CN115036516A - Cobalt and nitrogen co-doped hollow tubular porous carbon composite material and preparation method and application thereof - Google Patents

Cobalt and nitrogen co-doped hollow tubular porous carbon composite material and preparation method and application thereof Download PDF

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CN115036516A
CN115036516A CN202210462564.1A CN202210462564A CN115036516A CN 115036516 A CN115036516 A CN 115036516A CN 202210462564 A CN202210462564 A CN 202210462564A CN 115036516 A CN115036516 A CN 115036516A
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cobalt
nitrogen
composite material
porous carbon
carbon composite
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黄建林
徐玉婷
钟磊
潘文豪
彭嘉瑶
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South China University of Technology SCUT
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8605—Porous electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M12/00—Hybrid cells; Manufacture thereof
    • 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
    • H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
    • H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Abstract

The invention discloses a cobalt and nitrogen co-doped hollow tubular porous carbon composite material and a preparation method and application thereof. The cobalt and nitrogen co-doped hollow tubular porous carbon composite material is prepared by synthesizing hollow polypyrrole by taking methyl orange, ferric chloride and pyrrole as raw materials, carrying out surface modification on the hollow polypyrrole to enable the hollow polypyrrole to have negative charges, effectively adsorbing zinc ions and cobalt ions, realizing in-situ growth of ZnCo-ZIFs on the surface, and finally roasting at high temperature. The cobalt and nitrogen co-doped hollow tubular porous carbon composite material has a high specific surface area and a hierarchical porous structure, and can accelerate mass transfer and expose more active sites; the synergistic effect of the metal cobalt nanoparticles and the nitrogen-doped carbon can reduce the reaction energy barrier, facilitate the promotion of reaction kinetics and improve the electrocatalytic activity; in addition, the preparation method is simple, the production cost is low, and the zinc-air battery which is manufactured into the air cathode and assembled into the air cathode has excellent power density and specific capacity and has great potential in large-scale commercial application.

Description

Cobalt and nitrogen co-doped hollow tubular porous carbon composite material and preparation method and application thereof
Technical Field
The invention relates to the technical field of electrochemical energy storage devices, in particular to a cobalt and nitrogen co-doped hollow tubular porous carbon composite material and a preparation method and application thereof.
Background
With the depletion of traditional fossil fuels, environmental pollution and global warming, there is an urgent need to develop clean, sustainable energy conversion technologies. Zinc-air battery with high theoretical energy density (1086 W.h.kg) -1 ) The advantages of low cost, good safety and the like are more and more concerned by people. The energy conversion efficiency of zinc-air batteries is reported to depend on a key electrochemical reaction, namely the Oxygen Reduction Reaction (ORR). However, the oxygen-containing electrochemical reaction has a complicated electron transfer step and slow reaction kinetics, which prevent the practical application of the zinc-air battery. Therefore, much research has been devoted to the search for efficient electrocatalysts to accelerate the reaction process and reduce the overpotential. To date, platinum (Pt) -based materials have been considered the most effective catalysts by virtue of excellent ORR catalytic activity. However, the scarcity, high cost, and poor durability of platinum-based materials to methanol and CO have hindered their large-scale commercial application in electrochemical energy conversion systems. Therefore, it is of great importance to develop a high-efficiency, low-cost and stable noble-metal-free catalyst for ORR and accelerate the practical application of the catalyst in the energy conversion technology of zinc-air batteries.
MOFs are considered ideal precursors for the development of M-N-C catalyst systems because both intrinsic ligand heteroatoms and metal centers can be introduced into the carbon matrix by carbonization. However, high temperature processing of MOFs precursors often results in low catalyst yields and severe metal ion accumulation, which reduces the porosity and mass activity of MOFs derived catalysts. To alleviate this problem or to make efficient use of the inherent nitrogen and metal centers, composite structures can be formed by assembling MOFs to additional carbon substrates, such as graphene oxide, carbon nanotubes, etc. For example, Guo et al report that a nitrogen-doped porous graphene network is formed by carbonization of ZIF-67@ EGO at 450 ℃, resulting in a catalyst mass yield of over 65 wt%. It is noteworthy, however, that the decomposition of a small amount of residual oxygen functionality on EGO will lead to the destruction of the ZIF framework structure and to further oxidation of cobalt, resulting in a decrease in ORR performance; in addition, although large-sized nanoparticles formed by metal migration and crystallization can be mitigated under mild calcination conditions of 450 ℃, insufficient carbonization can result in an amorphous structure with greater electrical resistance, resulting in poor catalyst performance. (An effective carbon-based ORR catalyst from low-temperature implementation of ZIF-67 with ultra-small cobalt nanoparticles and high yield, J.Mater.chem.A., 2019,7,3544-
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to prepare the composite material of the bimetallic MOFs and the one-dimensional conductive substrate and use the composite material as an efficient and stable ORR electrocatalyst. The invention aims to provide a cobalt and nitrogen co-doped hollow tubular porous carbon composite material, a preparation method thereof and application thereof in a zinc-air battery.
