Room-temperature solid-phase synthesis method of zinc-based polyazole

Abstract

The room-temperature solid-phase synthesis method comprises the following steps: selecting a zinc-based oxide / hydroxide as a raw material, putting the zinc-based oxide / hydroxide into an agate mortar for preliminary grinding, and removing impurity particles; then selecting a polyazole ligand, weighing the ligand according to the coordination molar ratio of zinc ions to the ligand, and placing the ligand in a vacuum drying oven for low-temperature drying; and finally, mixing and fully grinding solid raw materials, namely zinc metal oxide or zinc metal hydroxide of the target zinc-based multi-nitrogen azole metal organic framework material and multi-nitrogen azole at normal temperature to obtain the zinc-based multi-nitrogen azole MOFs material. High-temperature and high-pressure conditions and organic solvents are not needed, energy consumption is low, no by-product is generated, and green and low-cost preparation is achieved. The obtained zinc-based polyazole MOFs material has high specific surface area, controllable aperture and good crystallinity, shows excellent performance in the fields of battery energy storage, electromagnetic wave absorption, gas adsorption separation and the like, and can be applied to industrial large-scale production and multiple fields.

Description

Technical Field

[0001] This invention relates to the field of metal-organic framework materials technology, specifically to a room-temperature solid-phase synthesis method for zinc-based polyazoles. Background Technology

[0002] Metal-organic frameworks (MOFs) are porous organic and inorganic hybrid materials composed of metal ions and organic ligands. They are synthesized under certain conditions through coordination bonds. These materials are also known as coordination polymers. MOFs, with their high porosity, large specific surface area, abundant active sites, pore size, and tunable structure, have shown excellent application prospects in many fields such as battery energy storage, electromagnetic wave absorption, gas adsorption and separation, and catalytic reactions.

[0003] In the research of MOF materials, the choice of metal ions as central ions plays a decisive role in the structural properties and functions of the materials. Zinc ions, as a common transition metal ion, possess unique electronic configurations and coordination capabilities, resulting in MOF materials with good chemical stability and compatibility, offering irreplaceable advantages in fields such as battery energy storage, electrochemical catalysis, and environmental pollutant adsorption. Polyazole organic ligands (such as pyrazole, triazole, tetraazole, and their derivatives) possess abundant nitrogen atom coordination sites, forming stable coordination bonds with zinc metal ions. By combining with different ligand structures, diverse zinc-based polyazole MOF materials can be constructed. These materials not only inherit the porous characteristics of MOFs but also exhibit superior performance in energy storage (providing more active sites and optimizing ion transport channels) and electromagnetic wave absorption (numerous heterojunction surfaces and interfacial polarization) due to the introduction of polyazole ligands, further broadening the application range of MOF materials.

[0004] However, the synthesis technology of zinc-based polyazole MOFs still faces significant bottlenecks. Traditional liquid-phase synthesis strategies, such as solvothermal and hydrothermal methods, have many limitations: First, they require long-term reactions at high temperatures and high pressures of 80-200℃, lasting 3-7 days. This process not only consumes a huge amount of energy, but the high temperature and high pressure conditions can also easily cause product structural collapse or side reactions, leading to a decrease in purity. Second, normal synthesis systems require large amounts of organic solvents, which are highly volatile, posing a risk of environmental pollution and significantly increasing production costs. This makes it difficult to meet the needs of continuous industrial production, becoming a major challenge for the large-scale production and application of zinc-based polyazole MOFs.

[0005] CN109734927B discloses "A Zinc-Based Metal Polyazole Framework Material DGUT-1 and Its Preparation Method." The problems with this invention are: 1. Incomplete solid-phase synthesis, requiring heating to drive the reaction. The milled mixture must be transferred to a closed system and subjected to subsequent reactions at 25-180°C. 2. Limited raw material selection, high cost, and potential introduction of byproducts or impact on purity. The zinc source used in this invention is zinc salts such as zinc acetate, zinc chloride, and zinc nitrate. These raw materials are expensive and unsuitable for industrial production. Furthermore, anions such as acetate and chloride may decompose or release during the reaction, potentially remaining as byproducts requiring additional washing steps. Incomplete removal may affect the purity of the final product. 3. The reaction cycle remains long, and efficiency needs improvement. After ball milling, the reaction time ranges from 5 minutes to 24 hours, but the preferred embodiment still requires 10 hours of reaction at 150°C. Summary of the Invention

[0006] The purpose of this invention is to address the technical challenges in the synthesis of zinc-based polyazole MOFs using solvothermal and hydrothermal methods, such as high energy consumption, long reaction cycles, significant organic solvent pollution, and poor industrial applicability.

