CN115662797A - Preparation method of ZIF-67 derived transition metal sulfide for electrode material - Google Patents
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Abstract
A preparation method of a ZIF-67 derived transition metal sulfide for an electrode material comprises the following steps: (1) Dissolving 2-methylimidazole and cobalt nitrate in an organic solvent, and standing at normal temperature for 24 hours to prepare a Metal Organic Framework (MOFs) ZIF-67; (2) ZIF-67, copper chloride, stannous chloride and thioacetamide are used as reactants, a precursor solution is formed in an organic solvent under the condition of stirring, and the reaction is carried out for 4 to 10 hours in a stainless steel reaction kettle at the temperature of between 90 and 120 ℃; (3) Waiting reaction kettleCooling to room temperature, decanting the supernatant clear solution, washing the product with absolute ethanol and deionized water, respectively, and drying in a vacuum oven to obtain ZIF-67-derived Cu 2 CoSnS 4 (CCTS) nanomaterials. The method has simple process and environmental protection, and the CCTS nano material has a porous structure, increases the specific surface area, accelerates the diffusion and transmission of electrolyte ions, and has excellent electrochemical performance. Therefore, the invention has wide application prospect in the field of high-performance super capacitors.
Description
Technical Field
The invention relates to the technical field of electrode materials of super capacitors, in particular to a preparation method of a transition metal sulfide derived from ZIF-67 for an electrode material.
Background
The increasing energy demand and ever-deteriorating environmental conditions around the world have prompted researchers to develop efficient energy storage and conversion technologies. Supercapacitors (SCs) are a promising charge storage system that have received much attention due to their fast charging and discharging speed, high power density and long lifetime. However, the lower energy density of supercapacitors compared to rechargeable batteries limits their practical use. Therefore, the search for high performance electrode materials is a significant challenge to meet the high demands of their practical applications.
To date, carbon materials, transition metal compounds (including transition metal oxides/hydroxides/sulfides), conductive polymers, and composites thereof have been extensively studied. However, the carbon material has a low specific capacitance and a low energy density, and the conductive polymer-based electrode exhibits poor cycle stability. The transition metal compound serving as a typical pseudocapacitance material has a plurality of oxidation states due to high theoretical capacitance and high electrochemical activity, and is a more preferable electrode material of the super capacitor. However, large-scale development of transition metal sulfides has been limited due to their inherent disadvantages of poor conductivity, low energy density, and the like.
Metal Organic Frameworks (MOFs) are a class of hybrid porous crystalline materials composed of organic ligands and metal ions, and have been widely studied in various fields. Especially ZIF-67 is a subfamily of MOFs, which due to its shape tunability, high porosity and excellent chemical stability, proved to be a good template or precursor for the preparation of micro-nanostructured electrode materials, commonly used for the fabrication of porous structures by simple ion etching/exchange. The electrode material with the structure can provide a large surface area, promote ion diffusion, enlarge the interface contact area of the electrode/electrolyte and relieve volume expansion, thereby improving the structural integrity. Therefore, deriving the transition metal sulfide electrode material by reasonably designing ZIF-67 as a template is an effective way to solve the above-mentioned problems.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of a transition metal sulfide derived from ZIF-67 for an electrode material, which has simple steps and mild conditions and is used for solving the problems of small specific capacitance, poor conductivity, low energy density, complex preparation process, environmental pollution and the like of the transition metal sulfide in the prior art.
In order to solve the technical problems, the invention provides a preparation method of a ZIF-67 derived transition metal sulfide for an electrode material, which comprises the following steps:
(1) Synthesis of ZIF-67: respectively dissolving 2-methylimidazole and cobalt nitrate hexahydrate in an organic solvent with the same volume, stirring for a certain time, quickly pouring a 2-methylimidazole solution into a cobalt nitrate hexahydrate solution under rapid stirring, standing at room temperature for 24 hours, centrifugally cleaning a product by using methanol, and drying in a vacuum drying oven to obtain ZIF-67;
(2) Synthesis of ZIF-67 derived CCTS: ZIF-67, copper chloride dihydrate, stannous chloride dihydrate and thioacetamide are used as reactants, a precursor solution is formed under the condition of stirring an organic solvent, and the mixture is reacted for 4 to 10 hours at the temperature of between 90 and 120 ℃ in a reaction kettle;
(3) Preparation of ZIF-67 derived CCTS nanomaterial: and when the reaction kettle is cooled to room temperature, pouring out the upper layer transparent solution, washing the product with absolute ethyl alcohol and deionized water, and drying in a vacuum drying oven to obtain the ZIF-67 derived CCTS nano material.