The technical scheme adopted by the invention is as follows.
A preparation method of a cobalt and nitrogen co-doped hollow tubular porous carbon composite material comprises the following steps:
(1) preparing a hollow polypyrrole nanotube PPy by taking methyl orange, ferric chloride and pyrrole as raw materials;
(2) carrying out surface treatment on the polypyrrole nanotube by using a surfactant to enable the surface of the polypyrrole nanotube to be negatively charged so as to obtain S-PPy;
(3) dispersing S-PPy, soluble zinc salt, soluble cobalt salt and 2-methylimidazole in a methanol solution, and performing coordination reaction on the surface of the S-PPy to obtain a precursor ZnCo-ZIFs @ S-PPy;
(4) and putting the precursor into a quartz tube for carbonization, and calcining in a protective atmosphere to obtain the cobalt and nitrogen co-doped hollow tubular porous carbon composite material.
Preferably, the mass ratio of the methyl orange to the ferric chloride in the step (1) is 1: 3-1: 5.
Preferably, in the step (2), the surface treatment of the polypyrrole nanotubes with the surfactant specifically comprises the following steps: dissolving a PPy nanotube in methanol, adding a surfactant into ultrapure water, mixing the two, forming a uniform suspension under the action of ultrasonic waves, and finally obtaining the PPy subjected to surface treatment through centrifugal washing and vacuum drying.
Preferably, the mass ratio of the polypyrrole nanotubes to the surfactant in the step (2) is 1: 3-1: 10.
Preferably, the soluble zinc salt in the step (3) is at least one of zinc nitrate, zinc chloride and zinc sulfate; further preferred is zinc nitrate hexahydrate.
Preferably, the soluble cobalt salt in the step (3) is at least one of cobalt nitrate, cobalt chloride and cobalt sulfate; cobalt nitrate hexahydrate is more preferable.
Preferably, the molar ratio of the soluble zinc salt to the soluble cobalt salt in the step (3) is 3: 1-1: 1.
Preferably, the reaction temperature of the coordination reaction in the step (3) is 25-35 ℃, and the reaction time is 12-24 h.
Preferably, in the step (4), the calcining conditions are as follows: the protective gas is nitrogen or argon, the calcining temperature is 910-1000 ℃, the heating rate is 3 ℃/min, and the temperature is kept for 1-3 h.
The invention provides a cobalt and nitrogen co-doped hollow tubular porous carbon composite material which is prepared by the method. The cobalt and nitrogen co-doped hollow tubular porous carbon composite material is prepared by synthesizing a hollow polypyrrole nanotube-shaped framework by taking methyl orange, ferric chloride and pyrrole as raw materials, carrying out surface modification on the hollow polypyrrole nanotube-shaped framework, effectively adsorbing zinc ions and cobalt ions by using the hollow polypyrrole with negative charges on the surface after modification, realizing in-situ growth of ZnCo-ZIFs on the surface of the hollow polypyrrole, and finally roasting at high temperature.
The invention also provides application of the cobalt and nitrogen co-doped hollow tubular porous carbon composite material in a zinc-air battery. And the cobalt and nitrogen co-doped hollow tubular porous carbon composite material is used as an active substance of the air cathode catalyst material of the zinc-air battery, and the zinc-air battery is obtained through assembling a positive electrode.
The beneficial effects of the invention are: the cobalt and nitrogen co-doped hollow tubular porous carbon composite material has a high specific surface area, is beneficial to exposing more active sites, can accelerate charge transfer and oxygen transmission, can realize high catalytic activity, excellent stability and strong methanol tolerance, is simple in preparation method and low in production cost, and has excellent power density and high specific capacity, so that a zinc-air battery assembled by preparing the air cathode has great potential in large-scale commercial application.
Specifically, the method comprises the following steps:
(1) the cobalt and nitrogen co-doped hollow tubular porous carbon composite material has a layered porous structure with high specific surface area and coexistence of micropores/mesopores/macropores, can accelerate the transmission of substances, expose more catalytic sites and promote the ORR process;
(2) the cobalt and nitrogen co-doped hollow tubular porous carbon composite material has high contents of graphite nitrogen and pyridine nitrogen, can effectively adjust the electron density, and reduces the reaction overpotential. In a typical example of the present invention, it exhibits a high start potential of 0.982V and a high half-wave potential of 0.864V. It has better stability and stronger methanol tolerance than commercial Pt/C, maintaining excellent durability of 97.0% of the initial capacity after current response at 40000 seconds.
