CN114188557A - Preparation method and application of multi-mesoporous transition metal-nitrogen-carbon catalyst - Google Patents
Preparation method and application of multi-mesoporous transition metal-nitrogen-carbon catalyst Download PDFInfo
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- H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
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Abstract
The invention relates to a preparation method and application of a multi-mesoporous transition metal-nitrogen-carbon catalyst, wherein the method comprises the following steps: dissolving a transition metal salt and polystyrene sulfonic acid in methanol to form a first mixed solution; dissolving 2-methylimidazole in methanol to form a second mixed solution; mixing the second mixed solution with the first mixed solution, standing and aging to obtain a metal organic framework material precursor; and calcining the metal organic framework material precursor in an argon atmosphere to obtain the multi-mesoporous transition metal-nitrogen-carbon catalyst. The preparation method of the invention effectively improves the specific surface area of the catalyst material and provides more active sites in the oxygen reduction reaction process of the battery.
Description
Technical Field
The invention belongs to the technical field of energy storage material application, and particularly relates to a preparation method and application of a multi-mesoporous transition metal-nitrogen-carbon catalyst.
Background
The rechargeable zinc-air battery has high theoretical energy density (1086Wh kg)-1) High abundance of anode material and safe water electrolyte. At present, zinc-air batteries have become a promising energy technology in the future. In particularAn oxygen reduction/evolution reaction (ORR/OER) occurs at the air cathode of a rechargeable zinc-air battery, however, the slow redox kinetics of ORR/OER severely degrade the energy conversion efficiency of the zinc-air battery device. Furthermore, the severe dependence of ORR/OER on precious metals also limits its widespread use.
Transition metal-nitrogen-carbon (M-N-C) catalysts are currently receiving increasing attention as bifunctional ORR/OER catalysts and are a promising candidate for ORR/OER. Metal-organic framework (MOF) materials have been widely selected as precursors for the preparation of M-N-C catalysts due to their advantages of adjustable size, morphology, relatively large surface area, and pre-formed M-Nx coordination structures. However, direct pyrolysis of MOFs will result in a significant reduction in specific surface area, which will reduce the utilization of active sites, resulting in poor ORR/OER activity performance. In addition, the performance of the ORR/OER catalyst is also affected by the problems of serious reduction of the specific surface area and few mesoporous structures of the current pyrolysis metal organic framework materials.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a preparation method and application of a multi-mesoporous transition metal-nitrogen-carbon catalyst. The technical problem to be solved by the invention is realized by the following technical scheme:
the invention provides a preparation method of a multi-mesoporous transition metal-nitrogen-carbon catalyst, which comprises the following steps:
dissolving a transition metal salt and polystyrene sulfonic acid in methanol to form a first mixed solution;
dissolving 2-methylimidazole in methanol to form a second mixed solution;
mixing the second mixed solution with the first mixed solution, standing and aging to obtain a metal organic framework material precursor;
and calcining the metal organic framework material precursor in an argon atmosphere to obtain the multi-mesoporous transition metal-nitrogen-carbon catalyst.
In one embodiment of the invention, the transition metal salt is at least one of a nitrate, sulfate or hydrochloride salt of cobalt, or at least one of a nitrate, sulfate or hydrochloride salt of zinc.
In one embodiment of the invention, the molar ratio of the transition metal salt to the polystyrene sulfonic acid is 16:1 to 0.5: 1.
In one embodiment of the invention, the concentration of the second mixed solution is 0.16-0.64 mol/L
In one embodiment of the invention, the standing and aging time is 0.5-24 h.
In one embodiment of the invention, the molar ratio of the first mixed solution to the second mixed solution is 1:2 to 1:10
In one embodiment of the invention, the calcination temperature is 700-1000 ℃ and the calcination time is 1-5 h.
The invention provides a multi-mesoporous transition metal-nitrogen-carbon catalyst which is prepared by adopting the preparation method in any one of the embodiments.
The invention provides an application of a multi-mesoporous transition metal-nitrogen-carbon catalyst obtained by the preparation method in any one of the embodiments in an electrocatalytic fuel cell and a metal air cell.
Compared with the prior art, the invention has the beneficial effects that:
1. the preparation method of the multi-mesoporous transition metal-nitrogen-carbon catalyst provided by the invention has the advantages that the surfactant polystyrene sulfonic acid is used as a soft template, the transition metal salt and the 2-methylimidazole organic ligand are used as raw materials, the metal organic framework material precursor is obtained by coprecipitation through an in-situ self-assembly method, and the multi-mesoporous transition metal-nitrogen-carbon material is obtained by calcining at high temperature.
