CN115275227A - Method for solid-phase macro synthesis of coral-shaped metal selenide composite nitrogen-doped carbon catalyst and application thereof - Google Patents

Method for solid-phase macro synthesis of coral-shaped metal selenide composite nitrogen-doped carbon catalyst and application thereof Download PDF

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CN115275227A
CN115275227A CN202210764297.3A CN202210764297A CN115275227A CN 115275227 A CN115275227 A CN 115275227A CN 202210764297 A CN202210764297 A CN 202210764297A CN 115275227 A CN115275227 A CN 115275227A
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doped carbon
coral
carbon catalyst
catalyst
shaped metal
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罗浩
齐盼
张大伟
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Intelligent Manufacturing Institute of Hefei University Technology
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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
    • H01M4/90—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

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Abstract

The invention discloses a method for solid-phase macro synthesis of a coralline metal selenide composite nitrogen-doped carbon catalyst and application thereof. The catalyst provided by the invention has excellent performance, can be used as a cathode catalyst of a fuel cell and a metal-air cell, is a potential substitute of a noble metal oxygen reduction catalyst, and is simple in synthesis method, convenient to operate, low in cost and easy for large-scale mass production.

Description

Method for solid-phase macro synthesis of coral-shaped metal selenide composite nitrogen-doped carbon catalyst and application thereof
Technical Field
The invention belongs to the field of catalysts, and particularly relates to a method for solid-phase mass synthesis of a coral-shaped metal selenide composite nitrogen-doped carbon catalyst and application thereof.
Background
With the continuous development of society, the attention degree of energy and environmental problems is getting larger, and the development of efficient, clean, safe and sustainable new energy has great demand. The fuel cell is a device for directly converting chemical energy into electric energy, has the characteristics of high conversion efficiency, high specific energy, environmental friendliness and the like, and is expected to become a substitute chemical power supply for future electric vehicles. The metal-air battery has great research value because of having the advantages of lower cost, high energy, environmental protection and the like. However, the kinetics of the oxygen reduction reaction in the key cathode processes of the two batteries are slow, and the platinum-based noble metal catalyst can solve the problem of the slow kinetics to a certain extent, but the platinum-based noble metal is expensive and has rare reserves, so that the development of fuel batteries and metal air batteries is not facilitated. Therefore, the development of a non-noble metal catalyst which can be prepared in a large scale and at low cost is urgently needed so as to promote the large-scale industrial development of fuel cells and metal-air cells.
At present, based on the high price and rare reserves of noble metal oxygen reduction catalysts, a large amount of research and development are carried out on oxygen reduction catalysts at home and abroad, a large amount of non-noble metal oxygen reduction catalysts are developed, wherein the main non-noble metal oxygen reduction catalysts are divided into the following categories: materials based on iron/cobalt/nickel and nitrogen doping modification, materials based on heteroatom doped carbon materials, materials based on transition metal selenide or sulfide complex nitrogen doped carbon modification, materials based on transition metal oxide or sulfide, and the like. The preparation process of the transition metal selenide or sulfide composite nitrogen-doped carbon material is complex, the process is complex, the reaction process is uncontrollable and the like, so that the catalysts are not suitable for mass production, for example, in the hydrothermal selenization process, only a small amount of material can be selenized each time, only a small amount of catalyst can be prepared once, and the catalysts are difficult to mass industrial production, so that the catalysts cannot be really applied to commercialization. Meanwhile, in the actual reaction process, the catalyst structure with the micro-mesopores with the specific morphology can increase active sites and is beneficial to mass transfer of chemical reaction, various porous structures and morphologies are constructed through a template method or solvothermal reaction, the template method is accompanied by template addition and final template removal, the process flow is complex, and the cost is greatly increased. The solvent thermal reaction requires high temperature and high pressure, and consumes a large amount of energy and is dangerous under working conditions. Therefore, the high-performance porous structure catalyst with a specific morphology can be obtained by solid-phase grinding and annealing selenization, and has numerous advantages, such as simple operation process, mass production, controllable process, safe experiment, low cost, environmental friendliness, capability of eliminating or reducing complex process flow and possible agglomeration in liquid-phase reaction, capability of greatly reducing process steps, improvement of production yield and great reduction of industrial mass production cost. Therefore, the development of the high-activity coral selenide composite nitrogen-doped carbon catalyst synthesized in a solid phase and in a macroscopic quantity has great significance for promoting the industrial development of fuel cells and metal-air cells.