Preferably, the amount ratio of the 2-methylimidazole to the cobalt nitrate hexahydrate in the step (1) is (2-4) to (0.6-1.2).
Preferably, the organic solvent in step (1) is N, N-dimethylformamide or methanol.
Preferably, in the step (1), the 2-methylimidazole and the cobalt nitrate hexahydrate are respectively dissolved in an equal volume of the organic solvent, and the stirring time is 30-60min.
Preferably, the methanol centrifugal washing in the step (1) is specifically methanol centrifugal washing for 20min, and is repeated three times.
Preferably, the ratio of the amount of copper chloride dihydrate, ZIF-67, stannous chloride dihydrate and thioacetamide in the step (2) is (1.5-2.5) to (0.08-0.3) to (0.8-1.5) to (3-4.5), and the ratio of the amount of organic solvent to all reactant substances is (140) (0.5-1).
Preferably, the organic solvent in the step (2) is N, N-dimethylformamide or ethanol.
Preferably, the stirring mode in the step (1) and the step (2) adopts magnetic stirring, and the rotating speed is 800-1000r/min.
Preferably, the washing product in the step (3) is firstly centrifuged by deionized water for 20min, then centrifuged by absolute ethyl alcohol for 20min, and the process is repeated three times.
Preferably, the temperature of the vacuum drying oven in the step (1) and the step (3) is 60-80 ℃, and the drying time of the vacuum drying oven is 10-14h.
The preparation method of the ZIF-67 derived transition metal sulfide for the electrode material has the advantages that:
(1) ZIF-67 is adopted as a template and is used as a source of Co element, and the process is innovative;
(2) A simple one-step hydrothermal method is adopted, so that the steps are simplified, the process is simple, and the green and environment-friendly effects are achieved;
(3) The CCTS material prepared by the invention has a pore structure, so that the specific surface area is increased, a large number of active sites and low resistance are provided, and the diffusion and transmission of electrolyte ions are accelerated. Meanwhile, the obvious synergistic effect among multiple transition metal ions is beneficial to improving the electrochemical performance;
(4) The invention provides a new idea for preparing the electrode material of the super capacitor. The prepared electrode material has high specific capacitance, high conductivity and good cycling stability, and has great application prospect and economic value in the field of super capacitors.
Drawings
FIG. 1 is a flow chart of a ZIF-67 derived CCTS nanomaterial prepared in example 1 of the present invention;
FIG. 2 is a Scanning Electron Microscope (SEM) view of a ZIF-67 derived CCTS nanomaterial prepared in example 1 of the present invention;
FIG. 3 is an energy dispersive X-ray spectroscopy (EDX) of a ZIF-67 derived CCTS nanomaterial prepared in example 1 of the present invention;
FIG. 4 is an X-ray diffraction pattern (XRD) of a ZIF-67 derived CCTS nanomaterial prepared in example 1 of the present invention;
FIG. 5 is a Cyclic Voltammogram (CV) of a ZIF-67 derived CCTS nanomaterial prepared in example 1 of the present invention;
FIG. 6 is a constant DC charge-discharge diagram (GCD) of a ZIF-67 derived CCTS nanomaterial prepared in example 1 of the present invention;
FIG. 7 is an alternating current impedance diagram (EIS) of a ZIF-67 derived CCTS nanomaterial prepared in example 1 of the present invention;
fig. 8 is a cycle stability test chart of the ZIF-67-derived CCTS nanomaterial prepared in example 1 of the present invention.
Detailed Description
The invention provides a preparation method of a ZIF-67 derived transition metal sulfide for an electrode material, which comprises the following steps:
(1) Synthesis of ZIF-67: respectively dissolving 2-methylimidazole and cobalt nitrate hexahydrate in an organic solvent with the same volume, stirring for 30-60min, quickly pouring the 2-methylimidazole solution into the cobalt nitrate hexahydrate solution under rapid stirring, standing at room temperature for 24h, centrifugally cleaning the product with methanol for 20min, repeating the steps for three times, and drying in a vacuum drying oven to obtain ZIF-67, wherein the drying temperature is 60-80 ℃, and the drying time is 10-14h; wherein the mass ratio of the 2-methylimidazole to the cobalt nitrate hexahydrate is (2-4) to (0.6-1.2), and the organic solvent is N, N-dimethylformamide or methanol.
