CN115490868A - Preparation method of HKUST-1 crystal - Google Patents
Preparation method of HKUST-1 crystal Download PDFInfo
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- CN115490868A CN115490868A CN202110672509.0A CN202110672509A CN115490868A CN 115490868 A CN115490868 A CN 115490868A CN 202110672509 A CN202110672509 A CN 202110672509A CN 115490868 A CN115490868 A CN 115490868A
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- 239000013148 Cu-BTC MOF Substances 0.000 title claims abstract description 87
- 239000013078 crystal Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000002245 particle Substances 0.000 claims abstract description 47
- 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
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000003960 organic solvent Substances 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- 239000002585 base Substances 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 239000003513 alkali Substances 0.000 claims description 16
- 230000001105 regulatory effect Effects 0.000 claims description 15
- 230000001276 controlling effect Effects 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 description 20
- 239000000243 solution Substances 0.000 description 14
- 239000000463 material Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 239000012621 metal-organic framework Substances 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 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
- 239000002253 acid Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 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
- 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
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 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
- 238000012512 characterization method Methods 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
- 239000000945 filler Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 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
- 230000002194 synthesizing effect Effects 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
Images
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 invention provides a preparation method of an HKUST-1 crystal, which comprises the following steps: adding 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. The method is simple to operate, can effectively control the particle size of the HKUST-1, and can synthesize the HKUST-1 with the required size in a large scale. The HKUST-1 with uniform particle size and good crystal form and the particle size of 50-850 nm can be synthesized on a large scale by the technical method.
Description
Technical Field
The invention relates to a metal organic framework material, in particular to a preparation method of the metal organic framework material.
Background
Crystal size is an important controlling factor, beyond chemical composition, affecting the physicochemical properties of substances in material science. For example, the crystal size and morphology of zeolites are closely related to the effectiveness of industrial catalysis. For Metal Organic Frameworks (MOFs), in addition to having important effects on adsorption, catalysis, photoelectric properties, etc., crystal size effects are still one of the most challenging issues for controlling framework flexibility in smart materials, and its understanding is still in its infancy.
HKUST-1, a metal organic framework material with readily available raw materials and relatively stable, has been used in a variety of fields. For example, it can be used as a nano filler to prepare high-efficiency ultrafiltration membrane with high water repellency and high water permeability. It can also be used as a coating material to wrap nano-scale copper oxide particles in the copper oxide, and hydrogen and methylene blue are 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 temperature. The high-pressure methane storage capacity of HKUST-1 can reach the standard of the U.S. department of energy at room temperature. However, the differences in properties of HKUST-1 of different sizes have yet to be explored. The technical problem to be solved by the technical personnel in the field is to synthesize a series of HKUST-1 crystals with good quality and uniform size.
Disclosure of Invention
In view of the above disadvantages of the prior art, the present invention provides a method for preparing a metal organic framework material, which is used to solve the problems of the prior art that the particle size cannot be controlled and the uniformity of the particle size is insufficient when synthesizing HKUST-1 having a good crystal form.
To achieve the above objects and other related objects, the present invention is achieved by the following technical solutions.
The invention provides a preparation method of an HKUST-1 crystal, which comprises the following steps:
adding 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.
Preferably, a base is also added to the reaction system.
Preferably, the alkali is added until the HKUST-1 crystal can not be separated out at room temperature in the reaction system. More preferably, the room temperature is 20 to 30 ℃.
More preferably, the base is reacted with Cu (NO) 3 ) 2 ·3H 2 O and PVP are mixed in an organic solvent.
Preferably, the base is selected from Cu (OAc) 2 、Zn(OAc) 2 、NaHCO 3 And Na 2 CO 3 One or more of (a).
More preferably, an organic solution of a base is used to add to the reaction system.