Disclosure of Invention
Based on the problems in the prior art, the invention provides a method for solid-phase macro synthesis of a coral-shaped metal selenide composite nitrogen-doped carbon catalyst, aiming at simplifying the preparation process, reducing the production cost, improving the production yield and enabling the obtained catalyst to have excellent performance, thereby being capable of replacing a noble metal oxygen reduction catalyst to be used as a cathode catalyst of a fuel cell and a metal-air cell.
The invention adopts the following technical scheme for realizing the purpose:
the invention firstly provides a general method for solid-phase macroscopic synthesis of the coral-shaped metal selenide composite nitrogen-doped carbon catalyst, which comprises the following steps:
(1) Fully and uniformly grinding and mixing an inorganic metal salt and a nitrogenous polydentate ligand in a solid phase to obtain a precursor;
(2) Putting a proper amount of selenium powder and the precursor obtained in the step (1) into a quartz boat, and then putting the quartz boat into a temperature control area of a tube furnace, wherein the selenium powder is positioned at the upstream of the precursor; and (3) heating under an inert atmosphere, and washing, centrifuging and drying the obtained product to obtain the coral-shaped metal selenide composite nitrogen-doped carbon catalyst.
Further, in the step (1), the inorganic metal salt may be one or more of inorganic metal salts of iron, cobalt and nickel, and preferably one or more of inorganic metal salts of cobalt.
Further, in step (1), the nitrogen-containing polydentate ligand may be one selected from nitrilotriacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, and ethyleneglycoldiethylenediaminetetraacetic acid, and most preferably, nitrilotriacetic acid.
Further, in the step (1), the molar ratio of the inorganic metal salt to the nitrogen-containing polydentate ligand is 1:0.5-2, preferably 1:1.
further, in the step (2), the mass ratio of the selenium powder to the precursor is 1:0.1 to 2, preferably 1:0.5-1.5.
Further, in the step (2), the conditions of the heat treatment are as follows: the temperature of the heating treatment is 400-900 ℃, preferably 700-900 ℃; the time of the heat treatment is 1 to 8 hours, preferably 2 to 2.5 hours; the heating rate of the heating treatment can be controlled to be 2 ℃/min-10 ℃/min; the inert gas can be one of argon, nitrogen and a mixed gas of nitrogen and argon.
The metal selenide composite nitrogen-doped carbon catalyst obtained by the invention has a coral-shaped appearance, and the specific appearance is beneficial to the increase of active sites on the surface of the catalyst and the transmission of reaction substances. The metal selenide composite nitrogen-doped carbon catalyst obtained by the invention has mesoporous distribution, and the aperture is 2-50nm.
The metal selenide composite nitrogen-doped carbon catalyst obtained by the invention can be used in the oxygen reduction reaction process, such as a fuel cell or a metal-air cell cathode oxygen reduction catalyst.
In the invention, the coralline cobalt selenide composite nitrogen-doped carbon catalyst is applied to a zinc-air battery, has better battery performance, and the maximum power density can reach 154mW/cm2And at j =2mA/cm21020 cycles can be stably performed under the current density, the cycle time is as long as 170h, and the potential difference between the highest charging potential and the lowest discharging potential is about 0.73V when the current density is cycled for 170h, so that the zinc-air battery has excellent performance.
The coral-shaped metal selenide composite nitrogen-doped carbon catalyst synthesized in a large amount in a solid phase can be used as a cathode catalyst of a fuel cell and a metal-air cell, has excellent performance, has extremely high oxygen reduction activity compared with other existing non-noble metal materials, and is a potential substitute of a noble metal oxygen reduction catalyst; the metal selenide composite nitrogen-doped carbon catalyst with the coralliform mesoporous structure can be obtained through solid-phase macro synthesis, complex wet chemical synthesis steps and a template method are not needed, the synthesis method is simple, convenient to operate, low in cost, easy for large-scale macro production, and extremely high in economic benefit for large-scale production.
Compared with the prior art, the invention has the following beneficial effects:
1. the raw materials required by the invention are low in price, the synthesis process is simple, and the method can be used for mass production.
2. The catalyst prepared by the invention has a coralline shape, a higher specific surface and mesoporous distribution, and a specific shape structure is beneficial to increasing active sites and a mass transfer process in a reaction process.
