S. department of energy standards. However, the differences in the nature of HKUST-1 of different sizes remain to be explored. The synthesis of HKUST-1 with good crystal quality and uniform size is always a technical problem to be solved by the person skilled in the art.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, the present application is directed to a preparation method of a metal organic framework material, which is used for solving the problems that the particle size cannot be controlled and the uniformity of the particle size is insufficient when the HKUST-1 with good crystal form is synthesized in the prior art.
To achieve the above and other related objects, the present application is achieved by the following technical solutions.
The application provides a preparation method of HKUST-1 crystals, which comprises the following steps:
cu (NO) 3 ) 2 ·3H 2 O, PVP and adding an organic solution of trimesic acid into the mixture, and reacting to obtain the HKUST-1 crystal.
Preferably, a base is also added to the reaction system.
Preferably, the alkali is added in an amount until the reaction system can not precipitate HKUST-1 crystals any more at room temperature. More preferably, the room temperature is 20 to 30 ℃.
More preferably, the base is mixed with Cu (NO 3 ) 2 ·3H 2 O, PVP in an organic solvent.
Preferably, the base is selected from Cu (OAc) 2 、Zn(OAc) 2 、NaHCO 3 And Na (Na) 2 CO 3 One or more of the following.
More preferably, an organic solution of a base is used to add to the reaction system.
Preferably, the particle size of the HKUST-1 crystal is regulated by regulating the addition rate of trimesic acid in the presence of a base, and more preferably, the addition rate of trimesic acid is at least 1mL/min.
More preferably, the concentration of the organic solvent solution of the base is 0.001 to 1mol/L.
Preferably, the organic solvent is methanol.
Preferably, the solvent in the organic solution of trimesic acid is methanol.
Preferably, the solvent in the organic solution of the base is methanol.
Preferably, the molar ratio of the copper nitrate trihydrate to the trimesic acid is (1-5): 2.
the application also discloses a method for regulating and controlling the grain diameter of the HKUST-1 crystal, cu (NO) 3 ) 2 ·3H 2 O and PVP are mixed in an organic solvent, and the particle size of HKUST-1 crystals obtained by the reaction is regulated and controlled by regulating and controlling the addition amount of alkali and the addition speed of trimesic acid.
In the preparation method of the application, the uniformity of the particle size of HKUST-1 can be regulated by PVP, and alkali comprises but is not limited to Cu (OAc) 2 ，Zn(OAc) 2 ，NaHCO 3 ，Na 2 CO 3 The particle size can be regulated and controlled, the more and the smaller the alkali is added, and the particle size can be regulated and controlled by regulating the dripping speed of the trimesic acid under the condition of adding the alkali, the faster the dropping speed is, the larger the particle size is, so the size of the HKUST-1 particle size can be regulated and controlled from two dimensions of the dropping speed and the addition amount of alkali to reach the required size. The method is simple to operate, can effectively control the particle size of HKUST-1, and can synthesize the HKUST-1 with the required size on a large scale. The HKUST-1 with the particle size of 50 nm-850 nm, uniform particle size and good crystal form can be synthesized on a large scale by the technical method.
Drawings
FIG. 1 is an SEM image of HKUST-1 prepared in example 1, with a scale of 1 μm.
FIG. 2 is an SEM image of HKUST-1 prepared in example 2, with a scale of 1 μm.
FIG. 3 is an SEM image of HKUST-1 prepared in example 3, with a scale of 1 μm.
FIG. 4 is an SEM image of HKUST-1 prepared in example 4, with a scale of 1 μm.
FIG. 5 is an SEM image of HKUST-1 prepared in example 5, with a scale of 1 μm.
FIG. 6 is an SEM image of HKUST-1 prepared in example 6, with a scale of 1 μm.
FIG. 7 is an SEM image of HKUST-1 prepared in example 7, with a scale of 1 μm.
FIG. 8 is an SEM image of HKUST-1 prepared in example 8, with a scale of 1 μm.
FIG. 9 is an SEM image of HKUST-1 prepared in example 9.
FIG. 10 is an SEM image of HKUST-1 prepared in example 10, with the scale of 100nm.
FIG. 11 is an SEM image of HKUST-1 prepared in example 11, the scale of the drawing being 1 μm.
FIG. 12 is an SEM image of HKUST-1 prepared in example 12, with a scale of 1 μm.
FIG. 13 is an SEM image of HKUST-1 prepared in example 13, the scale of the drawing being 1 μm.
