CN111100149A - Having a structure of C2H2And CH4Metal organic framework material with adsorption separation function and preparation method thereof - Google Patents
Having a structure of C2H2And CH4Metal organic framework material with adsorption separation function and preparation method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 67
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 44
- 238000000926 separation method Methods 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000013384 organic framework Substances 0.000 title description 2
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 57
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 44
- YNZDQQMTXDYPLK-UHFFFAOYSA-N 2,5-bis(2H-tetrazol-5-yl)terephthalic acid Chemical class N=1NN=NC=1C1=C(C(=O)O)C=C(C(=C1)C(=O)O)C=1N=NNN=1 YNZDQQMTXDYPLK-UHFFFAOYSA-N 0.000 claims abstract description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 16
- QOYRNHQSZSCVOW-UHFFFAOYSA-N cadmium nitrate tetrahydrate Chemical compound O.O.O.O.[Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QOYRNHQSZSCVOW-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000011148 porous material Substances 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 9
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims abstract description 4
- 150000001875 compounds Chemical class 0.000 claims abstract description 3
- 238000004729 solvothermal method Methods 0.000 claims abstract description 3
- 239000013078 crystal Substances 0.000 claims description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000007795 chemical reaction product Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 239000003446 ligand Substances 0.000 description 19
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
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- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 238000001338 self-assembly Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- KJUGUADJHNHALS-UHFFFAOYSA-N 1H-tetrazole Substances C=1N=NNN=1 KJUGUADJHNHALS-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- -1 dimethylamine cation Chemical class 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- ROSDSFDQCJNGOL-UHFFFAOYSA-N protonated dimethyl amine Natural products CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 150000003536 tetrazoles Chemical class 0.000 description 1
- 125000003831 tetrazolyl group Chemical group 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic System
- C07F3/08—Cadmium compounds
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a compound with C2H2And CH4The metal organic framework material with the adsorption and separation functions and the preparation method thereof, wherein the metal organic framework material has a three-dimensional structure, contains hexagonal pore canals and has a chemical formula of [ (CH)3)2NH2][Cd(dtztp)0.5(HCOO)]·1.5DMF·H2O, in the formula, dtztp is deprotonated 2, 5-di (tetrazolyl) terephthalic acid, DMF is N, N-dimethylformamide, and the metal organic framework material is prepared by adding cadmium nitrate tetrahydrate and 2, 5-di (tetrazolyl) terephthalic acid serving as raw materials into a mixed solvent consisting of N, N-dimethylformamide, water and hydrochloric acid at the temperature of 125-135 ℃ by adopting a solvothermal synthesis method. The invention has the advantages that: (1) the pair of metal-organic framework materials C2H2Has higher adsorption capacity but to CH4Has a very low adsorption capacity to C2H2And CH4Carrying out effective adsorption separation; (2) the preparation method has the advantages of simple process, mild reaction conditions, easily obtained raw materials and easy operation.
Description
Technical Field
The invention relates to a metal organic framework material and a preparation method thereof, in particular to a metal organic framework material with C2H2And CH4A metal organic framework material with adsorption and separation functions and a preparation method thereof, belonging to the technical field of inorganic material chemistry.
Background
Acetylene (C)2H2) Is an important fossil fuel and also a basic raw material for manufacturing acetaldehyde, acetic acid, benzene, synthetic rubber, synthetic fiber and the like in industry. C2H2Mainly from the pyrolysis process of petroleum, but some methane (CH) is also produced in this process4). Thus, C2H2The storage and isolation of (A) is of great importance in industry.
The metal organic framework material is a novel porous material with a periodic network structure formed by connecting single or multiple metal ion centers through organic bridging ligands. The changeability of metal ion species and the modifiability of organic ligands endow the characteristics of controllability of the structure and functionalization of pore channels of the metal-organic framework material, so that the metal-organic framework material has important application in the aspects of gas storage, adsorption separation, organic catalysis and the like.
The azole and the carboxylic acid are two most commonly used ligands for preparing the metal organic framework material, the carboxylic acid can show a flexible coordination mode, and the azole can form a strong coordination bond. However, the organic ligand containing the double-function coordination groups of the azole and the carboxylic acid is not commonly used in the preparation of the metal organic framework material.
Disclosure of Invention
The first purpose of the invention is to fuse the respective coordination advantages of the triazole and the carboxylic acid, design a ligand simultaneously containing two tetrazoles and two carboxyl groups, and then prepare a C with novel structure and better C by utilizing the ligand and cadmium through self-assembly2H2And CH4A metal organic framework material with adsorption and separation functions.
It is a second object of the present invention to provide a simple method for synthesizing the metal-organic framework material.