[0007] The present invention adopts the following technical solution: A room-temperature solid-phase synthesis method for zinc-based polyazoles includes the following steps: Step 1, Zinc source selection and grinding: Zinc oxide or zinc hydroxide is selected as the zinc source, and it is placed in an agate mortar for preliminary grinding to remove impurity particles and obtain zinc source powder with uniform particle size. Step 2, Polyazole ligand pretreatment: Select polyazole ligands, weigh the ligands according to the coordination stoichiometry of zinc ions and ligands, and dry the ligands in a vacuum drying oven to remove adsorbed water; Step 3: Material mixing and ball milling: Set the ball mill parameters, add the zinc source powder obtained from the initial grinding and the pretreated polyazole ligand to the agate ball mill jar of the planetary ball mill in a metered ratio, and add agate balls at the same time. Mix and grind the two thoroughly to obtain the final target product, which is zinc-based polyazole.

[0008] Furthermore, the molar ratio of zinc oxide or zinc hydroxide in step 1 to the polyazole ligand in step 2 is 1:2.

[0009] Furthermore, the initial grinding time in step 1 is 10-15 minutes.

[0010] Furthermore, the polyazole ligand used in step 2 is pyrazole or 1,2,4-triazole.

[0011] Furthermore, in step 2, the vacuum drying temperature is 60-80℃, and the drying time is 2-4 hours.

[0012] Furthermore, the ball mill parameters in step 3 are: rotation speed adjusted to 300 rpm, temperature at 25℃, and ball milling time at 3-5 hours.

[0013] Furthermore, in step 3, the ball mill operates by intermittent shutdown, stopping for 5 minutes every 30 minutes.

[0014] Furthermore, in step 3, the diameter of the agate ball is 10 mm, and the ratio of the mass of the agate ball to the total mass of the material is controlled to be 10:1.

[0015] Compared with the prior art, the beneficial effects of the present invention are: (1) Dual advantages in raw material cost and environmental friendliness: This invention innovatively selects industrial-grade zinc oxide or zinc hydroxide as the zinc source. Compared with conventional zinc salts such as zinc acetate, which are more expensive, this not only reduces the cost of raw materials, but also avoids the formation of byproducts by zinc salt anions in the reaction from the source. Apart from the possible generation of some water vapor, it achieves true zero byproduct emissions. At the same time, this invention found that pyrazole has a unique reaction compatibility with this zinc source ligand. Under the action of mechanical force, it can coordinate with the zinc site more efficiently, further improving the completeness of the reaction and the purity of the product.

[0016] (2) Precise control of raw material pretreatment ensures stable and efficient reaction: This invention innovatively introduces mechanical activation treatment of the zinc source and drying pretreatment of the ligands. Preliminary grinding of the zinc source is not only to remove impurity particles, but more importantly, to obtain uniformly sized active zinc source powder. This lays the foundation for subsequent homogeneous and efficient solid-phase reactions. Strict vacuum drying of the ligands completely eliminates the competition and interference of adsorbed water on the coordination reaction, ensuring that the N atoms of the ligands can directly and efficiently coordinate with Zn²⁺. These two pretreatment steps guarantee the purity and stability of the reaction from the source, which is a prerequisite for obtaining high-purity products.

[0017] (3) Rapid synthesis at room temperature throughout the process, with significantly improved efficiency: By optimizing the ball milling parameters (300 rpm, with an intermittent strategy of stopping for 5 minutes every 30 minutes), the reaction can be completed at room temperature (25°C) for a maximum of 5 hours, halving the reaction cycle. Moreover, since no solvent is required, the raw materials can achieve high-density loading of the packing material, and the yield of the final product formed per unit volume of ball mill jar is much larger than that of traditional synthesis. Most importantly, the reaction only requires ball milling and has no special requirements on the volume of the reaction vessel, proving that it is also suitable for industrial-scale mass production, realizing the conversion from gram-level to kilogram-level or even ton-level.