3. Compared with the synthesis of other various raw materials and complicated template method and solvent thermal coordination preparation process, the preparation method of the invention adopts cheap nitrogen-containing polydentate ligands such as nitrilotriacetic acid, ethylene diamine tetraacetic acid and the like as carbon sources and nitrogen sources, and adopts inorganic metal salts as metal sources, so that the subsequent nitrogen doping process, the complex processes of liquid phase, surfactant, template removal and the like are not needed, the feeding amount is easy to control, and the preparation process is very simple.
4. The selenide composite nitrogen-doped carbon catalyst prepared by the invention has excellent catalytic performance, has higher oxygen reduction activity compared with other non-noble metal catalysts reported in documents, and has excellent battery performance in metal-air batteries.
5. The solid-phase synthesis method has many unique advantages in a plurality of syntheses, such as concise operation process, controllable process, safe experiment, low cost and environmental protection. The solid-phase macro-synthesis method can greatly reduce the process steps and reduce the industrial production cost. Therefore, the method for synthesizing the high-activity non-noble metal oxygen reduction catalyst in a solid phase and on a large scale has great significance for promoting the industrial development of fuel cells and metal-air cells.
Drawings
Fig. 1 is an X-ray powder diffraction curve of the cobalt selenide complex nitrogen-doped carbon catalyst prepared in example 1 of the present invention.
Fig. 2 is a raman spectrum analysis curve of the cobalt selenide complex nitrogen-doped carbon catalyst coralline prepared in example 1 of the present invention.
Fig. 3 is an X-ray photoelectron spectrum of the cobalt selenide complex nitrogen-doped carbon catalyst prepared in example 1.
Fig. 4 is a scanning electron microscope photograph of the cobalt selenide coralliform composite nitrogen-doped carbon catalyst prepared in example 1 of the present invention.
Fig. 5 is a transmission electron microscope photograph of the cobalt selenide coralliform composite nitrogen-doped carbon catalyst prepared in example 1 of the present invention.
Fig. 6 shows a nitrogen adsorption-desorption isotherm curve (fig. 6 (a)) and a pore size distribution curve (fig. 6 (b)) of the cobalt selenide coralliform composite nitrogen-doped carbon catalyst prepared in example 1 of the present invention.
Fig. 7 is a graph showing oxygen reduction experiments of the cobalt selenide coralliform composite nitrogen-doped carbon catalyst prepared in example 1 of the present invention and a platinum carbon catalyst used commercially.
FIG. 8 shows the coral-shaped cobalt selenide composite nitrogen-doped carbon catalyst and noble metal oxygen reduction catalyst (20% Pt/C + IrO) prepared in example 1 of the present invention2) The discharge curves in the zinc-air cell and the power density map (fig. 8 (a)) and cycle performance map (fig. 8 (b)) corresponding to the discharge curves.
Fig. 9 is a scanning electron micrograph of the coralline iron selenide composite nitrogen-doped carbon catalyst prepared in example 2 of the present invention.
Fig. 10 is a graph showing oxygen reduction experiments of the coralline iron selenide composite nitrogen-doped carbon catalyst prepared in example 2 of the present invention and a platinum carbon catalyst used commercially.
Detailed Description
The present invention will be described below with reference to specific examples, but the present invention is not limited thereto. The experimental procedures used in the following examples are all conventional procedures unless otherwise specified. Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
Example 1
The preparation method comprises the following steps of:
(1) 0.72g of cobalt chloride hexahydrate and 0.58g of nitrilotriacetic acid were sufficiently ground for 30 minutes to be uniformly mixed, thereby obtaining a precursor.
(2) Loading 1.2g of selenium powder and 1.32g of the precursor obtained in the step (1) into a quartz boat, and then placing the quartz boat into a temperature control area of a tube furnace, wherein the selenium powder is positioned at the upstream of the precursor; heating under nitrogen atmosphere (reaction temperature 800 ℃, time 2h, heating rate 5 ℃/min), cooling to room temperature, washing, centrifuging and drying at 60 ℃ overnight to obtain the coralline cobalt selenide composite nitrogen-doped carbon catalyst.
The X-ray powder diffraction curve of the cobalt selenide coralliform composite nitrogen-doped carbon catalyst prepared in the example is shown in fig. 1, which shows that the catalyst contains cobalt selenide.
The raman spectrum analysis curve of the cobalt selenide coralliform composite nitrogen-doped carbon catalyst prepared in the example is shown in fig. 2, I of the catalystDAnd IGThe peak intensity ratio was 0.98, indicating the presence of graphitized carbon in the catalyst.
The photoelectron spectrum full scan spectrum of the coralline cobalt selenide composite nitrogen-doped carbon catalyst prepared by the embodiment is shown in fig. 3, which shows that the catalyst contains cobalt, selenium, carbon, nitrogen and oxygen elements.
A scanning electron microscope image of the cobalt coralliform selenide composite nitrogen-doped carbon catalyst prepared in the example is shown in fig. 4, which shows that the prepared catalyst has a rich coralliform structure.
A transmission electron micrograph of the cobalt selenide coralliform composite nitrogen-doped carbon catalyst prepared in this example is shown in fig. 5, which shows that the prepared catalyst contains blocky and burr-like components.