(3) The zinc-air battery assembled by the cobalt and nitrogen co-doped hollow tubular porous carbon composite material has the open-circuit voltage as high as 1.52V and the open-circuit voltage of 116 mW-cm -2 Peak power density of 784mAh g -1 The specific capacity of (A).
Drawings
FIG. 1 is an SEM and TEM image of Co @ N-CTs prepared in example 1.
FIG. 2 is a plot of the specific surface area of Co @ N-CTs prepared in example 1.
FIG. 3 is a graph of the electrochemical performance of Co @ N-CTs prepared in example 1.
FIG. 4 is a graph of cell performance of a zinc-air cell assembled from Co @ N-CTs prepared in example 1.
FIG. 5 is SEM images of N-CTs prepared in comparative example 1 and Co/N-CTs prepared in comparative example 2.
FIG. 6 is a graph showing electrochemical properties of N-CTs prepared in comparative example 1 and Co/N-CTs prepared in comparative example 2.
Detailed Description
The invention will be further explained and explained with reference to specific embodiments and the attached drawings.
Example 1
A preparation method of a cobalt and nitrogen co-doped hollow tubular porous carbon composite material comprises the following steps:
1. synthesis and pretreatment of hollow polypyrrole tube
0.5892g of methyl orange was dissolved in 360mL of deionized water and vigorously stirred, followed by the addition of 2.916g of FeCl to the above solution 3 ·6H 2 O and 1.26mL of pyrrole and stirred well for 24 h. And (3) carrying out suction filtration and washing on the obtained mixed solution by using ultrapure water, and then carrying out freeze drying to obtain the PPy nanotube. For better binding to metal ions in subsequent reactions, PPy needs to be pretreated to form a negatively charged surface. 100mg of PPy nanotubes were dissolved in 50mL of methanol, 1g of sodium dodecyl sulfate was added to 50mL of ultrapure water, and the two were mixed and subjected to ultrasonication to form a uniform suspension. Finally, carrying out centrifugal washing and drying in a vacuum oven at 60 ℃ for 12h to obtain final PPy subjected to surface treatment, and naming the final PPy as S-PPy;
2. in-situ growth of ZnCo-ZIF on surface of hollow polypyrrole tube
S-PPy was added to a solution containing 0.595g Zn (NO) 3 ) 2 ·6H 2 O and 0.291g Co (NO) 3 ) 2 ·6H 2 O(Zn 2+ And Co 2+ The molar ratio of the components is 2:1), and the mixture is ultrasonically vibrated for 3 hours in 40mL of methanol solution until the mixture is uniformly dispersed. Then 40mL of a methanol solution containing 24mmol of 2-methylimidazole was poured into the above solution and stirred vigorously at 25 ℃ for 24 hours. Centrifuging and washing the mixed solution by using methanol for 3 times, collecting a product, and drying the product in a vacuum oven at 60 ℃ for 12 hours to obtain a precursor, wherein the precursor is named as ZnCo-ZIFs @ S-PPy;
3. high-temperature carbonization synthesis of cobalt and nitrogen co-doped hollow tubular porous carbon composite material
The ZnCo-ZIFs @ S-PPy precursor is placed in a quartz tube for carbonization, kept at 910 ℃ for 60 minutes at the heating rate of 3 ℃/min under the Ar atmosphere, then cooled to 400 ℃ at the cooling rate of 5 ℃/min, and finally naturally cooled to room temperature, so that the target catalyst is obtained and named as Co @ N-CTs.
In FIG. 1, a and b are SEM images of Co @ N-CTs obtained in this example under different magnifications, and c in FIG. 1 is TEM image of Co @ N-CTs, it can be seen that after ZnCo-ZIFs @ PPy is pyrolyzed at high temperature, the obtained Co @ N-CTs still maintain good hollow tubular structure, and the polyhedron derived from ZnCo-ZIFs is tightly and uniformly loaded on the nanotube, and only shows slight shrinkage, and the average size is about 150 nm.
The specific surface area of Co @ N-CTs obtained in this example is shown in FIG. 2. Co @ N-CTs show a typical IV-type isotherm indicating the coexistence of micropores and mesopores. As can be seen from the inset in FIG. 2, different types of pores with the pore diameter ranging from 1 nm to 150nm exist in Co @ N-CTs, which shows that the material has a microporous/mesoporous/macroporous coexisting layered porous structure, and the specific surface area of the material is 228.9m 2 ·g -1 . The micropores and the mesopores are mainly attributed to the volatilization of metal substances in the carbonization process of the ZIFs frame, and as the boiling point of metal zinc is 907 ℃, the zinc substances in the ZIFs frame volatilize at the calcination temperature higher than 907 ℃, so that a porous structure is brought to the frame. While the macropores are due to the one-dimensional hollow PPy tubular framework.