2. The preparation method of the multi-mesoporous transition metal-nitrogen-carbon catalyst has the advantages of cheap and easily-obtained raw materials, simple and economical preparation method and suitability for industrial large-scale production.
The foregoing description is only an overview of the technical solutions of the present invention, and in order to make the technical means of the present invention more clearly understood, the present invention may be implemented in accordance with the content of the description, and in order to make the above and other objects, features, and advantages of the present invention more clearly understood, the following preferred embodiments are described in detail with reference to the accompanying drawings.
Drawings
Fig. 1 is a flow chart of a method for preparing a multi-mesoporous transition metal-nitrogen-carbon catalyst according to an embodiment of the present invention;
FIG. 2 is an SEM photograph of PSS-ZIF-67 in example 2;
FIG. 3 is a comparison of XRD patterns of PSS-ZIF-67 and ZIF-67 in example 2;
FIG. 4 is an SEM photograph and a TEM photograph of A-Co-N-C in example 2;
FIG. 5 is an SEM photograph of A-Co-N-C-1 in example 3;
FIG. 6 is an SEM photograph of A-Co-N-C-2 in example 4;
FIG. 7 is an SEM photograph of S-Co-N-C in comparative example 1;
FIG. 8 is an SEM photograph of L-Co-N-C in comparative example 2;
FIG. 9 is a graph of BET surface area measurements of various Co-N-C catalyst materials provided by an example of the present invention;
FIG. 10 is a graph of ORR performance test results for various Co-N-C catalyst materials provided by examples of the present invention;
FIG. 11 is a graph of the results of OER performance tests on various Co-N-C catalyst materials provided by examples of the present invention;
FIG. 12 is an SEM photograph of PEI-ZIF-67 in comparative example 3.
FIG. 13 is an SEM photograph of F127-ZIF-67 in comparative example 4.
Fig. 14 is a test chart of discharge power density according to an embodiment of the present invention.
Detailed Description
In order to further illustrate the technical means and effects of the present invention adopted to achieve the predetermined objects, the following detailed description will be made on the preparation method and application of the multi-mesoporous transition metal-nitrogen-carbon catalyst according to the present invention with reference to the accompanying drawings and the detailed description.
The foregoing and other technical matters, features and effects of the present invention will be apparent from the following detailed description of the embodiments, which is to be read in connection with the accompanying drawings. The technical means and effects of the present invention adopted to achieve the predetermined purpose can be more deeply and specifically understood through the description of the specific embodiments, however, the attached drawings are provided for reference and description only and are not used for limiting the technical scheme of the present invention.
Example 1
Referring to fig. 1, fig. 1 is a flowchart of a method for preparing a multi-mesoporous transition metal-nitrogen-carbon catalyst according to an embodiment of the present invention, specifically, the method includes the following steps:
step 1: dissolving a transition metal salt and polystyrene sulfonic acid in methanol to form a first mixed solution;
optionally, in this embodiment, the transition metal salt is at least one of a nitrate, sulfate, or hydrochloride salt of cobalt, or at least one of a nitrate, sulfate, or hydrochloride salt of zinc.
In the present embodiment, the molar ratio of the transition metal salt to the polystyrene sulfonic acid is 16:1 to 0.5: 1.
Step 2: dissolving 2-methylimidazole in methanol to form a second mixed solution;
in the embodiment, the concentration of the second mixed solution is 0.16-0.64 mol/L.
Optionally, in other embodiments, imidazole or 2-ethylimidazole may also be selected to be dissolved in methanol to form the second mixed solution.
In this example, 2-methylimidazole, imidazole, or 2-ethylimidazole is used as an organic ligand for binding metal to form a complex material.
And step 3: mixing the second mixed solution with the first mixed solution, standing and aging to obtain a metal organic framework material precursor;
specifically, in the step 3, the standing and aging time is 0.5-24 h.
Optionally, the molar ratio of the first mixed solution to the second mixed solution is 1:2 to 1: 10.
And 4, step 4: and calcining the metal organic framework material precursor in an argon atmosphere to obtain the multi-mesoporous transition metal-nitrogen-carbon catalyst.
Optionally, the calcination temperature is 700-1000 ℃, and the calcination time is 1-5 h.
The preparation method of the multi-mesoporous transition metal-nitrogen-carbon catalyst of the embodiment uses a surfactant polystyrene sulfonic acid (PSS) as a soft template, uses a transition metal salt and a 2-methylimidazole organic ligand as raw materials, adopts an in-situ self-assembly method to perform coprecipitation to obtain a metal organic framework material precursor, and calcines the precursor at a high temperature to obtain the multi-mesoporous transition metal-nitrogen-carbon material. In addition, the preparation method of the embodiment has the advantages of cheap and easily obtained raw materials, simple and economic preparation method, and suitability for industrial large-scale production.