Preferably, the particle size of the HKUST-1 crystals is controlled by controlling 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 size of HKUST-1 crystal, which is to mix Cu (NO) 3 ) 2 ·3H 2 Mixing O and PVP in an organic solvent, and regulating and controlling the grain size of HKUST-1 crystals obtained by reaction by regulating and controlling the addition amount of alkali and the addition speed of trimesic acid.
In the preparation method, the uniformity of HKUST-1 particle size can be controlled by PVP, and alkali including but not limited to Cu (OAc) 2 ，Zn(OAc) 2 ，NaHCO 3 ，Na 2 CO 3 The particle size of the HKUST-1 can be regulated and controlled, the more the alkali is added, the smaller the particle size is, and meanwhile, under the condition of adding the alkali, the particle size can also be regulated and controlled by regulating and controlling the dripping speed of the trimesic acid, and the quicker the dripping speed is, the larger the particle size is, so that the particle size of the HKUST-1 can be regulated and controlled from two dimensions of the dripping speed and the adding amount of the alkali, and the required size is achieved. The method is simple to operate, can effectively control the particle size of the HKUST-1, and can synthesize the HKUST-1 with the required size in a large scale. The HKUST-1 with uniform particle size and good crystal form and the particle size of 50-850 nm can be synthesized on a large scale by the technical method.
Drawings
FIG. 1 is an SEM photograph of HKUST-1 prepared in example 1, with a scale of 1 μm.
FIG. 2 is an SEM photograph of HKUST-1 prepared in example 2, with a scale of 1 μm.
FIG. 3 is an SEM photograph of HKUST-1 prepared in example 3, with a scale of 1 μm.
FIG. 4 is an SEM photograph of HKUST-1 prepared in example 4, with a scale of 1 μm.
FIG. 5 is an SEM photograph of HKUST-1 prepared in example 5, with a scale of 1 μm.
FIG. 6 is an SEM photograph of HKUST-1 prepared in example 6, with a scale of 1 μm.
FIG. 7 is an SEM photograph of HKUST-1 prepared in example 7, with a scale of 1 μm.
FIG. 8 is an SEM photograph of HKUST-1 prepared in example 8, with a scale of 1 μm.
FIG. 9 is an SEM photograph of HKUST-1 prepared in example 9.
FIG. 10 is an SEM photograph of HKUST-1 prepared in example 10, with scale of 100nm.
FIG. 11 is an SEM photograph of HKUST-1 prepared in example 11, with a scale of 1 μm.
FIG. 12 is an SEM photograph of HKUST-1 prepared in example 12, with scale of 1 μm.
FIG. 13 is an SEM photograph of HKUST-1 prepared in example 13, with scale of 1 μm.
FIG. 14 is an SEM photograph of HKUST-1 prepared in example 14, with the scale of 100nm.
FIG. 15 is an SEM photograph of HKUST-1 prepared in example 15, with the scale of 100nm.
FIG. 16 is an SEM photograph of HKUST-1 prepared in example 16, with a scale of 100nm.
FIG. 17 is an SEM photograph of HKUST-1 prepared in example 17, with scale of 100nm.
FIG. 18 is a graph of the X-ray diffraction characterization 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 representing the nitrogen adsorption 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. 20 is an SEM photograph of HKUST-1 prepared in comparative example 1.
FIG. 21 is an SEM photograph of HKUST-1 prepared in comparative example 2.
FIG. 22 is an SEM photograph of HKUST-1 prepared in comparative example 3.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be readily apparent to those skilled in the art from the disclosure of the present invention.
Before the present embodiments are further described, it is to be understood that the scope of the invention is not to be limited to the specific embodiments described below; it is also to be understood that the terminology used in the examples is for the purpose of describing particular embodiments only, and is not intended to limit the scope of the present invention. Test methods in which specific conditions are not specified in the following examples are generally carried out under conventional conditions or under conditions recommended by the respective manufacturers.