The Co @ N-CTs obtained in this example were subjected to electrochemical performance testing in an electrochemical workstation (CHI 760e) using a rotating disk glassy carbon electrode as the working electrode, an Ag/AgCl electrode as the reference electrode, a Pt foil as the counter electrode and 0.1M KOH as the electrolyte in a three-electrode system. The working electrode was prepared by ultrasonically dispersing 5mg Co @ N-CT in a mixture containing 300. mu.L ultrapure water, 700. mu.L ethanol and 50. mu.L of 5% Nafion, applying 10. mu.L of ink drop-wise to the surface of a polished glassy carbon electrode in a rotating disk electrode device, and allowing it to dry naturally for subsequent testing. The test results are shown in fig. 3. FIG. 3, a is a CV curve obtained from cyclic voltammetry tests, showing Co @ N-CTs at N 2 No redox peaks appear in the saturated electrolyte, whereas oxygen saturationAnd a clear oxygen reduction cathode peak was seen in the electrolyte indicating that it has the electrocatalytic activity of ORR. FIG. 3, b is an LSV curve from linear sweep voltammetry, showing that Co @ N-CTs have a high onset potential (0.982V) and a half-wave potential (0.864V), which are far superior to commercial Pt/C catalysts (0.974V, 0.836V); FIG. 3C shows that Co @ N-CTs exhibit greater stability than Pt/C, maintaining 97.0% of the original capacity after 40000s continuous oxygen reduction; FIG. 3, d, shows that Co @ N-CTs exhibit better methanol tolerance than Pt/C, with no significant change in current for Co @ N-CTs and a sharp drop in current for Pt/C when the methanol reagent is injected in a stable system.
The Co @ N-CTs obtained in the example were assembled into a zinc-air battery for battery performance testing, using carbon paper coated with a catalyst as an anode, a polished zinc sheet as a cathode, and electrolytes of 6M KOH and 0.2M Zn (Ac) 2 The solution was mixed. The preparation of the positive electrode is that 5mg of catalyst is dispersed into 1mL of ethanol mixed with 50 muL of 0.5% Nafion by ultrasonic to prepare catalyst ink, then 400 muL of the ink is uniformly dripped on hydrophobic carbon paper, and after natural drying, the battery can be assembled for testing. As shown in FIG. 4, the Co @ N-CTs-based battery had an open circuit voltage (a in FIG. 4) of up to 1.52V, 116mW · cm -2 Peak power density (b in FIG. 4), 784mAh g -1 The specific capacity (C in fig. 4) is superior to the performance of the battery assembled by Pt/C.
Example 2
A preparation method of a cobalt and nitrogen co-doped hollow tubular porous carbon composite material comprises the following steps:
1. synthesis and pretreatment of hollow polypyrrole tube
0.972g methyl orange was dissolved in 360mL deionized water and vigorously stirred, followed by the addition of 2.916g FeCl to the above solution 3 ·6H 2 O and 1.26mL pyrrole and stirred well for 24 h. And (3) carrying out suction filtration and washing on the obtained mixed solution by using ultrapure water, and then carrying out freeze drying to obtain the PPy nanotube. For better binding to metal ions in subsequent reactions, PPy needs to be pretreated to form a negatively charged surface. 100mg of PPy nanotubes were dissolved in 50mL of methanol, and 1g of decaSodium dialkyl sulfonate was added to 50mL of ultrapure water, and the two were mixed and subjected to ultrasonic waves to form a uniform suspension. Finally, carrying out centrifugal washing and drying in a vacuum oven at 60 ℃ for 12h to obtain final PPy subjected to surface treatment, and naming the final PPy as S-PPy;
2. in-situ growth of ZnCo-ZIF on surface of hollow polypyrrole tube
S-PPy was added to a solution containing 0.595g Zn (NO) 3 ) 2 ·6H 2 O and 0.291g Co (NO) 3 ) 2 ·6H 2 O(Zn 2+ And Co 2+ The molar ratio of the components is 2:1), and the mixture is ultrasonically vibrated for 3 hours in 40mL of methanol solution until the mixture is uniformly dispersed. Then, 40mL of a methanol solution containing 24mmol of 2-methylimidazole was poured into the above solution, and vigorously stirred at 30 ℃ for 12 hours. Centrifugally washing the mixed solution with methanol for 3 times, collecting a product, and drying the product in a vacuum oven at 60 ℃ for 12 hours to obtain a precursor ZnCo-ZIFs @ S-PPy;
3. high-temperature carbonization synthesis of cobalt and nitrogen co-doped hollow tubular porous carbon composite material
The ZnCo-ZIFs @ S-PPy precursor is placed in a quartz tube to be carbonized, the temperature is kept for 60 minutes at 910 ℃ at the heating rate of 3 ℃/min under the Ar atmosphere, then the temperature is reduced to 400 ℃ at the cooling rate of 5 ℃/min, and finally the temperature is naturally cooled to the room temperature, so that the target catalyst is obtained.