In order to achieve the first object, the invention adopts the following technical scheme:
has a shape of C2H2And CH4The metal organic framework material with the adsorption and separation functions is characterized by having a three-dimensional structure and containing hexagonal pore channels, and the chemical formula is [ (CH)3)2NH2][Cd(dtztp)0.5(HCOO)]·1.5DMF·H2O, wherein dtztp is deprotonated 2, 5-bis (tetrazolyl) terephthalic acid and DMF is N, N-dimethylformamide, wherein dtztp has the following structural formula:
in order to achieve the second objective, the invention adopts the following technical scheme:
the foregoing has C2H2And CH4The preparation method of the metal organic framework material with the adsorption separation function is characterized in that the preparation method adopts a solvothermal synthesis method by taking cadmium nitrate tetrahydrate and 2, 5-bis (tetrazolyl) terephthalic acid as raw materials, and comprises the following steps:
step 1: adding cadmium nitrate tetrahydrate and 2, 5-bis (tetrazolyl) terephthalic acid into a mixed solvent consisting of N, N-dimethylformamide, water and hydrochloric acid;
step 2: placing the mixture in a high-pressure reaction kettle, heating to 125-135 ℃ in a sealed manner, keeping for 65-75 h, and then cooling to room temperature at the speed of 0.15-0.25 ℃/min;
and step 3: taking out the reaction product, and filtering to obtain colorless prismatic crystals;
and 4, step 4: exchanging the colorless prismatic crystal with methanol for 72h, and heating at 150 deg.C under vacuum for 5-6 h to obtain the compound C2H2And CH4A metal organic framework material with adsorption and separation functions.
The above production method is characterized in that the molar ratio of the cadmium nitrate tetrahydrate to the 2, 5-bis (tetrazolyl) terephthalic acid is 9 to 11: 4 to 6.
The preparation method is characterized in that the volume ratio of the N, N-dimethylformamide to the water to the hydrochloric acid is 28-32: 38-42: 4 to 5.
The above-mentioned production method is characterized in that the ratio of the total amount of the cadmium nitrate tetrahydrate and the 2, 5-bis (tetrazolyl) terephthalic acid to the amount of the mixed solvent is 0.13 to 0.17 mmol: 7.0-7.9 mL.
The invention has the advantages that:
(1) metal organic framework material
The metal organic framework material takes deprotonated 2, 5-di (tetrazolyl) terephthalic acid as a ligand, and the ligand is fused with respective coordination advantages of azole and carboxylic acid;
the metal organic framework material has a three-dimensional structure and contains hexagonal pores (the size is about the same as that of the pores of the metal organic framework material)
) Porosity of 28.2% and BET specific surface area of 575.8m2g-1To C2H2Has higher adsorption capacity but to CH4Has a very low adsorption capacity to C2H2And CH4Effective adsorption separation is carried out.
(2) Preparation method of metal organic framework material
The preparation method has the advantages of simple process, mild reaction conditions, easily obtained raw materials and easy operation.
Drawings
FIG. 1 is a schematic representation of a block diagram of the present invention having C2H2And CH4Cd in metal organic framework material with adsorption and separation functions2+A coordination environment diagram of ions;
FIG. 2 is a schematic representation of a circuit having C provided by the present invention2H2And CH4Metal organic frame material with adsorption and separation functionsA three-dimensional structure diagram of the material;
FIG. 3 is a powder X-ray diffraction pattern of an initial sample and a sample after activation of the metal-organic framework material prepared in example 1;
FIG. 4 is a nitrogen adsorption curve at 77K for the metal organic framework material prepared in example 1;
FIG. 5 is C at 273K for the metal-organic framework material prepared in example 12H2And CH4Adsorption isotherms of (a);
FIG. 6 shows C at 298K for the metal organic framework material prepared in example 12H2And CH4Adsorption isotherms of (a);
FIG. 7 shows the equivalent (equimolar) C of the metal organic framework material obtained in example 1 calculated by the ideal adsorption solution theory2H2And CH4C of mixture at 298K2H2/CH4Adsorption selectivity curve.
Detailed Description
The invention is described in detail below with reference to the figures and the embodiments.
One, having C2H2And CH4Structure of metal organic framework material with adsorption and separation functions
The invention fuses respective coordination advantages of azole and carboxylic acid, firstly designs a ligand dtztp which simultaneously contains two tetrazolyl groups and two carboxyl groups, wherein the dtztp is deprotonated 2, 5-di (tetrazolyl) terephthalic acid, and the structural formula is as follows:
then the ligand dtztp and cadmium are utilized to prepare the ligand through self-assembly, and the ligand which has novel structure and is proved to have C2H2And CH4The metal organic framework material with the adsorption and separation functions has the chemical formula as follows:
[(CH3)2NH2][Cd(dtztp)0.5(HCOO)]·1.5DMF·H2O
wherein DMF is N, N-dimethylformamide.