(2) Synthesis of ZIF-67 derived CCTS: ZIF-67, copper chloride dihydrate, stannous chloride dihydrate and thioacetamide are used as reactants, a precursor solution is formed under the condition of stirring an organic solvent, and the mixture is reacted for 4 to 10 hours at the temperature of between 90 and 120 ℃ in a reaction kettle; wherein the mass ratio of the copper chloride dihydrate, the ZIF-67, the stannous chloride dihydrate and the thioacetamide is (1.5-2.5) to (0.08-0.3) to (0.8-1.5) to (3-4.5), the mass ratio of the organic solvent to all reactant substances is (140) to (0.5-1), and the organic solvent is N, N-dimethylformamide or ethanol.
(3) Preparation of ZIF-67 derived CCTS nanomaterial: and (3) after the reaction kettle is cooled to room temperature, pouring out the upper layer transparent solution, washing the product with absolute ethyl alcohol and deionized water, firstly centrifuging for 20min with the deionized water, then centrifuging for 20min with the absolute ethyl alcohol, repeating the process for three times, and drying in a vacuum drying oven at the drying temperature of 60-80 ℃ for 10-14h to obtain the ZIF-67 derived CCTS nano material.
The stirring modes in the step (1) and the step (2) adopt magnetic stirring, and the rotating speed is 800-1000r/min.
The technical solution of the present invention is further illustrated by the accompanying drawings and examples.
Example 1
(1) Synthesis of ZIF-67: 44.32mmol of 2-methylimidazole, 14.10mmol of Co (NO) 3 ) 2 ·6H 2 O is respectively dissolved in 200mL of methanol, and the mixture is magnetically stirred for 30min at the rotating speed of 800r/min. The 2-methylimidazole solution was then poured rapidly into Co (NO) with magnetic stirring 3 ) 2 ·6H 2 Standing the solution in O solution for 24h at room temperature, centrifugally cleaning the product with methanol, repeating the process for three times, and drying the product in a vacuum drying oven at 60 ℃ for 12h to obtain ZIF-67;
(2) Sequentially adding 2mmol CuCl of reactant precursor 2 ·2H 2 O、0.3mmolZIF-67、 1mmolSnCl 2 ·2H 2 O and 4mmol thioacetamide were added to the polytetrafluoroethylene liner. Weighing 1.65mol of ethanol, adding into the lining, adding magnetons, magnetically stirring for 30min under heating conditions at a rotation speed of 800r/min, placing the lining into a stainless steel autoclave, and then placing the autoclave into a 120 ℃ oven for reaction for 4h;
(3) After the reaction kettle is cooled to room temperature, the upper layer transparent solution is poured out, the product is sequentially centrifugally cleaned for 20min by deionized water and absolute ethyl alcohol and the process is repeated for three times, and the cleaned product is placed in a vacuum oven at 60 ℃ for vacuum drying for 12h.
The Scanning Electron Microscope (SEM) of the product is shown in FIG. 2, and FIG. 2 (a) is an SEM of ZIF-67, from which the typical polyhedral structure of ZIF-67, uniform in size and distribution, can be seen, indicating that ZIF-67 was successfully synthesized. Fig. 2 (b) shows a ZIF-67 derived CCTS material, which exhibits a porous structure, and a large number of pore structures increase the specific surface area of the material, provide low resistance and a large number of active sites, and facilitate the diffusion and transport of electrolyte ions, thereby improving the electrochemical performance of the material.
The energy dispersive X-ray (EDX) spectrum of the product is shown in fig. 3, from which it can be seen that peaks exist for each element, demonstrating the presence of Cu, co, sn, S elements in the ZIF-67 derived CCTS material.