FIG. 14 is an SEM image of HKUST-1 prepared in example 14, the scale of the drawing being 100nm.
FIG. 15 is an SEM image of HKUST-1 prepared in example 15, the scale of the drawing being 100nm.
FIG. 16 is an SEM image of HKUST-1 prepared in example 16, the scale of the drawing being 100nm.
FIG. 17 is an SEM image of HKUST-1 prepared in example 17, the scale of the drawing being 100nm.
FIG. 18 is a chart showing the X-ray diffraction patterns of HKUST-1 in example 10 (corresponding to 70 nm), example 7 (corresponding to 110 nm), example 6 (corresponding to 145 nm) and example 5 (corresponding to 200 nm).
FIG. 19 is a graph showing the adsorption characterization of HKUST-1 in examples 10 (corresponding to 70 nm), 7 (corresponding to 110 nm), 6 (corresponding to 145 nm) and 5 (corresponding to 200 nm).
FIG. 20 is an SEM image of HKUST-1 prepared in comparative example 1.
FIG. 21 is an SEM image of HKUST-1 prepared in comparative example 2.
FIG. 22 is an SEM image of HKUST-1 prepared in comparative example 3.
Detailed Description
Further advantages and effects of the present application will become apparent to those skilled in the art from the disclosure of the present application, which is described by the following specific examples.
Before the embodiments of the application are explained in further detail, it is to be understood that the application is not limited in its scope to the particular embodiments described below; it is also to be understood that the terminology used in the examples of the application is for the purpose of describing particular embodiments only, and is not intended to limit the scope of the application. The test methods in the following examples, in which specific conditions are not noted, are generally conducted under conventional conditions or under conditions recommended by the respective manufacturers.
Where numerical ranges are provided in the examples, it is understood that unless otherwise stated herein, both endpoints of each numerical range and any number between the two endpoints are significant both in the numerical range. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. In addition to the specific methods, devices, materials used in the embodiments, any methods, devices, and materials of the prior art similar or equivalent to those described in the embodiments of the present application may be used to practice the present application according to the knowledge of one skilled in the art and the description of the present application.
The preparation method of the HKUST-1 crystal in the embodiment comprises the following steps:
cu (NO) 3 ) 2 ·3H 2 O and PVP are mixed in an organic solvent, an organic solution of trimesic acid is added, and the HKUST-1 crystal is obtained through reaction.
Preferably, a base is also added to the reaction system. More preferably, the base is mixed with Cu (NO 3 ) 2 ·3H 2 O, PVP in an organic solvent.
The base of the present application is used for adjusting the pH of the reaction system, and is selected from Cu (OAc) 2 、Zn(OAc) 2 、NaHCO 3 And Na (Na) 2 CO 3 One or more of the following.
More preferably, an organic solution of a base is used to add to the reaction system. The concentration of the organic solvent solution of the base may be determined according to the solubility properties of the base. More preferably, the concentration of the organic solvent solution of the base is 0.001 to 1mol/L.
In a specific embodiment of the present application, the organic solvent is methanol.
In a specific embodiment of the present application, the solvent in the organic solution is methanol.
In a specific embodiment of the application, the molar ratio of the copper nitrate trihydrate to the trimesic acid is (1-5): 2.
under the condition of adding alkali, the adding rate of the trimesic acid can adjust the particle size of HKUST-1. The rate of addition of trimesic acid may be determined based on the size of the desired HKUST-1 particle size. In a specific embodiment of the application, the rate of addition of trimesic acid is at least 1mL/min. In the application, the injection can be added at a certain rate, such as 1mL/min, 2mL/min,3mL/min, 4mL/min and the like, or directly injected.
According to the application, the particle size of HKUST-1 is regulated and controlled by controlling the two dimensions of the dripping speed of trimesic acid and the addition amount of alkali, so that the particle size reaches the required size.
When no alkali is added, experiments show that the dropping speed can hardly regulate the particle size. From 1mL/min (20 min) to 5mL/min (4 min) to direct injection (10 s), there was little change in particle size. In FIGS. 20, 21 and 22 corresponding to comparative examples 1 to 3, the particle diameters were almost 800 nm.
When the alkali is added, there is a tendency that the particle diameter is reduced with the same dropping speed as the amount of the added alkali increases. The addition of alkali has previously been reported to reduce particle size but due to the common basic ion OH - And CO 3 2- Middle Cu (OH) 2 Is a precipitate, and CuCO 3 Can become Cu (OH) after meeting water 2 And Cu 2 (OH) 2 CO 3 It is therefore relatively difficult to think of adjusting the size of HKUST-1 particle size by the amount of alkali added.