When numerical ranges are given in the examples, it is understood that both endpoints of each of the numerical ranges and any value therebetween can be selected unless the invention otherwise indicated. 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 invention belongs. In addition to the specific methods, devices, and materials used in the examples, the invention may be practiced using any method, device, and material that is similar or equivalent to the methods, devices, and materials described in examples herein, in addition to those described in prior art practice and the description herein.
The preparation method of the HKUST-1 crystal in the embodiment comprises the following steps:
adding 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.
Preferably, a base is also added to the reaction system. More preferably, the base is reacted with Cu (NO) 3 ) 2 ·3H 2 Mixing O and PVP in an organic solvent。
The base used in the present application is selected from the group consisting of Cu (OAc) for adjusting the pH of the reaction system 2 、Zn(OAc) 2 、NaHCO 3 And Na 2 CO 3 One or more of (a).
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 organic solvent is methanol.
In a specific embodiment of the present application, the molar ratio of copper nitrate trihydrate to trimesic acid is (1 to 5): 2.
under the condition of adding alkali, the addition rate of the trimesic acid can adjust the particle size of the HKUST-1. The addition rate of trimesic acid can be determined according to the size of the required HKUST-1 particle size. In a specific embodiment of the present application, the trimesic acid is added at a rate of at least 1mL/min. In the application, the addition can be carried out at a certain rate, for example, the addition can be carried out at the speed of 1mL/min, 2mL/min,3mL/min, 4mL/min and the like, or the addition can be carried out by direct injection.
In the application, the particle size of the HKUST-1 is regulated and controlled by controlling two dimensions, namely the dropping speed of the trimesic acid and the adding amount of the alkali, so that the particle size reaches the required size.
When alkali is not added, experiments show that the dropping speed can hardly regulate the particle size. There was little change in particle size from 1mL/min (20 min) to 5mL/min (4 min) to direct injection (10 s). In FIGS. 20, 21 and 22 corresponding to comparative examples 1 to 3, the particle diameters were almost all around 800 nm.
When the base is added, the tendency is that when the amount of the base added increases, the same dropping speed results in a decrease in particle size. The addition of a base has been previously 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 Therefore, it is difficult to conceive of the adjustment of the particle size of HKUST-1 by the addition of the alkali.
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 a target product. In the present application, the alkali is added in an amount until the reaction system cannot precipitate crystals of HKUST-1 at room temperature, for example, 20 to 30 ℃ in the present example, until the reaction system cannot precipitate crystals of HKUST-1 at 25 ℃. For Cu (OAc) in the above-listed bases 2 In contrast, when the reaction system was 500mL, the concentration of Cu (OAc) was 0.004mol/L 2 The amount of the methanol solution (2) is not more than 70mL.
The application also discloses a method for regulating and controlling the grain diameter of HKUST-1 crystal, which is to use Cu (NO) as a material 3 ) 2 ·3H 2 Mixing O and PVP in an organic solvent, and regulating and controlling the grain size of HKUST-1 crystals obtained by reaction by regulating and controlling the addition amount of alkali and the addition speed of trimesic acid.
Specific examples of the technical solution in the present application are shown in tables 1 and 2.