[0018] (4) Excellent product structure and performance: Experiments show that the zinc-based polyazole framework material prepared by the method of this invention exhibits sharp characteristic peaks in its X-ray diffraction pattern at 2θ of 10.5°, 15.2°, and 20.8°, indicating that it has a crystal structure and high crystallinity superior to those in the prior art. High yield, high purity, and high specific surface area, along with a complete porous structure and uniform pore size distribution, lay a solid foundation for its excellent application performance in fields such as battery energy storage and electromagnetic wave absorption. Attached Figure Description

[0019] Figure 1 This is a flowchart of the room-temperature solid-phase synthesis method of zinc-based polyazoles according to the present invention; Figure 2 This is the XRD pattern (matched with standard card) of the zinc-based polyazole material synthesized from zinc oxide, zinc hydroxide and pyrazole after one hour of ball milling in this invention. Figure 3 This is the XRD pattern (matched with standard card) of the zinc-based polyazole material synthesized from zinc oxide, zinc hydroxide and pyrazole after ball milling for three hours in this invention. Figure 4 This is the XRD pattern (matched with the standard card) of the zinc-based polyazole material synthesized from zinc oxide, zinc hydroxide and pyrazole after ball milling for five hours in this invention. Detailed Implementation

[0020] To further understand the present invention, the present invention will be described below with reference to embodiments. These descriptions are only for further explaining the features and advantages of the present invention and are not intended to limit the claims of the present invention.

[0021] This invention provides a room-temperature solid-phase synthesis method for zinc-based polyazoles. First, zinc-based oxides / hydroxides are selected as raw materials and pre-ground in an agate mortar to remove impurities. Next, polyazole ligands are selected, and the ligands are weighed according to the coordination stoichiometry between zinc ions and the ligands. The ligands are then dried at low temperature in a vacuum drying oven to eliminate adsorbed water on the ligand surface, ensuring efficient coordination between the ligands and the zinc group during subsequent grinding. Finally, the solid raw materials—zinc oxide or zinc hydroxide—and the polyazoles in the stoichiometric ratio of the target zinc-based polyazole metal-organic framework material are mixed and thoroughly ground at room temperature to obtain the final target product.

[0022] The synthesis principle of the key steps in this invention: In a ball mill, agate balls impact, compress, and shear the zinc source and organic ligands under varying rotational speeds. This mechanical force causes localized lattice fracture in the zinc-based metal, leading to partial dissociation of Zn-O or Zn-OH bonds. The longer the milling time, the better the dissociation effect, resulting in unsaturated coordinated Zn. 2+The loss of electrons causes it to move closer to the polyazole ligand. Under the force generated by ball milling, the azole ligand undergoes a molecular configuration that makes it easier for the isolated electrons in the N atom to bind with Zn. 2+ By combining these elements, the reaction energy barrier is lowered, achieving an organic combination of the two and ultimately forming a zinc-based metal-organic framework material.

[0023] Example 1: The method for room-temperature solid-phase synthesis of zinc-based polyazoles of the present invention is as follows: Figure 1 As shown, the specific operation steps are as follows: (1) Select zinc oxide (0.561 g, 1 mol) as the zinc source, place it in an agate mortar, add agate balls with a diameter of 10 mm (the ball-to-material ratio is controlled at 10:1), grind for 10 minutes to remove impurity particles and obtain zinc source powder with uniform particle size.

[0024] (2) Pyrazole (0.867 g, 1 mol) was selected as the raw material for polyazole ligand. The ligand was weighed according to the molar ratio of zinc ions to ligand at 1:2. The ligand was placed in a vacuum drying oven and dried at 60°C for 4 hours to remove adsorbed water and avoid moisture affecting the coordination reaction, thus ensuring that the N atom of the ligand could coordinate directly and efficiently with Zn²⁺.

[0025] (3) The pretreated zinc oxide powder and pyrazole ligand were added to the agate ball mill jar of the ball mill at a molar ratio of 1:2, along with agate balls (ball-to-material ratio controlled at 10:1). The ball mill speed was set to 300 rpm. The mechanical energy provided at this speed was sufficient to effectively activate the zinc source lattice and drive the coordination reaction, while avoiding local overheating caused by excessive energy. The ball milling reaction was carried out at room temperature (25°C) and normal pressure for 3 hours. During the ball milling process, the machine was stopped intermittently for 5 minutes every 30 minutes to avoid local overheating that could lead to ligand decomposition, ensuring that the materials were fully mixed and reacted to form the final product, zinc-based polyazole material.

[0026] Example 2: (1) Select zinc hydroxide (0.633 g, 1 mol) as the zinc source, place it in an agate mortar, add agate balls with a diameter of 10 mm (the ball-to-material ratio is controlled at 10:1), grind for 15 minutes to remove impurity particles and obtain zinc source powder with uniform particle size.