Example 3
A preparation method of a cobalt and nitrogen co-doped hollow tubular porous carbon composite material comprises the following steps:
1. synthesis and pretreatment of hollow polypyrrole tube
0.5892g methyl orange was dissolved in 360mL deionized water and stirred vigorously, followed by the addition of 2.916g FeCl to the above solution 3 ·6H 2 O and 1.26mL pyrrole and stirred well for 24 h. And carrying out suction filtration and washing on the obtained mixed solution by using ultrapure water, and then carrying out freeze drying to obtain the PPy nanotube. For better binding to metal ions in subsequent reactions, PPy needs to be pretreated to form a negatively charged surface. Dissolving 100mg PPy nanotube in 50mL methanol, adding 300mg sodium dodecyl sulfate into 50mL ultrapure water, mixing the two, and forming under the action of ultrasonic waveTo form a uniform suspension. Finally, carrying out centrifugal washing and drying in a vacuum oven at 60 ℃ for 12h to obtain final PPy subjected to surface treatment, and naming the final PPy as S-PPy;
2. in-situ growth of ZnCo-ZIF on surface of hollow polypyrrole tube
S-PPy was added to a solution containing 0.273g of ZnCl 2 And 0.238g CoCl 2 ·6H 2 O(Zn 2+ And Co 2+ The molar ratio of the components is 2:1), and the mixture is ultrasonically vibrated for 3 hours in 40mL of methanol solution until the mixture is uniformly dispersed. Then 40mL of a methanol solution containing 24mmol of 2-methylimidazole was poured into the above solution, and stirred vigorously at 25 ℃ for 12 hours. Centrifugally washing the mixed solution with methanol for 3 times, collecting a product, and drying the product in a vacuum oven at 60 ℃ for 12 hours to obtain a precursor ZnCo-ZIFs @ S-PPy;
3. high-temperature carbonization synthesis of cobalt and nitrogen co-doped hollow tubular porous carbon composite material
Putting the ZnCo-ZIFs @ S-PPy precursor into a quartz tube for carbonization, keeping the temperature at 910 ℃ for 60 minutes at the heating rate of 3 ℃/min under the Ar atmosphere, then reducing the temperature to 400 ℃ at the cooling rate of 5 ℃/min, and finally naturally cooling to the room temperature, thereby obtaining the target catalyst.
Example 4
A preparation method of a cobalt and nitrogen co-doped hollow tubular porous carbon composite material comprises the following steps:
1. synthesis and pretreatment of hollow polypyrrole tube
0.5892g of methyl orange was dissolved in 360mL of deionized water and vigorously stirred, followed by the addition of 2.916g of FeCl to the above solution 3 ·6H 2 O and 1.26mL of pyrrole and stirred well for 24 h. And carrying out suction filtration and washing on the obtained mixed solution by using ultrapure water, and then carrying out freeze drying to obtain the PPy nanotube. For better binding to metal ions in subsequent reactions, PPy needs to be pretreated to form a negatively charged surface. 100mg of PPy nanotubes were dissolved in 50mL of methanol, 500mg of sodium dodecyl sulfate was added to 50mL of ultrapure water, and the two were mixed and subjected to ultrasonic waves to form a uniform suspension. Finally obtaining the final surface treated PPy by centrifugal washing and drying in a vacuum oven at 60 ℃ for 12hNamed S-PPy;
2. in-situ growth of ZnCo-ZIF on surface of hollow polypyrrole tube
S-PPy was added to a solution containing 0.575g of ZnSO 4 ·7H 2 O and 0.281g CoSO 4 ·7H 2 O(Zn 2+ And Co 2+ The molar ratio of the components is 2:1), and the mixture is ultrasonically vibrated for 3 hours in 40mL of methanol solution until the mixture is uniformly dispersed. Then 40mL of a methanol solution containing 24mmol of 2-methylimidazole was poured into the above solution and stirred vigorously at 25 ℃ for 24 hours. Centrifugally washing the mixed solution with methanol for 3 times, collecting a product, and drying the product in a vacuum oven at 60 ℃ for 12 hours to obtain a precursor ZnCo-ZIFs @ S-PPy;
3. high-temperature carbonization synthesis of cobalt and nitrogen co-doped hollow tubular porous carbon composite material
Putting the ZnCo-ZIFs @ S-PPy precursor into a quartz tube for carbonization, keeping the temperature at 1000 ℃ for 60 minutes at the heating rate of 3 ℃/min under the Ar atmosphere, then reducing the temperature to 400 ℃ at the cooling rate of 5 ℃/min, and finally naturally cooling to the room temperature, thereby obtaining the target catalyst.