Example 2
The transition metal salt in this example is the nitrate of cobalt, Co (NO)3)2·6H2O, the molar ratio of the transition metal salt to the polystyrene sulfonic acid (PSS) is 4:1, the concentration of the second mixed solution is 0.32mol/L, and the molar ratio of the first mixed solution to the second mixed solution is 1: 4.
In this embodiment, an in-situ self-assembly method is adopted to obtain a metal organic framework material precursor material through co-precipitation, the metal organic framework material precursor material is calcined according to specific reaction conditions to obtain a multi-mesoporous transition metal-nitrogen-carbon catalyst, and the performance of the multi-mesoporous transition metal-nitrogen-carbon catalyst is tested.
The preparation method of the multi-mesoporous transition metal-nitrogen-carbon catalyst of the embodiment specifically includes the following steps:
step 1: 1.16g of Co (NO)3)2·6H2O and 0.2g of PSS were dissolved in 50mL of methanol, and the solution was stirred for 0.5h to dissolve sufficiently.
Step 2: dissolving 1.32g of 2-methylimidazole in 50mL of methanol to prepare a methanol solution of 2-methylimidazole, adding the methanol solution of 2-methylimidazole into the mixed solution obtained in the step 1, standing, aging for 24 hours, and evaporating to obtain purple powder, namely the metal organic framework material precursor material, which is marked as PSS-ZIF-67.
As shown in FIG. 2, FIG. 2 is an SEM photograph of the PSS-ZIF-67 of example 2, wherein a and b are SEM photographs at different magnifications, and it can be seen from FIG. 2 that the mean diameter of the PSS-ZIF-67 is 1 μm, which is assembled from ZIF-67, and the mean diameter of the ZIF-67 is about 100 nm. FIG. 3 is a comparison of XRD patterns of PSS-ZIF-67 and ZIF-67 of example 2, wherein ZIF-67 is a simulated XRD pattern in FIG. 3, from which FIG. 3 it can be confirmed that ZIF-67 is formed and the XRD structure of PSS-ZIF-67 is still ZIF-67.
And step 3: the PSS-ZIF-67 was calcined at 900 deg.C for 3h under argon atmosphere to obtain a Co-N-C catalyst material, denoted A-Co-N-C, as shown in FIG. 4, FIG. 4 is SEM and TEM images of A-Co-N-C in example 2, wherein, a and b are SEM images, C and d are TEM images. As can be seen from the SEM image, the particles after high-temperature calcination do not collapse, the spherical particles are still kept, and the surface has more mesoporous structures, which is beneficial to the mass transfer process of the catalytic reaction. As can be seen from the TEM image, the A-Co-N-C particles have obvious existence of cobalt metal particles and are wrapped in the multilayer graphene carbon layer, and the existence of the metal cobalt and the multilayer graphene and the microstructure thereof are further proved by the lattice fringe spacing in the high-power TEM image.
Example 3
The transition metal salt in this example is the nitrate of cobalt, Co (NO)3)2·6H2O, the molar ratio of the transition metal salt to the polystyrene sulfonic acid (PSS) is 16:1, the concentration of the second mixed solution is 0.32mol/L, and the molar ratio of the first mixed solution to the second mixed solution is 1:4
In this embodiment, an in-situ self-assembly method is adopted to obtain a metal organic framework material precursor material through co-precipitation, the metal organic framework material precursor material is calcined according to specific reaction conditions to obtain a multi-mesoporous transition metal-nitrogen-carbon catalyst, and the performance of the multi-mesoporous transition metal-nitrogen-carbon catalyst is tested.
The preparation method of the multi-mesoporous transition metal-nitrogen-carbon catalyst of the embodiment specifically includes the following steps:
step 1: 1.16g of Co (NO)3)2·6H2O and 0.05g of PSS were dissolved in 50mL of methanol, and the solution was stirred for 0.5h to dissolve sufficiently.
Step 2: dissolving 1.32g of 2-methylimidazole in 50mL of methanol to prepare a methanol solution of 2-methylimidazole, adding the methanol solution of 2-methylimidazole into the mixed solution obtained in the step 1, standing, aging for 24 hours, and evaporating to obtain purple powder, namely the metal organic framework material precursor material, which is marked as PSS-ZIF-67-1.
And step 3: the PSS-ZIF-67-1 is calcined at 900 ℃ for 3h under the argon atmosphere to obtain a Co-N-C catalyst material, marked as A-Co-N-C-1, as shown in FIG. 5, and FIG. 5 is an SEM image of the A-Co-N-C-1 in the example 3.