[0027] (2) 1,2,4-triazole (0.869 g, 1 mol) was selected as the raw material for polyazole ligand. The ligand was weighed at a molar ratio of zinc ion to ligand of 1:2. The ligand was placed in a vacuum drying oven and dried at 60°C for 4 hours to remove adsorbed water and avoid moisture affecting the coordination reaction, thus ensuring that the N atom of the ligand could coordinate directly and efficiently with Zn²⁺.

[0028] (3) The pretreated zinc oxide powder and pyrazole ligand were added to the agate ball mill jar of the ball mill at a molar ratio of 1:2, along with agate balls (ball-to-material ratio controlled at 10:1). The ball mill speed was set to 300 rpm. The mechanical energy provided at this speed was sufficient to effectively activate the zinc source lattice and drive the coordination reaction, while avoiding local overheating caused by excessive energy. The ball milling reaction was carried out at room temperature (25°C) and normal pressure for 3 hours. During the ball milling process, the machine was stopped intermittently for 5 minutes every 30 minutes to avoid local overheating that could lead to ligand decomposition, ensuring that the materials were fully mixed and reacted to form the final product, zinc-based polyazole material.

[0029] Example 3: (1) Select zinc oxide (0.561 g, 1 mol) as the zinc source, place it in an agate mortar, add agate balls with a diameter of 10 mm (the ball-to-material ratio is controlled at 10:1), grind for 15 minutes to remove impurity particles and obtain zinc source powder with uniform particle size.

[0030] (2) Pyrazole (0.867 g, 1 mol) was selected as the raw material for polyazole ligand. The ligand was weighed according to the molar ratio of zinc ions to ligand at 1:2. The ligand was placed in a vacuum drying oven and dried at 70°C for 3 hours to completely remove adsorbed water and avoid moisture affecting the coordination reaction, thus ensuring that the N atom of the ligand can coordinate directly and efficiently with Zn²⁺.

[0031] (3) The pretreated zinc oxide powder and pyrazole ligand were added to the agate ball mill jar of the ball mill at a molar ratio of 1:2, along with agate balls (ball-to-material ratio controlled at 10:1). The ball mill speed was set to 300 rpm. The mechanical energy provided at this speed was sufficient to effectively activate the zinc source lattice and drive the coordination reaction, while avoiding local overheating caused by excessive energy. The ball milling reaction was carried out at room temperature (25°C) and normal pressure for 4 hours. During the ball milling process, the machine was stopped intermittently for 5 minutes every 30 minutes to avoid local overheating that could lead to ligand decomposition, ensuring that the materials were fully mixed and reacted to form the final product, zinc-based polyazole material.

[0032] Example 4: (1) Select zinc hydroxide (0.633 g, 1 mol) as the zinc source, place it in an agate mortar, add agate balls with a diameter of 10 mm (the ball-to-material ratio is controlled at 10:1), grind for 15 minutes to remove impurity particles and obtain zinc source powder with uniform particle size.

[0033] (2) Pyrazole (0.867 g, 1 mol) was selected as the raw material for polyazole ligand. The ligand was weighed according to the molar ratio of zinc ions to ligand at 1:2. The ligand was placed in a vacuum drying oven and dried at 70°C for 3 hours to completely remove adsorbed water and avoid moisture affecting the coordination reaction, thus ensuring that the N atom of the ligand can coordinate directly and efficiently with Zn²⁺.

[0034] (3) The pretreated zinc oxide powder and pyrazole ligand were added to the agate ball mill jar of the ball mill at a molar ratio of 1:2, along with agate balls (ball-to-material ratio controlled at 10:1). The ball mill speed was set to 300 rpm. The mechanical energy provided at this speed was sufficient to effectively activate the zinc source lattice and drive the coordination reaction, while avoiding local overheating caused by excessive energy. The ball milling reaction was carried out at room temperature (25°C) and normal pressure for 4 hours. During the ball milling process, the machine was stopped intermittently for 5 minutes every 30 minutes to avoid local overheating that could lead to ligand decomposition, ensuring that the materials were fully mixed and reacted to form the final product, zinc-based polyazole material.

[0035] Example 5: (1) Select zinc oxide (0.561 g, 1 mol) as the zinc source, place it in an agate mortar, add agate balls with a diameter of 10 mm (the ball-to-material ratio is controlled at 10:1), grind for 15 minutes to remove impurity particles and obtain zinc source powder with uniform particle size.