The addition amount of the alkali can be regulated and controlled according to the strength and concentration of the alkali and the particle size of the target product. In the present application, the amount of the alkali is added until the reaction system cannot precipitate HKUST-1 crystals at room temperature, e.g., 20 to 30 ℃, and in the present embodiment, the amount of the alkali is added until the reaction system cannot precipitate HKUST-1 crystals at 25 ℃. For Cu (OAc) in the above listed base 2 In the case of 500m of the reaction systemIn the case of L, the concentration of Cu (OAc) was 0.004mol/L 2 The addition amount of the methanol solution is not more than 70mL.
The application also discloses a method for regulating and controlling the grain diameter of HKUST-1 crystal, cu (NO) 3 ) 2 ·3H 2 O and PVP are mixed in an organic solvent, and the particle size of HKUST-1 crystals obtained by the reaction is regulated and controlled by regulating and controlling the addition amount of alkali and the addition speed of trimesic acid.
Specific examples of the technical scheme in the application are shown in tables 1 and 2.
Wherein, in tables 1 and 2, the alkali solution is an alkali methanol solution in which Cu (OAc) 2 ，Zn(OAc) 2 ，Na 2 CO 3 At a concentration of 0.004mol/L, naHCO 3 The concentration of (C) was 0.008mol/L.
TABLE 1
| Examples | Cu(NO 3 ) 2 ·3H 2 O | PVP | MeOH | Cu(OAc) 2 | C 9 H 6 O 6 | Speed of addition |
| 1 | 0.7731 g | 0.4g | 72mL | 8mL | 20mL | 1mL/min |
| 2 | 1.9328g | 1g | 180mL | 20mL | 50mL | 2mL/min |
| 3 | 3.8655g | 2g | 360mL | 40mL | 100mL | 2mL/min |
| 4 | 7.731g | 4g | 720mL | 80mL | 200mL | 3mL/min |
| 5 | 3.8655g | 2g | 365mL | 35mL | 100mL | 4mL/min |
| 6 | 3.8655g | 2g | 360mL | 40mL | 100mL | 4mL/min |
| 7 | 3.8655g | 2g | 355mL | 45mL | 100mL | 4mL/min |
| 8 | 3.8655g | 2g | 350mL | 50mL | 100mL | 4mL/min |
| 9 | 3.8655g | 2g | 345mL | 55mL | 100mL | 4mL/min |
| 10 | 3.8655g | 2g | 340mL | 60mL | 100mL | 4mL/min |
| 11 | 0.7731g | 0.4g | 72mL | 8mL | 20mL | 2mL/min |
| 12 | 0.7731g | 0.4g | 72mL | 8mL | 20mL | 4mL/min |
| 13 | 0.7731g | 0.4g | 72mL | 8mL | 20mL | Injection addition |
| 14 | 0.7731g | 0.4g | 68mL | 12mL | 20mL | 1mL/min |
TABLE 2
| Examples | Cu(NO 3 ) 2 ·3H 2 O | PVP | MeOH | 8mL | C 9 H 6 O 6 | Speed of addition |
| 15 | 0.7731 g | 0.4g | 72mL | Zn(OAc) 2 | 20mL | 1mL/min |
| 16 | 0.7731g | 0.4g | 72mL | NaHCO 3 | 20mL | 1mL/min |
| 17 | 0.7731g | 0.4g | 72mL | Na 2 CO 3 | 20mL | 1mL/min |
TABLE 3 Table 3
| Comparative example | Cu(NO 3 ) 2 ·3H 2 O | PVP | MeOH | Cu(OAc) 2 | C 9 H 6 O 6 | Speed of addition |
| 1 | 0.7731 g | 0.4g | 80mL | 0mL | 20mL | 1mL/min |
| 2 | 0.7731g | 0.4g | 80mL | 0mL | 20mL | 5mL/min |
| 3 | 0.7731g | 0.4g | 80mL | 0mL | 20mL | Injection addition |
SEM pictures of the crystals of HKUST-1 formed in tables 1 and 2 are shown in FIGS. 1-16, wherein:
FIG. 1 shows the synthesis of 100mL HKUST-1 from example 1; the grain diameter is 220nm;
FIG. 2 shows the synthesis of 250mL HKUST-1 from example 2; the grain diameter is 200nm;
FIG. 3 shows the synthesis of 500mL HKUST-1 from example 3; the grain diameter is 180nm;
FIG. 4 is a 1000mL HKUST-1 synthesized in example 4; particle size is 150nm;
FIG. 5 shows HKUST-1 with a particle size of 200nm synthesized in example 5;
FIG. 6 shows HKUST-1 having a particle size of 145nm prepared in example 6;
FIG. 7 is a graph of HKUST-1 having a particle size of 110nm prepared in example 7;
FIG. 8 is a graph of HKUST-1 having a particle size of 90nm prepared in example 8;
FIG. 9 is HKUST-1 having a particle size of 70nm prepared in example 9;
FIG. 10 is HKUST-1 having a particle size of 55nm prepared in example 9;
FIG. 11 is HKUST-1 having a particle size of 300nm prepared in example 11;
FIG. 12 is HKUST-1 having a particle size of 500nm prepared in example 12;
