CN110993975B - Nitrogen-doped porous carbon non-metal catalyst, preparation method thereof and application thereof in redox reaction - Google Patents
Nitrogen-doped porous carbon non-metal catalyst, preparation method thereof and application thereof in redox reaction Download PDFInfo
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Abstract
The invention discloses a nitrogen-doped porous carbon non-metal catalyst, a preparation method thereof and application thereof in redox reaction, and belongs to the technical field of energy and nano material preparation. The method prepares the non-metal nitrogen-doped porous carbon catalyst by combining hydrothermal polymerization with a high-temperature carbonization doping process. The non-metal nitrogen-doped porous carbon catalytic material shows similar oxygen reduction reaction electrocatalytic activity as a commercial platinum-carbon catalyst in alkaline electrolyte, and is superior to the stability and methanol resistance of the commercial platinum-carbon catalyst. The method has the advantages of simple process and wide raw material source, and is expected to realize high-efficiency and low-cost large-scale production. The oxygen reduction reaction electrocatalyst can be applied to the fields of alkaline fuel cells, metal-air cell cathode materials and the like.
Description
Technical Field
The invention relates to the technical field of energy and nano material preparation, in particular to a nitrogen-doped porous carbon non-metal catalyst, a preparation method thereof and application thereof in redox reaction.
Background
With the rapid development of human civilization, the energy consumption rapidly rises. The scheme of utilizing traditional fossil fuels, such as petroleum, coal and natural gas, as national energy supply faces a plurality of problems. First, fossil energy reserves are limited. Secondly, fossil energy combustion produces large quantities of greenhouse gases. Studies have shown that the large emission of greenhouse gases is a major cause of global warming in recent years. Furthermore, fossil energy is extremely unevenly distributed. At present, the international situation is increasingly tense, the energy independence is realized, and the significance is great for the national security. Therefore, a flexible distributed energy scheme is urgently needed to be proposed.
Hydrogen energy is a secondary energy source that facilitates distributed energy solutions. Fuel cells have received much attention from all countries around the world as a key ring to the ground of hydrogen energy. As an energy conversion device, the hydrogen and oxygen are reacted to generate water, and heat energy and electric energy are simultaneously released, so that the device has the advantages of low working temperature, no pollution, high mass energy density and the like. However, the cathode reaction of a fuel cell is generally six orders of magnitude slower than the anode reaction thereof, and a larger overpotential is required for the reaction to proceed, so that the energy utilization efficiency thereof cannot be sufficiently high. Platinum and its alloy are used as the current widely-used oxygen reduction reaction electrocatalyst, and still have the defects of scarce reserves, high price, easy poisoning and the like, thus hindering the commercial popularization of fuel cells in the world. The existing research shows that the nonmetal carbon-based material is expected to break through the defects of the platinum-based material, so that a novel high-efficiency catalytic material with multiple characteristics of high activity, strong stability, methanol resistance, low price, rich sources and the like is developed.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a nitrogen-doped porous carbon non-metal catalyst, a preparation method thereof and application thereof in redox reaction. The catalytic material does not use any noble metal, even can be free of metal, has rich raw material sources, and solves the problems of production cost and quality stability which can be faced after the scale production of the fuel cell. In particular, the non-metallic catalytic material can achieve the catalytic performance of the same level as that of the current commercial platinum-carbon, and has more excellent stability and methanol resistance.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a nitrogen-doped porous carbon nonmetal catalyst has a three-dimensional hierarchical pore structure, wherein the hierarchical pore structure comprises mesopores formed between glucose carbon spheres which are mutually adhered and micropores on the carbon spheres, and the size of the glucose carbon spheres is 100-300 nm.
The hierarchical pore structure comprises pores having different pore diameters, including pore diameters in the range of 0.1-1nm, 2-5nm, and 50-100 nm.