Example 5
A preparation method of a cobalt and nitrogen co-doped hollow tubular porous carbon composite material comprises the following steps:
1. synthesis and pretreatment of hollow polypyrrole tube
0.5892g methyl orange was dissolved in 360mL deionized water and stirred vigorously, followed by the addition of 2.916g FeCl to the above solution 3 ·6H 2 O and 1.26mL pyrrole and stirred well for 24 h. And carrying out suction filtration and washing on the obtained mixed solution by using ultrapure water, and then carrying out freeze drying to obtain the PPy nanotube. For better binding to metal ions in subsequent reactions, PPy needs to be pretreated to form a negatively charged surface. 100mg of PPy nanotubes were dissolved in 50mL of methanol, 1g of sodium dodecyl sulfate was added to 50mL of ultrapure water, and the two were mixed and subjected to ultrasonic waves to form a uniform suspension. Finally, carrying out centrifugal washing and drying in a vacuum oven at 60 ℃ for 12h to obtain final PPy subjected to surface treatment, and naming the final PPy as S-PPy;
2. in-situ growth of ZnCo-ZIF on surface of hollow polypyrrole tube
S-PPy was added to a solution containing 0.446g Zn (NO) 3 ) 2 ·6H 2 O and 0.436g Co (NO) 3 ) 2 ·6H 2 O(Zn 2+ And Co 2+ The molar ratio of the components is 1:1), and the mixture is ultrasonically vibrated for 3 hours in 40mL of methanol solution until the mixture is uniformly dispersed. Then 40mL of a methanol solution containing 24mmol of 2-methylimidazole was poured into the above solution and stirred vigorously at 25 ℃ for 24 hours. Centrifugally washing the mixed solution with methanol for 3 times, collecting a product, and drying the product in a vacuum oven at 60 ℃ for 12 hours to obtain a precursor ZnCo-ZIFs @ S-PPy;
3. high-temperature carbonization synthesis of cobalt and nitrogen co-doped hollow tubular porous carbon composite material
The ZnCo-ZIFs @ S-PPy precursor is placed in a quartz tube to be carbonized, the temperature is kept at 910 ℃ for 120 minutes at the heating rate of 3 ℃/min under the Ar atmosphere, then the temperature is reduced to 400 ℃ at the cooling rate of 5 ℃/min, and finally the temperature is naturally cooled to the room temperature, so that the target catalyst is obtained.
Example 6
A preparation method of a cobalt and nitrogen co-doped hollow tubular porous carbon composite material comprises the following steps:
1. synthesis and pretreatment of hollow polypyrrole tube
0.5892g methyl orange was dissolved in 360mL deionized water and stirred vigorously, followed by the addition of 2.916g FeCl to the above solution 3 ·6H 2 O and 1.26mL pyrrole and stirred well for 24 h. And (3) carrying out suction filtration and washing on the obtained mixed solution by using ultrapure water, and then carrying out freeze drying to obtain the PPy nanotube. For better binding to metal ions in subsequent reactions, PPy needs to be pretreated to form a negatively charged surface. 100mg of PPy nanotubes were dissolved in 50mL of methanol, 1g of sodium dodecyl sulfate was added to 50mL of ultrapure water, and the two were mixed and subjected to ultrasonic waves to form a uniform suspension. Finally, carrying out centrifugal washing and drying in a vacuum oven at 60 ℃ for 12h to obtain final PPy subjected to surface treatment, and naming the final PPy as S-PPy;
2. in-situ growth of ZnCo-ZIF on surface of hollow polypyrrole tube
S-PPy was added to a solution containing 0.669g Zn (NO) 3 ) 2 ·6H 2 O and 0.218g Co (NO) 3 ) 2 ·6H 2 O(Zn 2+ And Co 2+ In 40mL of methanol solution with the molar ratio of 3:1), and oscillating for 3h by ultrasonic waves until the solution is uniformly dispersed. Then, 40mL of a methanol solution containing 24mmol of 2-methylimidazole was poured into the above solution, and stirred vigorously at 30 ℃ for 24 hours. Centrifugally washing the mixed solution with methanol for 3 times, collecting the product, and drying the product in a vacuum oven at 60 ℃ for 12 hours to obtain a precursor ZnCo-ZIFs @ S-PPy;
3. high-temperature carbonization synthesis of cobalt and nitrogen co-doped hollow tubular porous carbon composite material
Putting the ZnCo-ZIFs @ S-PPy precursor into a quartz tube for carbonization, keeping the temperature at 910 ℃ for 180 minutes at the heating rate of 3 ℃/min under the Ar atmosphere, then reducing the temperature to 400 ℃ at the cooling rate of 5 ℃/min, and finally naturally cooling to the room temperature, thereby obtaining the target catalyst.