The X-ray diffraction pattern (XRD) of the material is shown in fig. 4, which is used to study the crystal and phase structure of CCTS nanostructures. As can be seen from the figure, there are more distinct diffraction peaks at 28.5 DEG, 32.6 DEG, 47.5 DEG and 56.1 DEG 2 theta, which correspond to the (112), (004), (204) and (312) crystal planes of CCTS, respectively, further illustrating the success of preparing ZIF-67 derived CCTS electrode materials.
The Cyclic Voltammogram (CV) of the material is shown in fig. 5, the cyclic voltammetry test is performed in a three-electrode system, foamed nickel attached with CCTS (the foamed nickel is ultrasonically cleaned for 20min by acetone, 3M hydrochloric acid, deionized water and absolute ethyl alcohol respectively and is dried in vacuum at 60 ℃ for 12 h) is taken as a working electrode, a platinum sheet is taken as a counter electrode, and a saturated calomel electrode is taken as a reference electrode, so as to research the electrochemical performance of the material. As can be seen, there are distinct redox peaks in the CV curve at scan rates of 5-50 mV/s. As the scan rate increased, there was no significant change in the shape of the CV curve, but the anode and cathode peaks were slightly shifted to positive and negative potentials, respectively, indicating good rate performance and reversible characteristics.
Constant direct current charge-discharge diagram (GCD) of the material as shown in FIG. 6, all GCD curves at different current densities of 0.7-5A/g are symmetrical in shape, which shows that the Faraday redox reaction has good reversibility, which is consistent with the CV curve. When the current density is 0.7A/g, the specific capacitance of the CCTS nano material is as high as 393.5F/g, and the CCTS nano material has excellent electrochemical performance.
The alternating current impedance plot (EIS) of the material is shown in fig. 7, and the rapid ion diffusion and the efficient electron transfer of the CCTS nanomaterial were further studied by the EIS test. The image consists of quasi-semi-circles in the high frequency region and linear portions in the low frequency region. The intercept on the real axis of the high frequency region represents the internal resistance (Rs) of the electrode. The diameter of the semicircle indicates the charge transfer resistance (Rct). In the low frequency region, the slope of the straight line is larger, indicating that the diffusion resistance is lower. As shown in an inset in the figure, the equivalent circuit for fitting the EIS spectrum has the advantages that the fitted internal resistance Rs is 0.66 omega, the fitted internal resistance Rct is 0.92 omega, and the resistance values are small, so that the rapid diffusion of ions and the effective transfer of electrons are facilitated.
The results of the cycling stability test of the material are shown in figure 8. The cycling stability of the CCTS electrode was tested at a current density of 7A/g. After 3000 times of charge and discharge cycles, the initial specific capacitance still maintains 78.07 percent, and the excellent cycle stability is shown. Thus, these results demonstrate that CCTS electrodes have excellent capacitive properties. Meanwhile, the GCD image of the last six circles of the cycle is shown in the figure, and the shape of the curve is almost kept unchanged, which shows that the stability of the material is better. The analysis result shows that the transition metal sulfide material has high specific capacitance, low resistance value and good cycling stability, and is the preferred material as the electrode material of the super capacitor.
Example 2
(1) Synthesis of ZIF-67: 44.32mmol of 2-methylimidazole, 14.10mmol of Co (NO) 3 ) 2 ·6H 2 O is respectively dissolved in 200mL of methanol, and the mixture is magnetically stirred for 40min at the rotating speed of 800r/min. Then the 2-methylimidazole solution was poured rapidly into Co (NO) under magnetic stirring 3 ) 2 ·6H 2 And standing the mixture in the O solution for 24 hours at room temperature, centrifugally cleaning the product by using methanol, repeating the process for three times, and drying the product in a vacuum drying oven at 70 ℃ for 11 hours to obtain ZIF-67.
(2) Sequentially adding 1.8mmol of CuCl serving as a reactant precursor 2 ·2H 2 O、0.2mmolZIF-67、 0.8mmolSnCl 2 ·2H 2 O and 3.5mmol thioacetamide were added to the polytetrafluoroethylene liner. Weighing 1.7mol of ethanol, adding into the lining, adding magnetons, magnetically stirring for 30min under heating conditions at a rotation speed of 800r/min, placing the lining into a stainless steel autoclave, and then placing the autoclave into a 110 ℃ oven for reaction for 6h.