Example 4
The transition metal salt in this example is the nitrate of cobalt, Co (NO)3)2·6H2O, the molar ratio of the transition metal salt to the polystyrene sulfonic acid (PSS) is 0.8:1, the concentration of the second mixed solution is 0.32mol/L, and the ratio of the first mixed solution to the second mixed solution is 1: 4.
In this embodiment, an in-situ self-assembly method is adopted to obtain a metal organic framework material precursor material through co-precipitation, the metal organic framework material precursor material is calcined according to specific reaction conditions to obtain a multi-mesoporous transition metal-nitrogen-carbon catalyst, and the performance of the multi-mesoporous transition metal-nitrogen-carbon catalyst is tested.
The preparation method of the multi-mesoporous transition metal-nitrogen-carbon catalyst of the embodiment specifically includes the following steps:
step 1: 1.16g of Co (NO)3)2·6H2O and 1.0g of PSS were dissolved in 50mL of methanol, and the solution was stirred for 0.5h to dissolve sufficiently.
Step 2: dissolving 1.32g of 2-methylimidazole in 50mL of methanol to prepare a methanol solution of 2-methylimidazole, adding the methanol solution of 2-methylimidazole into the mixed solution obtained in the step 1, standing, aging for 24 hours, and evaporating to obtain purple powder, namely the metal organic framework material precursor material, which is marked as PSS-ZIF-67-2.
And step 3: the PSS-ZIF-67-2 was calcined at 900 ℃ for 3h under argon atmosphere to obtain a Co-N-C catalyst material, denoted A-Co-N-C-2, as shown in FIG. 6, FIG. 6 is an SEM image of A-Co-N-C-2 in example 4.
By comparing examples 2 to 4, it can be seen that when the PSS is added in a small amount, the particles are significantly agglomerated but are not uniform in size, and as the PSS is increased, the particles self-assemble into spherical particles and are uniform in size; as PSS continues to increase, the particles remain spherical aggregates, but increase in size.
Comparative example 1
Ordinary ZIF-67 nanoparticles having an average size of 1 μm were prepared, and the ZIF-67 nanoparticles were calcined and pyrolyzed to obtain a Co-N-C catalyst material, denoted as S-Co-N-C, as shown in FIG. 7, which is an SEM image of S-Co-N-C in comparative example 1.
Comparative example 2
Ordinary ZIF-67 nanoparticles with the average size of 100nm are prepared, and the ZIF-67 nanoparticles are calcined and pyrolyzed to obtain a Co-N-C catalyst material, which is marked as L-Co-N-C, as shown in FIG. 8, wherein FIG. 8 is an SEM image of L-Co-N-C in comparative example 2.
The BET surface areas of the Co-N-C catalyst materials of example 2, comparative example 1 and comparative example 2 were measured, and as shown in fig. 9, fig. 9 is a graph of BET surface area measurements of different Co-N-C catalyst materials provided in examples of the present invention, wherein a is a graph of a-Co-N-C measurement of example 2, b is a graph of S-Co-N-C measurement of comparative example 1, and C is a graph of L-Co-N-C measurement of comparative example 2. From N2Adsorption/desorption isotherms it can be seen that all Co-N-C catalyst materials exhibit a microporous/mesoporous structure. The specific measurement results are shown in Table 1, in which the specific surface area of A-Co-N-C is 455m2 g-1With micropores 101m2 g-1And a mesopore 354m2 g-1In contrast, the BET surface area of S-Co-N-C is 233m2 g-1L-Co-N-C has a BET surface area of 111m2 g-1It can be seen that A-Co-N-C increases the microporous structure and the mesoporous structure compared to S-Co-N-C and L-Co-N-C.
TABLE 1 BET surface area measurements of different Co-N-C catalyst materials
The ORR performance of the Co-N-C catalyst materials of example 2, comparative example 1, comparative example 2 and commercial Pt/C (20 wt%) were evaluated at 1600 rpm. As shown in FIG. 10, FIG. 10 is a graph of the ORR performance test results of different Co-N-C catalyst materials provided by the present invention, according to the Linear Sweep Voltammetry (LSV) data measured at 1600rpm, the half-wave potential E of A-Co-N-C1/20.853V (vs-RHE), corresponding to the half-wave potential (E) of Pt/C1/20.856V (vs-RHE)), in contrast, half-wave potential E of S-Co-N-C1/2A half-wave potential E of 0.838V (vs-RHE), L-Co-N-C1/2It was 0.810V (vs-RHE).