The nitrogen adsorption-desorption isotherm curve and the pore size distribution test curve of the coralline cobalt selenide composite nitrogen-doped carbon catalyst prepared in the example are shown in fig. 6, which shows that the specific surface area of the prepared catalyst material is 70m2(ii) in terms of/g. From the pore size distribution curve, the catalyst has mesoporous distribution.
An oxygen reduction experimental curve of the coralline cobalt selenide composite nitrogen-doped carbon catalyst prepared by the embodiment is shown in fig. 7, and the specific experimental method comprises the following steps: oxygen reduction experiments were performed using a rotating disk electrode rotating at 1600rpm in 0.1mol/L potassium hydroxide solution at a sweep rate of 10mV/s. The commercial carbon-supported platinum catalyst used as a control had a platinum content of 20% by weight. Comparing the two curves, it can be seen that the catalyst prepared in this example shows a half-wave potential of 0.80 v (relative to the standard hydrogen electrode) in the oxygen reduction experiment, which is only 50 mv lower than the half-wave potential of 0.85 v of the commercial carbon-supported platinum catalyst, and shows excellent oxygen reduction catalytic performance.
The cobalt selenide coralliform composite nitrogen-doped carbon catalyst and the noble metal oxygen reduction catalyst (20% Pt/C + IrO) prepared in this example2) The discharge curve and the power density corresponding to the discharge curve in the zinc-air battery are shown in fig. 8, and the specific experimental method is as follows: the discharge curve scan rate of the zinc-air cell was 10mV/s, measured in a mixed solution of 6mol/L potassium hydroxide and 0.2mol/L zinc acetate. It can be seen from FIG. 8 (a) that the maximum power density of the non-noble metal catalyst is 154mW/cm2High Yu Shangyong noble metal catalyst 20% Pt/C + IrO2Maximum power density (96 mW/cm)2) The zinc-air battery has good performance; FIG. 8 (b) is a graph of the cycling performance of the cobalt selenide coralliform composite nitrogen doped carbon catalyst prepared in example 1 in a Zn-air cell, from which it can be seen that the non-noble metal catalyst has j =2mA/cm2Under the current density, 1020 cycles of stable circulation can be realized, the circulation time is as long as 170h, and after the catalyst is subjected to 170h of circulation, the potential difference between the highest charging potential and the lowest discharging potential is about 0.74V, and excellent circulation performance is shown.
Example 2
A non-noble metal catalyst was prepared in substantially the same manner as in example 1, except that ferrous chloride was used in place of cobalt chloride hexahydrate.
As shown in fig. 9 and 10, the morphology of the catalyst prepared in this example is similar to that of the catalyst prepared in example 1, and the half-wave potential obtained by testing the oxygen reduction curve in 0.1mol/L potassium hydroxide solution is equivalent to that of example 1, and the half-wave potential exhibited in the oxygen reduction experiment is 0.79 v (relative to a standard hydrogen electrode).
Example 3
A non-noble metal catalyst was prepared in essentially the same manner as in example 1, except that nickel chloride was used instead of cobalt chloride, and the resulting material had a morphology similar to that obtained in example 1.
Example 4
A non-noble metal catalyst was prepared in substantially the same manner as in example 1, except that the nitrogen used in example 1 was changed to argon, and the resulting material had a morphology similar to that of example 1.
The catalyst prepared in this example has the same composition as the catalyst prepared in example 1, and the half-wave potential obtained by testing the oxygen reduction curve in 0.1mol/L potassium hydroxide solution is equivalent to that of example 1, and the half-wave potential exhibited in the oxygen reduction experiment is about 0.80V (relative to a standard hydrogen electrode).
Example 5
A non-noble metal catalyst was prepared essentially as in example 1, except that the selenization temperature used in example 1 was changed from 600 c to 800 c, and the resulting material had a morphology similar to that of example 1.
The catalyst prepared in this example has the same composition as the catalyst prepared in example 1, and the half-wave potential obtained by testing the oxygen reduction curve in 0.1mol/L potassium hydroxide solution is equivalent to that of example 1, and the half-wave potential exhibited in the oxygen reduction experiment is about 0.80V (relative to a standard hydrogen electrode).
Example 6
A non-noble metal catalyst was prepared in substantially the same manner as in example 1, except that the selenization time used in example 1 was changed from 2 hours to 4 hours, and the resulting material had a morphology similar to that obtained in example 1.
The catalyst prepared in this example has the same composition as the catalyst prepared in example 1, and the half-wave potential obtained by testing the oxygen reduction curve in 0.1mol/L potassium hydroxide solution is equivalent to that of example 1, and the half-wave potential exhibited in the oxygen reduction experiment is about 0.80V (relative to a standard hydrogen electrode).
The above are merely exemplary embodiments of the present invention, and are not intended to limit the present invention.