Wherein, in tables 1 and 2, the solution of the base is a methanol solution of the base, wherein, cu (OAc) 2 ，Zn(OAc) 2 ，Na 2 CO 3 Is 0.004mol/L, and NaHCO 3 The concentration of (b) 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 | Rate of addition |
| 1 | 0.7731 g | 0.4g | 72mL | 8mL | 20mL | 1mL/ |
| 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/ |
| 5 | 3.8655g | 2g | 365mL | 35mL | 100mL | 4mL/ |
| 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/ |
| 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 | Rate 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
| Comparative example | Cu(NO 3 ) 2 ·3H 2 O | PVP | MeOH | Cu(OAc) 2 | C 9 H 6 O 6 | Rate of addition |
| 1 | 0.7731 g | 0.4g | 80mL | 0mL | 20mL | 1mL/ |
| 2 | 0.7731g | 0.4g | 80mL | 0mL | 20mL | 5mL/min |
| 3 | 0.7731g | 0.4g | 80mL | 0mL | 20mL | Injection addition |
SEM photographs of the HKUST-1 crystals formed in tables 1 and 2 are shown in FIGS. 1 to 16, in which:
in FIG. 1, 100mL of HKUST-1 was synthesized for example 1; the particle size is 220nm;
FIG. 2 shows the synthesis of 250mL of HKUST-1 in example 2; the grain diameter is 200nm;
FIG. 3 shows the synthesis of 500mL of HKUST-1 in example 3; the grain diameter is 180nm;
FIG. 4 shows the synthesis of 1000mL of HKUST-1 for example 4; the grain diameter is 150nm;
FIG. 5 shows HKUST-1 synthesized in example 5 and having a particle size of 200nm;
FIG. 6 shows HKUST-1 having a particle size of 145nm prepared in example 6;
FIG. 7 shows HKUST-1 having a particle size of 110nm prepared in example 7;
FIG. 8 is a graph showing 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 of 55nm particle size prepared in example 9;
FIG. 11 is a particle size of 300nm of HKUST-1 prepared in example 11;
FIG. 12 is HKUST-1 having a particle size of 500nm prepared in example 12;
FIG. 13 is a HKUST-1 having a particle size of 850nm prepared in example 13;
FIG. 14 is HKUST-1 of 55nm particle size prepared in example 14;
FIG. 15 is HKUST-1 of 100nm particle size prepared in example 15;
FIG. 16 is HKUST-1 of 200nm particle size prepared in example 16;
FIG. 17 is a 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 representing nitrogen adsorption for 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 HKUST-1 having a particle size of 800nm 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: because HKUST-1 is composed of trimesic acid and Cu 2+ The network structure formed by coordination, but the trimesic acid must remove the proton in the acid radical first to carry out the coordination reaction, so when the reaction system has alkaline ions, the proton of the acid radical is easy to remove, the subsequent reaction can be carried out to generate crystal nuclei, and the crystal nuclei can be grown from the crystal nuclei subsequently to obtain the final productHKUST-1 grains. And when the amount of the basic ion is large, the amount of nuclei that can be generated is large, and thus the particle diameter is reduced. If the dropping speed is higher, the acid radical ions are increased in a short time, and the basic ions disappear in a short time, so that the proportion of deprotonated trimesic acid in the dropping reaction system is relatively low, the generated crystal nuclei are reduced, and the particle size is increased.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (10)
1. A preparation method of HKUST-1 crystal comprises the following steps: adding 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.
2. The preparation method according to claim 1, wherein a base is further added to the reaction system; and/or the solvent in the organic solution and the organic solvent are both methanol.
3. The method according to claim 2, wherein the alkali is added in an amount such that no HKUST-1 crystal is precipitated at room temperature in the reaction system.
4. The method of claim 2, wherein the base is selected from the group consisting of Cu (OAc) 2 、Zn(OAc) 2 、NaHCO 3 And Na 2 CO 3 One or more of (a).
5. The method according to claim 2, wherein an organic solution of a base is used.
6. The method according to claim 5, wherein the concentration of the organic solution of the base is 0.001 to 1mol/L; and/or the solvent in the organic solution of the base is methanol.
7. The method of claim 1, wherein Cu (NO) 3 ) 2 ·3H 2 The molar ratio of O to trimesic acid is (1-5): 2.
8. the method according to claim 2, wherein the particle size of the crystals of HKUST-1 is controlled by controlling the addition rate of trimesic acid.
9. The method of claim 8, wherein the trimesic acid is added at a rate of at least 1mL/min.
10. A method for regulating and controlling the grain diameter of HKUST-1 crystal is characterized in that Cu (NO) is added 3 ) 2 ·3H 2 Mixing O and PVP in an organic solvent, and regulating the grain size of the HKUST-1 crystal obtained by the reaction by regulating the addition amount of alkali and the addition speed of trimesic acid.
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