Co-N-C catalyst materials of example 2, comparative example 1, comparative example 2 and commercial RuO in 1.0M KOH Using a glassy carbon electrode2The OER activity of (2) was evaluated by the test. As shown in FIG. 11, FIG. 11 is a graph of the results of OER performance tests on different Co-N-C catalyst materials provided by examples of the present invention, according to LSV data, at the same current density of 10mA cm-2Under the condition, the overpotential of A-Co-N-C is 363mV, and compared with the overpotential of S-Co-N-C of 387mV and the overpotential of L-Co-N-C of 413mV, the overpotential of A-Co-N-C is the minimum.
Comparative example 3
In this example, the surfactant polystyrene sulfonic acid (PSS) in example 2 was replaced with Polyethyleneimine (PEI), and the other parameters were consistent with those of example 2, and the prepared catalyst material, denoted as PEI-ZIF-67, was represented by fig. 12, which is an SEM image of PEI-ZIF-67 in comparative example 3.
Comparative example 4
In this example, the surfactant polystyrene sulfonic acid (PSS) in example 2 was replaced with polyether (F127), and the other parameters were identical to those of example 2, and the catalyst material obtained was designated as F127-ZIF-67, as shown in fig. 13, which is an SEM image of F127-ZIF-67 in comparative example 4.
In comparing the SEM images of example 2, comparative example 3 and comparative example 4, it can be seen that the surfactant polystyrene sulfonic acid (PSS) plays a key soft template role during the self-assembly of the metal organic framework material particles, which is beneficial for the formation of spherical nanoparticle aggregates.
Application example 1
A zinc-air secondary battery was prepared using the A-Co-N-C catalyst of example 2 as an air cathode and a zinc plate as a metal anode, and the discharge power density thereof was measured, as shown in FIG. 14, where FIG. 14 is a test chart of the discharge power density provided in the example of the present invention, and it can be seen that A-Co-N-C shows a larger discharge power density (239mV cm)-2) Greater than Pt/C + RuO2Discharge power density (146mV cm)-2)。
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that an article or device that comprises a list of elements does not include only those elements but may include other elements not expressly listed. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of additional like elements in the article or device comprising the element.
The foregoing is a more detailed description of the invention in connection with specific preferred embodiments and it is not intended that the invention be limited to these specific details. For those skilled in the art to which the invention pertains, several simple deductions or substitutions can be made without departing from the spirit of the invention, and all shall be considered as belonging to the protection scope of the invention.
Claims (9)
1. A preparation method of a multi-mesoporous transition metal-nitrogen-carbon catalyst is characterized by comprising the following steps:
dissolving a transition metal salt and polystyrene sulfonic acid in methanol to form a first mixed solution;
dissolving 2-methylimidazole in methanol to form a second mixed solution;
mixing the second mixed solution with the first mixed solution, standing and aging to obtain a metal organic framework material precursor;
and calcining the metal organic framework material precursor in an argon atmosphere to obtain the multi-mesoporous transition metal-nitrogen-carbon catalyst.
2. The method for preparing a multi-mesoporous transition metal-nitrogen-carbon catalyst according to claim 1, wherein the transition metal salt is at least one of nitrate, sulfate or hydrochloride of cobalt, or at least one of nitrate, sulfate or hydrochloride of zinc.
3. The method for preparing the multi-mesoporous transition metal-nitrogen-carbon catalyst according to claim 1, wherein the molar ratio of the transition metal salt to the polystyrene sulfonic acid is 16:1 to 0.5: 1.
4. The method for preparing the multi-mesoporous transition metal-nitrogen-carbon catalyst according to claim 1, wherein the concentration of the second mixed solution is 0.16 to 0.64 mol/L.
5. The method for preparing the multi-mesoporous transition metal-nitrogen-carbon catalyst according to claim 1, wherein the standing and aging time is 0.5-24 hours.
6. The method for preparing the multi-mesoporous transition metal-nitrogen-carbon catalyst according to claim 1, wherein a molar ratio of the first mixed solution to the second mixed solution is 1:2 to 1: 10.
7. The method for preparing the multi-mesoporous transition metal-nitrogen-carbon catalyst according to claim 1, wherein the calcination temperature is 700 to 1000 ℃ and the calcination time is 1 to 5 hours.
8. A multi-mesoporous transition metal-nitrogen-carbon catalyst, which is prepared by the preparation method of any one of claims 1 to 7.
9. Use of the multi-mesoporous transition metal-nitrogen-carbon catalyst obtained by the preparation method according to any one of claims 1 to 7 in electrocatalytic fuel cells and metal air cells.
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