Claims (10)

1. A method for solid-phase macro synthesis of a coral-shaped metal selenide composite nitrogen-doped carbon catalyst is characterized by comprising the following steps:
(1) Fully carrying out solid-phase grinding on inorganic metal salt and a nitrogenous polydentate ligand to obtain a precursor;
(2) Putting a proper amount of selenium powder and the precursor obtained in the step (1) into a quartz boat, and then putting the quartz boat into a temperature control area of a tube furnace, wherein the selenium powder is positioned at the upstream of the precursor; and (3) heating under an inert atmosphere, and washing, centrifuging and drying the obtained product to obtain the coral-shaped metal selenide composite nitrogen-doped carbon catalyst.
2. The method for solid-phase macro-synthesis of the coral-shaped metal selenide composite nitrogen-doped carbon catalyst as claimed in claim 1, wherein the method comprises the following steps: in the step (1), the inorganic metal salt is at least one of inorganic metal iron salt, cobalt salt and nickel salt.
3. The method for solid-phase macro-synthesis of the coral-shaped metal selenide composite nitrogen-doped carbon catalyst as claimed in claim 1, wherein the method comprises the following steps: in the step (1), the nitrogen-containing polydentate ligand is one of nitrilotriacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid and ethyleneglycoldiethylenediaminetetraacetic acid.
4. The method for solid-phase macro-synthesis of the coral-shaped metal selenide composite nitrogen-doped carbon catalyst as claimed in claim 1, wherein the method comprises the following steps: in the step (1), the molar ratio of the inorganic metal salt to the nitrogen-containing polydentate ligand is 1:0.5-2.
5. The method for solid-phase macro-synthesis of the coral-shaped metal selenide composite nitrogen-doped carbon catalyst as claimed in claim 1, wherein the method comprises the following steps: in the step (2), the mass ratio of the selenium powder to the precursor is 1:0.1-2.
6. The method for solid-phase mass synthesis of the coral-shaped metal selenide composite nitrogen-doped carbon catalyst as claimed in claim 1, wherein the method comprises the following steps: in the step (2), the temperature of the heating treatment is 400-900 ℃, and the treatment time is 1-8 hours.
7. A coral-shaped metal selenide composite nitrogen-doped carbon catalyst prepared by the method of any one of claims 1 to 6.
8. The coral-shaped metal selenide composite nitrogen-doped carbon catalyst as set forth in claim 7, wherein: the catalyst has mesoporous distribution, and the aperture is 2-50nm.
9. Use of the coral-shaped metal selenide composite nitrogen-doped carbon catalyst of claim 7 or 8 in a fuel cell or metal-air cell cathode oxygen reduction catalyst.
10. A fuel cell or a metal-air cell using the coral-shaped metal selenide composite nitrogen-doped carbon catalyst as set forth in claim 7 or 8 as a cathode oxygen reduction catalyst.
CN202210764297.3A 2022-06-29 2022-06-29 Method for solid-phase macro synthesis of coral-shaped metal selenide composite nitrogen-doped carbon catalyst and application thereof Pending CN115275227A (en)

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