(3) And after the reaction kettle is cooled to room temperature, pouring out the upper layer transparent solution, centrifugally cleaning the product for 20min by using deionized water and absolute ethyl alcohol in sequence, repeating the process for three times, and placing the cleaned product in a vacuum oven at 70 ℃ for vacuum drying for 11h.
Example 3
(1) Synthesis of ZIF-67: 22.16mmol of 2-methylimidazole, 7.03mmol of Co (NO) 3 ) 2 ·6H 2 O is respectively dissolved in 200mL of methanol, and the mixture is magnetically stirred for 50min at the rotating speed of 900r/min. The 2-methylimidazole solution was then poured rapidly into Co (NO) with magnetic stirring 3 ) 2 ·6H 2 And standing the solution in the O solution for 24 hours at room temperature, centrifugally cleaning the product by using methanol, repeating the process for three times, and drying the product in a vacuum drying oven at the temperature of 80 ℃ for 10 hours to obtain the ZIF-67.
(2) Sequentially adding 2.5mmol CuCl of reactant precursor 2 ·2H 2 O、0.08mmolZIF-67、1.5mmolSnCl 2 ·2H 2 O and 4.5mmol of sulfurThe acetamide was added to the teflon liner. Measuring 1.0mol N, adding N-dimethylformamide into the lining, adding magnetons, magnetically stirring for 30min under heating conditions at a rotation speed of 900r/min, placing the lining into a stainless steel autoclave, and then placing the autoclave into an oven at 100 ℃ for reaction for 8h.
(3) After the reaction kettle is cooled to room temperature, the upper layer transparent solution is poured out, the product is sequentially centrifugally cleaned for 20min by deionized water and absolute ethyl alcohol and the process is repeated for three times, and the cleaned product is placed in a vacuum oven at 80 ℃ for vacuum drying for 10h.
Example 4
(1) Synthesis of ZIF-67: 56.28mmol of 2-methylimidazole, 17.86mmol of Co (NO) 3 ) 2 ·6H 2 O is respectively dissolved in 200mL of methanol, and the mixture is magnetically stirred for 60min at the rotating speed of 1000r/min. The 2-methylimidazole solution was then poured rapidly into Co (NO) with magnetic stirring 3 ) 2 ·6H 2 And standing the mixture in the O solution for 24 hours at room temperature, centrifugally cleaning the product by using methanol, repeating the process for three times, and drying the product in a vacuum drying oven at 60 ℃ for 14 hours to obtain ZIF-67.
(2) Sequentially adding 1.5mmol CuCl of reactant precursor 2 ·2H 2 O、0.1mmolZIF-67、 1.3mmolSnCl 2 ·2H 2 O and 3mmol thioacetamide were added to the polytetrafluoroethylene liner. Measuring 1.2molN, adding N-dimethylformamide into the lining, adding magnetons, magnetically stirring for 30min under heating conditions at the rotation speed of 1000r/min, placing the lining into a stainless steel autoclave, and then placing the autoclave into an oven at 120 ℃ for reaction for 6h.
(3) After the reaction kettle is cooled to room temperature, the upper layer transparent solution is poured out, the product is sequentially centrifugally cleaned for 20min by deionized water and absolute ethyl alcohol and the process is repeated for three times, and the cleaned product is placed in a vacuum oven at 60 ℃ for vacuum drying for 14h.
Therefore, the preparation method of the transition metal sulfide derived from the ZIF-67 for the electrode material has simple steps and mild conditions, is used for solving the problems of small specific capacitance, poor conductivity, low energy density, complex preparation process, environmental pollution and the like of the transition metal sulfide in the prior art, and the prepared transition metal sulfide electrode material has a porous structure of an electrolyte ion transmission channel and a large specific surface area of electrolyte ion storage, and is favorable for improving the electrochemical performance of the electrode material.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting the same, and although the present invention is described in detail with reference to the preferred embodiments, those of ordinary skill in the art should understand that: modifications and equivalents may be made to the disclosure without departing from the scope of the disclosure.