The X-ray diffraction pattern of the catalyst has a wide diffraction peak in the range of 10-30 degrees, and a diffraction peak at 55 degrees. The preparation method of the nitrogen-doped porous carbon nonmetal catalyst comprises the following steps:
(1) hydrothermal polymerization: preparing a glucose solution, and carrying out hydrothermal polymerization reaction at the temperature of 120-250 ℃ and the pressure of 0.5-3MPa for 4-24 h; obtaining precursor carbon spheres after centrifugation, washing and drying;
(2) high-temperature carbonization: and (2) grinding and mixing the precursor carbon spheres obtained in the step (1), nitrogen source and zinc salt, putting the mixture into a tube furnace, protecting the mixture for 1 to 3 hours in advance in an inert atmosphere, heating the mixture to the temperature of 800-1000 ℃, preserving the heat for 0.5 to 4 hours, and cooling the mixture along with the furnace to obtain the nitrogen-doped porous carbon non-metal catalyst.
In the step (1), the solvent of the glucose solution is water, and the concentration of the glucose solution is 0.01-2.0 mol/L.
In the step (1), the drying temperature is 50-100 ℃, and the drying time is 5-30 h.
In the step (2), the weight ratio of the precursor carbon spheres, the nitrogen source and the zinc salt is (1-2): (10-20): (1-4).
In the step (2), the nitrogen source is ammonia gas, urea, melamine or ammonium chloride, the zinc salt is zinc chloride, zinc nitrate, zinc acetate or zinc sulfate, and the inert atmosphere is helium, argon or nitrogen.
The nitrogen-doped porous carbon non-metal catalyst is applied to catalyzing and reducing oxygen in alkaline electrolyte, and the initial potential, half-wave potential and limiting current density of the nitrogen-doped porous carbon non-metal catalyst relative to a reversible hydrogen electrode are respectively 0.6-1.0V, 0.5-0.9V and 3.0-6.0mA cm-2。
The design idea of the invention is as follows:
the reason for the limited activity of the electrocatalytic materials for oxygen reduction reactions is mainly two-fold: on one hand, the electron transfer capacity of the solid-liquid interface is limited, and the problem can be solved by improving the intrinsic activity of the active sites and increasing the number of the active sites; another aspect is the mass transfer process around the catalytic material, the three-dimensional structure of which has a non-negligible effect on the process. In order to design the three-dimensional structure of the non-metal carbon-based material and improve the catalytic activity of the non-metal carbon-based material, the invention adopts hydrothermal polymerization glucose carbon spheres with rich mesoporous structures as carbon precursors and zinc salt as a microporous pore-forming agent to prepare the nitrogen-doped porous carbon catalytic material.
The invention mainly discloses a fuel cell cathode catalytic material, which is applied to a fuel cell cathode taking potassium hydroxide as alkaline electrolyte and is used for catalytically reducing oxygen in the fuel cell cathode. The non-metal carbon-based material needs to ensure enough excellent conductivity and load enough abundant active sites to ensure a faster transfer rate of electrons at an interface: with the increase of the carbonization temperature, the carbon material tends to be graphitized, the proportion of pyridine nitrogen in the total nitrogen species content is increased, but the total nitrogen element content is reduced, so that the higher the carbonization temperature is, the better the conductivity is; there is an optimum carbonization temperature in terms of the number of active sites. The oxygen reduction electrocatalytic material needs to consider improving the electron transfer rate and also needs to consider realizing rich hierarchical pore structures in the material so as to be beneficial to accelerating the substance transfer effect, exert the advantage of space limitation and promote the oxygen reduction reaction to proceed to a four-electron process. The invention utilizes the three-dimensional network formed by hydrothermal polymerization glucose carbon spheres and the physical characteristics of zinc salt heat volatilization to construct a multi-level pore structure, thereby being beneficial to the substance transfer of reactants and products. Meanwhile, the hierarchical pore structure also has a domain limiting effect on the intermediate product so as to promote the intermediate product to be further reduced and realize a four-electron process.