Comparative example 1
A preparation method of a nitrogen-doped hollow tubular porous carbon composite material comprises the following steps:
1. synthesis and pretreatment of hollow polypyrrole tube
0.5892g methyl orange was dissolved in 360mL deionized water and stirred vigorously, followed by the addition of 2.916g FeCl to the above solution 3 ·6H 2 O and 1.26mL pyrrole and stirred well for 24 h. And carrying out suction filtration and washing on the obtained mixed solution by using ultrapure water, and then carrying out freeze drying to obtain the PPy nanotube. 100mg of PPy nanotubes were dissolved in 50mL of methanol, 1g of sodium dodecyl sulfate was added to 50mL of ultrapure water, and the two were mixed and subjected to ultrasonication to form a uniform suspension. Finally, carrying out centrifugal washing and drying in a vacuum oven at 60 ℃ for 12h to obtain final PPy subjected to surface treatment, and naming the final PPy as S-PPy;
2. in-situ growth of ZIF-8 on the surface of hollow polypyrrole tube
S-PPy was added to a solution containing 0.297g Zn (NO) 3 ) 2 ·6H 2 And O in 40mL of methanol solution, and ultrasonically oscillating for 3 hours until the mixture is uniformly dispersed. Then 40mL of a methanol solution containing 8mmol of 2-methylimidazole was poured into the above solution and stirred vigorously at 25 ℃ for 24 hours. The mixture was washed with methanol by centrifugation 3 times to collect the productDrying the precursor in a vacuum oven at 60 ℃ for 12 hours to obtain a ZIF-8@ S-PPy precursor;
3. high-temperature carbonization synthesis of nitrogen-doped hollow tubular porous carbon composite material
And (2) putting the ZIF-8@ S-PPy precursor into a quartz tube for carbonization, keeping the temperature at 910 ℃ for 60 minutes at the heating rate of 3 ℃/min under the Ar atmosphere, then reducing the temperature to 400 ℃ at the cooling rate of 5 ℃/min, and finally naturally cooling to room temperature, thereby obtaining the target catalyst N-CTs.
SEM images of the N-CTs obtained in comparative example 1 are shown in a and b of FIG. 5. ZIF-8 derived polyhedral nanocrystals shrink severely, with an average size of about 80 nm.
Comparative example 2
A preparation method of a cobalt and nitrogen co-doped hollow tubular porous carbon composite material comprises the following steps:
1. synthesis and pretreatment of hollow polypyrrole tube
0.5892g of methyl orange was dissolved in 360mL of deionized water and vigorously stirred, followed by the addition of 2.916g of FeCl to the above solution 3 ·6H 2 O and 1.26mL pyrrole and stirred well for 24 h. And carrying out suction filtration and washing on the obtained mixed solution by using ultrapure water, and then carrying out freeze drying to obtain the PPy nanotube. 100mg of PPy nanotubes were dissolved in 50mL of methanol, 1g of sodium dodecyl sulfate was added to 50mL of ultrapure water, and the two were mixed and subjected to ultrasonic waves to form a uniform suspension. Finally, carrying out centrifugal washing and drying in a vacuum oven at 60 ℃ for 12h to obtain final PPy subjected to surface treatment, and naming the final PPy as S-PPy;
2. in-situ growth of ZIF-67 on surface of hollow polypyrrole tube
S-PPy was added to a solution containing 0.291g of Co (NO) 3 ) 2 ·6H 2 And O in 40mL of methanol solution, and ultrasonically oscillating for 3 hours until the mixture is uniformly dispersed. Then 40mL of a methanol solution containing 8mmol of 2-methylimidazole was poured into the above solution and stirred vigorously at 25 ℃ for 24 hours. Centrifugally washing the mixed solution with methanol for 3 times, collecting a product, and drying the product in a vacuum oven at 60 ℃ for 12 hours to obtain a precursor ZIF-67@ S-PPy;
3. high-temperature carbonization synthesis of cobalt and nitrogen co-doped hollow tubular porous carbon composite material
And (2) putting the ZIF-67@ S-PPy precursor into a quartz tube for carbonization, keeping the temperature at 910 ℃ for 60 minutes at the heating rate of 3 ℃/min under the Ar atmosphere, then reducing the temperature to 400 ℃ at the cooling rate of 5 ℃/min, and finally naturally cooling to room temperature, thereby obtaining the target catalyst Co/N-CTs.