FIG. 13 is a particle size of 850nm HKUST-1 prepared in example 13;
FIG. 14 is HKUST-1 having a particle size of 55nm prepared in example 14;
FIG. 15 is HKUST-1 having a particle size of 100nm prepared in example 15;
FIG. 16 is HKUST-1 having a particle size of 200nm prepared in example 16;
FIG. 17 is HKUST-1 having a particle size of 50nm prepared in example 17;
FIG. 18 is an XRD pattern of HKUST-1 prepared in examples 5, 6, 7 and 10;
FIG. 19 is a graph showing the nitrogen adsorption characterization of HKUST-1 prepared in examples 5, 6, 7 and 10;
FIG. 20 is HKUST-1 having a particle size of 800nm prepared in comparative example 1;
FIG. 21 is a particle size of 800nm HKUST-1 prepared in comparative example 2;
FIG. 22 is HKUST-1 having a particle size of 800nm prepared in comparative example 3.
As can be seen from tables 1, 2 and 3: since HKUST-1 is composed of trimesic acid and Cu 2+ The coordination reaction of trimesic acid can be realized only by removing protons in acid radical, so that when alkaline ions exist in the reaction system, acid radical protons are easy to remove, subsequent reactions can be performed to generate crystal nuclei, and the crystal nuclei can be grown subsequently to obtain the final HKUST-1 crystal grains. And when the alkali ions are more, more crystal nuclei can be generated, so that the particle size is reduced. If the dropping speed is high, the alkali ions disappear in a short time due to the increase of acid radical ions in a short time, so that the ratio of the deprotonated trimesic acid dropped into the reaction system is relatively low, the generated crystal nucleus is reduced, and the particle size is increased.
The above embodiments are merely illustrative of the principles of the present application and its effectiveness, and are not intended to limit the application. Modifications and variations may be made to the above-described embodiments by those skilled in the art without departing from the spirit and scope of the application. Accordingly, it is intended that all equivalent modifications and variations of the application be covered by the claims, which are within the ordinary skill of the art, be within the spirit and scope of the present disclosure.
Claims (3)
1. A preparation method of HKUST-1 crystal comprises the following steps: cu (NO) 3 ) 2 ·3H 2 Mixing O and PVP in an organic solvent, adding an organic solution of trimesic acid, and reacting to obtain the HKUST-1 crystal; alkali is also added into the reaction system; the base is selected from Cu (OAc) 2 、Zn(OAc) 2 、NaHCO 3 And Na (Na) 2 CO 3 One or more of the following; regulating and controlling the adding rate of the trimesic acid to regulate and control the particle size of HKUST-1 crystals; the adding rate of the trimesic acid is at least 1mL/min; the particle size of the HKUST-1 crystal is 50 nm-850 nm;
Cu(NO 3 ) 2 ·3H 2 the mol ratio of O to trimesic acid is (1-5): 2; the addition amount of the alkali is added until the HKUST-1 crystal can not be separated out any more at room temperature; adding an organic solution of alkali into a reaction system; the concentration of the organic solution of the alkali is 0.001-1 mol/L; the solvent in the organic solution of the base is methanol.
2. The method according to claim 1, wherein the solvent in the organic solution and the organic solvent are both methanol.
3. A method for controlling the particle size of HKUST-1 crystals by the production process as claimed in any one of claims 1 to 2, characterized in that Cu (NO 3 ) 2 ·3H 2 O and PVP are mixed in an organic solvent, and the particle size of HKUST-1 crystals obtained by the reaction is regulated and controlled by regulating and controlling the addition amount of alkali and the addition speed of trimesic acid.
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