The invention has the following advantages and beneficial effects:
1. the invention utilizes glucose, nitrogen source and zinc salt with rich sources to prepare the nitrogen-doped porous carbon material with rich pore structure. The method has simple process, abundant and controllable raw materials, and high large-scale production value.
2. According to the invention, through adjustment of hydrothermal polymerization and high-temperature carbonization processes, the optimization of the catalytic performance of the nitrogen-doped porous carbon in the four-electron oxygen reduction reaction in an alkaline environment can be realized, and the equivalent level, more excellent stability and methanol resistance of a commercial platinum-carbon catalyst can be achieved.
Drawings
Fig. 1 is a scanning electron microscope image of nitrogen-doped porous carbon of the oxygen reduction electrocatalyst obtained in example 1.
Fig. 2 is an X-ray diffraction pattern of nitrogen-doped porous carbon of the oxygen reduction electrocatalyst prepared in example 1.
Fig. 3 is a hierarchical pore size distribution diagram of nitrogen-doped porous carbon of the oxygen reduction electrocatalyst prepared in example 1.
Fig. 4 is a nitrogen adsorption/desorption curve of the oxygen reduction electrocatalyst nitrogen-doped porous carbon obtained in example 2.
FIG. 5 is a cyclic voltammogram of the nitrogen-doped porous carbon of the electrocatalyst for oxygen reduction obtained in example 3 in a 0.1mol/L potassium hydroxide solution saturated with oxygen.
FIG. 6 is a polarization curve of the oxygen reduction electrocatalyst, nitrogen-doped porous carbon obtained in example 3, rotating at 1600rpm in 0.1mol/L potassium hydroxide solution saturated with oxygen.
Detailed Description
The present invention will be further described with reference to specific examples.
Example 1
Pouring 80mL of 0.5mol/L glucose solution into a 100mL polytetrafluoroethylene reaction kettle liner, sealing the stainless steel reaction kettle, and then putting the stainless steel reaction kettle into an oven for heat preservation at 180 ℃ for 10 hours; and centrifuging the materials obtained after the reaction at 9500rpm, washing the materials for 3 times by using deionized water, and drying the materials in a blast oven at 60 ℃ for 24 hours to obtain the hydrothermal glucose carbon spheres.
Grinding and mixing the prepared hydrothermal glucose carbon spheres with urea and zinc chloride according to the mass ratio of 1:10:1, putting the mixture into an alumina ark, and putting the alumina ark into a quartz tube in a tube furnace. Introducing nitrogen for more than 60min, ensuring that air is exhausted, raising the temperature in the tubular furnace to 900 ℃ at the temperature rise speed of 5 ℃/min, preserving the temperature for 2h, and cooling along with the furnace to obtain the oxygen reduction reaction electrocatalyst-nitrogen doped porous carbon catalyst.
Fig. 1 is a scanning electron microscope image of the nitrogen-doped porous carbon catalyst obtained in example 1. As shown in the figure, the carbon spheres have the size of 100nm-250nm and are contacted and adhered with each other to form a mesoporous structure. The surface of the carbon spheres is not completely smooth, and a microporous structure exists.
Fig. 2 is an X-ray diffraction spectrum of the nitrogen-doped porous carbon catalyst obtained in example 1, and it can be seen that a broad diffraction peak exists in a range of 10 to 30 °, indicating that a carbon simple substance in the nitrogen-doped porous carbon exists mainly in an amorphous carbon form; a weak diffraction peak exists at 55 degrees, which is related to the high-index crystal face of the graphite carbon.
Fig. 3 is a hierarchical pore size distribution diagram of the nitrogen-doped porous carbon catalyst obtained in example 1, and it can be seen that there are three types of pores with different sizes. The micropores with the size of 0.1-1nm are mainly related to zinc volatilization at high temperature, the micropores with the size of 2-5nm are mainly related to the surface concave-convex of the glucose polymerization carbon sphere, and the mesopores with the size of 50-100nm are mainly related to the carbon spheres which are mutually adhered.