Claims (10)
1. A preparation method of a ZIF-67 derived transition metal sulfide for an electrode material is characterized by comprising the following steps of:
(1) Synthesis of ZIF-67: respectively dissolving 2-methylimidazole and cobalt nitrate hexahydrate in an organic solvent with the same volume, stirring for a certain time, quickly pouring the 2-methylimidazole solution into the cobalt nitrate hexahydrate solution under quick stirring, standing at room temperature for 24 hours, centrifugally cleaning a product by using methanol, and drying in a vacuum drying oven to obtain ZIF-67;
(2) Synthesis of ZIF-67 derived CCTS: ZIF-67, copper chloride dihydrate, stannous chloride dihydrate and thioacetamide are used as reactants, a precursor solution is formed under the condition of stirring an organic solvent, and the mixture is reacted for 4 to 10 hours at the temperature of between 90 and 120 ℃ in a reaction kettle;
(3) Preparation of ZIF-67 derived CCTS nanomaterial: and when the reaction kettle is cooled to room temperature, pouring out the upper layer transparent solution, washing the product with absolute ethyl alcohol and deionized water, and drying in a vacuum drying oven to obtain the ZIF-67 derived CCTS nano material.
2. The method for preparing a transition metal sulfide derived from ZIF-67 for an electrode material according to claim 1, wherein: the mass ratio of the 2-methylimidazole to the cobalt nitrate hexahydrate in the step (1) is (2-4) to (0.6-1.2).
3. The method for preparing a transition metal sulfide derived from ZIF-67 for an electrode material according to claim 1, wherein: the organic solvent in the step (1) is N, N-dimethylformamide or methanol.
4. The method for preparing a transition metal sulfide derived from ZIF-67 for an electrode material according to claim 1, wherein: in the step (1), the 2-methylimidazole and the cobalt nitrate hexahydrate are respectively dissolved in an organic solvent with the same volume, and the stirring time is 30-60min.
5. The method for preparing a transition metal sulfide derived from ZIF-67 for an electrode material according to claim 1, wherein: the methanol centrifugal cleaning in the step (1) is specifically methanol centrifugal cleaning for 20min, and the steps are repeated for three times.
6. The method for preparing a transition metal sulfide derived from ZIF-67 for an electrode material according to claim 1, wherein: in the step (2), the mass ratio of the copper chloride dihydrate, the ZIF-67, the stannous chloride dihydrate and the thioacetamide is (1.5-2.5) to (0.08-0.3) to (0.8-1.5) to (3-4.5), and the mass ratio of the organic solvent to all reactant substances is (140) to (0.5-1).
7. The method for preparing a transition metal sulfide derived from ZIF-67 for an electrode material according to claim 1, wherein: the organic solvent in the step (2) is N, N-dimethylformamide or ethanol.
8. The method for preparing a transition metal sulfide derived from ZIF-67 for an electrode material according to claim 1, wherein: the stirring modes in the step (1) and the step (2) adopt magnetic stirring, and the rotating speed is 800-1000r/min.
9. The method for preparing a transition metal sulfide derived from ZIF-67 for an electrode material according to claim 1, wherein: and (4) specifically, the product cleaned in the step (3) is firstly centrifuged for 20min by using deionized water, then is centrifuged for 20min by using absolute ethyl alcohol, and the process is repeated for three times.
10. The method for preparing a transition metal sulfide derived from ZIF-67 for an electrode material according to claim 1, wherein: the temperature of the vacuum drying oven in the step (1) and the step (3) is 60-80 ℃, and the drying time of the vacuum drying oven is 10-14h.
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| ZA2023/02741A ZA202302741B (en) | 2022-10-17 | 2023-02-27 | A preparation method of transition metal sulfide derived from zif-67 for electrode material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114235920A (en) * | 2021-12-20 | 2022-03-25 | 天津工业大学 | NiCo LDH/NiCoS @ C composite material and preparation method and application thereof |
| CN118527177A (en) * | 2024-07-25 | 2024-08-23 | 浙江工业大学 | Nano ZnS@ZIF-67 composite catalyst and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114235920A (en) * | 2021-12-20 | 2022-03-25 | 天津工业大学 | NiCo LDH/NiCoS @ C composite material and preparation method and application thereof |
| CN114235920B (en) * | 2021-12-20 | 2024-06-28 | 天津工业大学 | NiCo LDH/NiCoS@C composite material and preparation method and application thereof |
| CN118527177A (en) * | 2024-07-25 | 2024-08-23 | 浙江工业大学 | Nano ZnS@ZIF-67 composite catalyst and preparation method and application thereof |
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