[0036] (2) Pyrazole (0.867 g, 1 mol) was selected as the raw material for polyazole ligand. The ligand was weighed according to the molar ratio of zinc ions to ligand at 1:2. The ligand was placed in a vacuum drying oven and dried at 80°C for 2 hours to completely remove adsorbed water and avoid moisture affecting the coordination reaction, thus ensuring that the N atom of the ligand can coordinate directly and efficiently with Zn²⁺.

[0037] (3) The pretreated zinc oxide powder and pyrazole ligand were added to the agate ball mill jar of the ball mill at a molar ratio of 1:2, along with agate balls (ball-to-material ratio controlled at 10:1). The ball mill speed was set to 300 rpm. The mechanical energy provided at this speed was sufficient to effectively activate the zinc source lattice and drive the coordination reaction, while avoiding local overheating caused by excessive energy. The ball milling reaction was carried out at room temperature (25°C) and normal pressure for 5 hours. During the ball milling process, the machine was stopped intermittently for 5 minutes every 30 minutes to avoid local overheating that could lead to ligand decomposition, ensuring that the materials were fully mixed and reacted to form the final product, zinc-based polyazole material.

[0038] Example 6: (1) Select zinc hydroxide (0.633 g, 1 mol) as the zinc source, place it in an agate mortar, add agate balls with a diameter of 10 mm (the ball-to-material ratio is controlled at 10:1), grind for 15 minutes to remove impurity particles and obtain zinc source powder with uniform particle size.

[0039] (2) Pyrazole (0.867 g, 1 mol) was selected as the raw material for polyazole ligand. The ligand was weighed according to the molar ratio of zinc ions to ligand at 1:2. The ligand was placed in a vacuum drying oven and dried at 80°C for 2 hours to completely remove adsorbed water and avoid moisture affecting the coordination reaction, thus ensuring that the N atom of the ligand can coordinate directly and efficiently with Zn²⁺.

[0040] (3) The pretreated zinc oxide powder and pyrazole ligand were added to the agate ball mill jar of the ball mill at a molar ratio of 1:2, along with agate balls (ball-to-material ratio controlled at 10:1). The ball mill speed was set to 300 rpm. The mechanical energy provided at this speed was sufficient to effectively activate the zinc source lattice and drive the coordination reaction, while avoiding local overheating caused by excessive energy. The ball milling reaction was carried out at room temperature (25°C) and normal pressure for 5 hours. During the ball milling process, the machine was stopped intermittently for 5 minutes every 30 minutes to avoid local overheating that could lead to ligand decomposition, ensuring that the materials were fully mixed and reacted to form the final product, zinc-based polyazole material.

[0041] like Figure 2This is the XRD pattern of the zinc-based polyazole material synthesized from zinc oxide, zinc hydroxide, and pyrazole after one hour of ball milling, as part of the comparative experiment of this invention. Comparison with standard charts shows that the characteristic peaks of zinc oxide and zinc hydroxide are still clearly visible. Although the peak shapes are slightly wider than those of the unmilled raw material, the peak intensity is only reduced by about 10%, and the match with the standard spectrum is still over 90%. This indicates that ball milling for 1 hour only produces a slight mechanical effect on the zinc oxide and zinc hydroxide particles. It breaks up some surface agglomerates but does not significantly damage the crystal structure. The Zn²⁺ active sites are less exposed, the coordination reaction has not yet fully occurred, and the main body of the raw material still maintains the crystal structure of zinc oxide and zinc hydroxide.

[0042] Figure 3 shows the XRD patterns of zinc-based polyazole materials synthesized from zinc oxide, zinc hydroxide, and pyrazole after ball milling for three hours in Examples 1 and 2 of this invention. Comparison with standard charts reveals that the characteristic peak intensities of zinc oxide and zinc hydroxide are lower than those after ball milling for 1 hour, the peak shapes are significantly broadened, and the patterns are more consistent with standard spectra. Furthermore, some weak characteristic peaks are blurred. This indicates that the mechanical force of ball milling for 3 hours has disrupted a large number of the lattices of zinc oxide and zinc hydroxide, resulting in significant distortion of the crystal structure. More Zn²⁺ detaches from the lattice and becomes active sites, initiating coordination reactions with polyazole ligands, thus increasing the raw material conversion rate. Zinc hydroxide exhibits lower lattice stability, and its coordination reaction rate is much faster than that of zinc oxide.