SEM images of the Co/N-CTs obtained in comparative example 2 are shown in c and d in FIG. 5. The ZIF-67 derived polyhedral nanocrystal is large in size (about 400nm), shrinks and deforms, metal cobalt particles are seriously agglomerated, and the carbon skeleton collapses to cause precipitation.
The Co @ N-CTs prepared in example 1, the N-CTs prepared in comparative example 1, and the Co/N-CTs prepared in comparative example 2 were subjected to electrochemical performance tests, and the test results are shown in FIG. 6. FIG. 6, a is the CV curve obtained from the cyclic voltammetry test, showing that Co @ N-CTs have the highest oxygen reduction peak in oxygen-saturated electrolytes, followed by Co/N-CTs, with the lowest N-CTs; b in FIG. 6 is the LSV curve obtained by linear sweep voltammetry, and it can be seen that the initial potential of Co @ N-CTs is 0.982V and the half-wave potential is 0.864V; the initial potential of Co/N-CTs is 0.959V, and the half-wave potential is 0.849V; the initial potential of N-CTs was 0.955V and the half-wave potential was 0.832V. The result of fig. 6 shows that the cobalt and nitrogen co-doped hollow tubular porous carbon composite material prepared by the invention has better electrocatalytic performance and is an ideal oxygen electrocatalyst applied to a zinc-air battery.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (10)

1. The preparation method of the cobalt and nitrogen co-doped hollow tubular porous carbon composite material is characterized by comprising the following steps of:
(1) preparing a hollow polypyrrole nanotube PPy by taking methyl orange, ferric chloride and pyrrole as raw materials;
(2) carrying out surface treatment on the polypyrrole nanotube by using a surfactant to enable the surface of the polypyrrole nanotube to have negative charges, so as to obtain S-PPy;
(3) dispersing S-PPy, soluble zinc salt, soluble cobalt salt and 2-methylimidazole in a methanol solution, and carrying out coordination reaction on the surface of the S-PPy to obtain a precursor ZnCo-ZIFs @ S-PPy;
(4) and putting the precursor into a quartz tube for carbonization, and calcining in a protective atmosphere to obtain the cobalt and nitrogen co-doped hollow tubular porous carbon composite material.
2. The preparation method of the cobalt and nitrogen co-doped hollow tubular porous carbon composite material according to claim 1, wherein the mass ratio of methyl orange to ferric chloride in the step (1) is 1: 3-1: 5.
3. The preparation method of the cobalt-nitrogen co-doped hollow tubular porous carbon composite material according to claim 1, wherein in the step (2), the surface treatment of the polypyrrole nanotube with a surfactant specifically comprises the following steps: dissolving a PPy nanotube in methanol, adding a surfactant into ultrapure water, mixing the surfactant and the ultrapure water to form a uniform suspension under the action of ultrasonic waves, and finally performing centrifugal washing and vacuum drying to obtain surface-treated PPy; the mass ratio of the polypyrrole nanotubes to the surfactant in the step (2) is 1: 3-1: 10.
4. The preparation method of the cobalt and nitrogen co-doped hollow tubular porous carbon composite material according to claim 1, wherein the soluble zinc salt in the step (3) is at least one of zinc nitrate, zinc chloride and zinc sulfate; and (3) the soluble cobalt salt is at least one of cobalt nitrate, cobalt chloride and cobalt sulfate.
5. The preparation method of the cobalt and nitrogen co-doped hollow tubular porous carbon composite material according to claim 1, wherein the molar ratio of the soluble zinc salt to the soluble cobalt salt in the step (3) is 3: 1-1: 1.
6. The preparation method of the cobalt and nitrogen co-doped hollow tubular porous carbon composite material according to claim 1, wherein the reaction temperature of the coordination reaction in the step (3) is 25-35 ℃, and the reaction time is 12-24 hours.
7. The preparation method of the cobalt-nitrogen co-doped hollow tubular porous carbon composite material according to claim 1, wherein in the step (4), the calcination conditions are as follows: the protective gas is nitrogen or argon, the calcining temperature is 910-1000 ℃, the heating rate is 3 ℃/min, and the temperature is kept for 1-3 h.
8. A cobalt and nitrogen co-doped hollow tubular porous carbon composite material is characterized by being prepared by the preparation method of any one of claims 1-7.
9. The use of the cobalt and nitrogen co-doped hollow tubular porous carbon composite material of claim 8 in a zinc-air battery.
10. The application of the composite material according to claim 9, wherein the cobalt and nitrogen co-doped hollow tubular porous carbon composite material is used as an active substance of an air cathode catalyst material of a zinc-air battery, and the zinc-air battery is obtained through positive electrode assembly.
CN202210462564.1A 2022-04-28 2022-04-28 Cobalt and nitrogen co-doped hollow tubular porous carbon composite material and preparation method and application thereof Pending CN115036516A (en)

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