Secondly, preparation method of the metal organic framework material
Example 1
0.10mmol of cadmium nitrate tetrahydrate (metal salt) and 0.05mmol of 2, 5-bis (tetrazolyl) terephthalic acid (ligand) were added to a mixed solvent composed of 3.0ml of N, N-dimethylformamide, 4.0ml of water and 0.45ml of hydrochloric acid. The mixture was placed in a 25ml autoclave, heated to 130 ℃ in a closed state for 70 hours, and then cooled to room temperature at a rate of 0.20 ℃/min. The reaction product was taken out and filtered to obtain colorless prismatic crystals (initial sample). And (3) exchanging the colorless prismatic crystal by using methanol, exchanging the solvent once every 12h for 6 times for total 72h, and then heating the colorless prismatic crystal for 5.5h in vacuum at 150 ℃ to obtain the activated metal organic framework material.
Example 2
0.09mmol of cadmium nitrate tetrahydrate (metal salt) and 0.04mmol of 2, 5-bis (tetrazolyl) terephthalic acid (ligand) were added to a mixed solvent consisting of 2.8ml of N, N-dimethylformamide, 3.8ml of water and 0.4ml of hydrochloric acid. The mixture was placed in a 25ml autoclave, heated to 125 ℃ in a closed manner and held for 65 hours, and then cooled to room temperature at a rate of 0.15 ℃/min. The reaction product was taken out and filtered to obtain colorless prismatic crystals (initial sample). And (3) exchanging the colorless prismatic crystal with methanol, exchanging the solvent once every 12h for 6 times for total 72h, and then heating the mixture in vacuum at 150 ℃ for 5h to obtain the activated metal organic framework material.
Example 3
0.11mmol of cadmium nitrate tetrahydrate (metal salt) and 0.06mmol of 2, 5-bis (tetrazolyl) terephthalic acid (ligand) were added to a mixed solvent composed of 3.2ml of N, N-dimethylformamide, 4.2ml of water and 0.5ml of hydrochloric acid. The mixture was placed in a 25ml autoclave, heated to 135 ℃ in a closed environment for 75 hours, and then cooled to room temperature at a rate of 0.25 ℃/min. The reaction product was taken out and filtered to obtain colorless prismatic crystals (initial sample). And (3) exchanging the colorless prismatic crystal with methanol, exchanging the solvent once every 12h for 6 times for total 72h, and then heating the mixture in vacuum at 150 ℃ for 6h to obtain the activated metal organic framework material.
Thirdly, identifying the structure of the metal organic framework material
The single crystal crystals of the metal organic framework materials prepared in example 1, example 2 and example 3 were structurally characterized and analyzed by a single crystal diffractometer to determine the spatial structure thereof. The results are as follows:
the structures of the single crystal crystals of the metal organic framework materials prepared in the three embodiments are completely the same, the crystals belong to a trigonal R-3 space group, and the asymmetric unit comprises one Cd2+Ions, half dtztp ligand, one formate anion ligand and one dimethylamine cation. Cd [ Cd ]2+The ion has a heptagonally coordinated penta-bipyramidal coordination configuration in which the equatorial plane is occupied by four O atoms and one N atom, respectively from three dtztp ligands and one formate anion, whereas the apex position is occupied by two N atoms of two dtztp ligands, as shown in fig. 1. Further, each dtztp ligand is connected with eight Cd2+Ions, simultaneously each Cd2+Four dtztp ligands are connected through ions to finally form a metal organic framework with a three-dimensional structure, and the framework contains hexagonal pore channels with the size being about the same as that of the pore channels
The porosity was 28.2%, as shown in fig. 2.
Since the structures of the metal organic frame materials prepared in example 1, example 2 and example 3 are completely consistent, the metal organic frame material prepared in example 1 is subjected to characterization and adsorption tests.
The phase purity of the metal organic frame material obtained in example 1 was measured using a powder X-ray diffractometer, and the powder X-ray diffraction result of the metal organic frame material is shown in fig. 3, and it can be seen from fig. 3 that the metal organic frame material has a very high phase purity.
The thermal stability of the metal organic framework material prepared in example 1 was measured using a thermal analyzer, and the results of the measurements show: the metal organic framework material has a thermal stability temperature of about 300 ℃, and has high thermal stability.
Fourthly, adsorption test of the metal organic framework material
The gas adsorption test was carried out using an ASAP 2020M specific surface area meter from mack usa.
The metal organic frame material prepared in example 1 was tested.