[0043] Figure 4 shows the XRD patterns of zinc-based polyazole materials synthesized from zinc oxide, zinc hydroxide, and pyrazole after ball milling for five hours in Examples 5 and 6 of this invention. By comparing with the standard chart, it can be observed that the characteristic peaks of zinc oxide and zinc hydroxide completely disappeared, with no residual signals, and the matching degree with the standard spectrum was better, indicating that the conversion of zinc oxide and zinc hydroxide was completed. Moreover, the characteristic peaks at 2θ=10.5°, 15.2°, and 20.8° completely corresponded to the characteristic peaks of the standard spectrum, with sharp peak shapes and high peak intensities, indicating that the zinc-based polyazole MOFs generated by the conversion of zinc hydroxide had good crystallinity and a complete three-dimensional coordination framework structure.

[0044] Based on Figures 2-4, as the ball milling time increases, the XRD characteristics exhibit a pattern of "gradual decrease in raw material peak intensity → increased peak broadening → complete disappearance of raw material peaks → clear formation of product peaks." Furthermore, zinc hydroxide, due to its lower lattice stability, consistently converts faster than zinc oxide. The room-temperature ball milling time is a key factor driving the conversion of the zinc source into zinc-based polyazole MOFs. Zinc hydroxide is more susceptible to coordination reactions under mechanical forces, making it a superior zinc source choice. The obtained zinc-based polyazole MOFs exhibit good crystallinity and are free of byproducts, meeting the synthesis objectives of this invention.

[0045] Of the above embodiments, embodiment 5 is the best embodiment.

[0046] The preferred embodiments of the present invention disclosed above are merely illustrative of the invention. These preferred embodiments do not exhaustively describe all details, nor do they limit the invention to any specific implementation. Clearly, many modifications and variations can be made based on the content of this specification. This specification selects and specifically describes these embodiments to better explain the principles and practical applications of the invention, thereby enabling those skilled in the art to better understand and utilize the invention. The invention is limited only by the claims and their full scope and equivalents.

Claims

1. A process for the room temperature solid phase synthesis of zinc based polyazoles, characterized by, The method comprises the following steps: Step 1, selection and grinding of zinc source: Selecting zinc oxide or zinc hydroxide as the zinc source, and initially grinding the zinc source in an agate mortar to remove impurity particles and obtain zinc source powder with uniform particle size; Step 2, pretreatment of polyazole ligand: Selecting a polyazole ligand, weighing the ligand according to the coordination stoichiometric ratio of zinc ions and the ligand, and drying the ligand in a vacuum drying box to remove adsorbed water; Step 3, mixing and ball milling of materials: Setting the parameters of the ball mill, adding the zinc source powder obtained by initial grinding and the pretreated polyazole ligand into an agate ball mill tank of the planetary ball mill according to the measurement ratio, and adding agate balls, so that the two are fully mixed and ground, and the final target product, i.e., zinc-based polyazoles, is obtained.

2. A process for room temperature solid phase synthesis of zinc based polyazoles as claimed in claim 1 wherein: The molar ratio of the zinc oxide or zinc hydroxide in step 1 to the polyazole ligand in step 2 is 1:

2.

3. A process for room temperature solid phase synthesis of zinc based polyazoles as claimed in claim 2, wherein the process comprises of: The initial grinding time in step 1 is 10-15 minutes.

4. The method for room temperature solid phase synthesis of zinc-based polyazoles according to claim 3, characterized by the fact that: The polyazole ligand in step 2 is pyrazole or 1,2,4-triazole.

5. A process for room temperature solid phase synthesis of zinc based polyazoles as claimed in claim 4, wherein the process comprises of: The vacuum drying temperature in step 2 is 60-80°C, and the drying time is 2-4 hours.

6. The method of claim 5, wherein the zinc-based polyazolate is synthesized at room temperature. The ball mill parameters in step 3 are as follows: the rotation speed is adjusted to 300 rmp, the temperature is 25°C, and the ball milling time is 3-5 hours.

7. The method of claim 6, wherein the zinc-based polyazolate is synthesized at room temperature in a solid phase. The ball mill works in an intermittent stop mode, i.e., stopping every 30 minutes for 5 minutes.

8. The method of claim 7, wherein the zinc-based polyazolate is synthesized at room temperature. The diameter of the agate balls in step 3 is 10 mm, and the ratio of the mass of the agate balls to the total mass of the materials is controlled to be 10:1.

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