The test results were as follows:
(1) the nitrogen adsorption curve of the metal-organic framework material at 77K is shown in FIG. 4, and it can be seen from FIG. 4 that the nitrogen adsorption amount of the metal-organic framework material at 77K and 1 atmosphere is 177.2cm3(STP)g-1The BET specific surface area of the metal-organic framework material was calculated to be 575.8m2g-1；
(2) The metal organic framework material is applied to C at 273K2H2And CH4As shown in FIG. 5, it can be seen from FIG. 5 that the organometallic framework material was applied to C at 273K and 1 atm2H2Has an adsorption amount of 129.7cm3(STP)g-1To CH4Has an adsorption capacity of 12.7cm3(STP)g-1；
(3) The metal organic framework material is applied to C under 298K2H2And CH4The adsorption isotherms of (A) are shown in FIG. 6, and it can be seen from FIG. 6 that the metal-organic framework material was aligned with C at 298K and 1 atm2H2The adsorption amounts of (A) and (B) were all 89.3cm3(STP)g-1To CH4The adsorption amount of (2) was 8.0cm3(STP)g-1。
Thus, at 298K and 1 atmosphere, the metal organic framework material pair C provided by the invention2H2And CH4Showing obvious adsorption selectivity.
In addition, as can be seen from fig. 5 and 6, C2H2Has obvious lagging behavior, which means that the metal organic framework material and C provided by the invention2H2Strong adsorption exists between moleculesAnd (4) acting. The main reason is that the pore channel surface of the metal organic framework material provided by the invention contains a large amount of uncoordinated N atoms, formic acid O atoms, aromatic rings and the like, and polar groups can be reacted with C2H2A different form of force is created resulting in a higher amount of adsorption.
The metal organic framework material pair C can be calculated by utilizing the theory of ideal adsorption solution2H2And CH4C of the mixture2H2/CH4And (4) adsorption selectivity. At 298K and 1 atm for C containing equal parts (equimolar)2H2And CH4Mixture of the metal-organic framework material and C of the mixture2H2/CH4The adsorption selectivity curve of (a) is shown in FIG. 7.
As can be seen from FIG. 7, the metal-organic framework material has equivalent components (equimolar) C2H2And CH4The separation ratio of the mixture at 298K reached 49.1.
Therefore, the metal organic framework material provided by the invention has high C2H2/CH4Adsorption selectivity with separation C2H2And CH4Can be applied to C2H2And CH4In the separation and purification of (3). It should be noted that the above-mentioned embodiments do not limit the present invention in any way, and all technical solutions obtained by using equivalent alternatives or equivalent variations fall within the protection scope of the present invention.
Claims (5)
1. Has a shape of C2H2And CH4The metal organic framework material with the adsorption and separation functions is characterized by having a three-dimensional structure and containing hexagonal pore channels, and the chemical formula is [ (CH)3)2NH2][Cd(dtztp)0.5(HCOO)]·1.5DMF·H2O, wherein dtztp is deprotonated 2, 5-bis (tetrazolyl) terephthalic acid and DMF is N, N-dimethylformamide, wherein dtztp has the following structural formula:
2. having C as claimed in claim 12H2And CH4The preparation method of the metal organic framework material with the adsorption separation function is characterized in that the preparation method adopts a solvothermal synthesis method by taking cadmium nitrate tetrahydrate and 2, 5-bis (tetrazolyl) terephthalic acid as raw materials, and comprises the following steps:
step 1: adding cadmium nitrate tetrahydrate and 2, 5-bis (tetrazolyl) terephthalic acid into a mixed solvent consisting of N, N-dimethylformamide, water and hydrochloric acid;
step 2: placing the mixture in a high-pressure reaction kettle, heating to 125-135 ℃ in a sealed manner, keeping for 65-75 h, and then cooling to room temperature at the speed of 0.15-0.25 ℃/min;
and step 3: taking out the reaction product, and filtering to obtain colorless prismatic crystals;
and 4, step 4: exchanging the colorless prismatic crystal with methanol for 72h, and heating at 150 deg.C under vacuum for 5-6 h to obtain the compound C2H2And CH4A metal organic framework material with adsorption and separation functions.
3. The method according to claim 2, wherein the molar ratio of the cadmium nitrate tetrahydrate to the 2, 5-bis (tetrazolyl) terephthalic acid is 9 to 11: 4 to 6.
4. The preparation method according to claim 2, wherein the volume ratio of the N, N-dimethylformamide to the water to the hydrochloric acid is 28-32: 38-42: 4 to 5.
5. The preparation method according to claim 2, wherein the ratio of the total amount of the cadmium nitrate tetrahydrate and the 2, 5-bis (tetrazolyl) terephthalic acid to the amount of the mixed solvent is 0.13 to 0.17 mmol: 7.0-7.9 mL.
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