Example 2
Pouring 80mL of 0.5mol/L glucose solution into a 100mL polytetrafluoroethylene reaction kettle liner, sealing the stainless steel reaction kettle, and then putting the stainless steel reaction kettle into an oven for heat preservation at 180 ℃ for 10 hours; and (3) centrifuging the materials obtained after the reaction at 9500rpm, washing the materials for 3 times by using deionized water, and drying the materials in a blast oven at 60 ℃ for 24 hours to obtain the hydrothermal glucose carbon spheres.
Grinding and mixing the prepared hydrothermal glucose carbon spheres with urea and zinc chloride according to the mass ratio of 1:10:1, putting the mixture into an alumina ark, and putting the alumina ark into a quartz tube in a tube furnace. Introducing nitrogen for more than 60min, ensuring that air is exhausted, raising the temperature in the tubular furnace to 1000 ℃ at the temperature rise speed of 5 ℃/min, preserving the temperature for 2h, and cooling along with the furnace to obtain the oxygen reduction reaction electrocatalyst-nitrogen doped porous carbon catalyst.
Fig. 4 is a nitrogen adsorption/desorption curve of the oxygen reduction electrocatalyst nitrogen-doped porous carbon obtained in example 2. Vacuum degassing for 8h at 300 ℃, and then testing to obtain a sample with the BET specific surface area of 1786.4083m2 g-1. As shown in the figure, the nitrogen adsorption and desorption curve is an I-shaped curve, and the gas adsorption quantity rapidly rises under low pressure, which indicates that the number of micropores is large. The specific surface area of the micropore obtained by the t-Plot method is 1564.5669m2 g-1。
Example 3
Pouring 80mL of 0.5mol/L glucose solution into a 100mL polytetrafluoroethylene reaction kettle inner container, sealing the stainless steel reaction kettle, and then putting the stainless steel reaction kettle into an oven for heat preservation at 180 ℃ for 10 hours; and centrifuging the materials obtained after the reaction at 9500rpm, washing the materials for 3 times by using deionized water, and drying the materials in a blast oven at 60 ℃ for 24 hours to obtain the hydrothermal glucose carbon spheres.
Grinding and mixing the prepared hydrothermal glucose carbon spheres with urea and zinc chloride according to the mass ratio of 1:10:1, putting the mixture into an alumina ark, and putting the alumina ark into a quartz tube in a tube furnace. Introducing nitrogen for more than 60min, ensuring that air is exhausted, raising the temperature in the tubular furnace to 900 ℃ at the temperature rise speed of 5 ℃/min, preserving the temperature for 2h, and cooling along with the furnace to obtain the oxygen reduction reaction electrocatalyst nitrogen-doped porous carbon catalyst.
In a three-electrode system, a rotating disc electrode modified by a catalytic material surface is used as a working electrode, a graphite rod is used as a counter electrode, a silver/silver chloride electrode is used as a reference electrode, 0.1mol/L potassium hydroxide solution is used as electrolyte, and the electrochemical test of cyclic voltammetry and a rotating disc polarization curve is carried out within the voltage range of-0.8V-0.2V.
FIG. 5 is a cyclic voltammetry curve of the nitrogen-doped porous carbon of the oxygen reduction electrocatalyst obtained in example 3 in an oxygen-saturated 0.1mol/L KOH solution at a scan rate of 50mV/s, showing a distinct peak characteristic of oxygen reduction reaction, which is about 0.81V relative to the peak potential of the reversible hydrogen electrode, indicating that the catalyst of the present invention has a better catalytic performance for oxygen reduction reaction in an alkaline medium.
FIG. 6 is a polarization curve of the oxygen reduction electrocatalyst nitrogen-doped porous carbon obtained in example 3 in oxygen-saturated 0.1mol/L potassium hydroxide solution at different rotation speeds with a scan speed of 10 mV/s. As can be seen from the figure, the nitrogen-doped porous carbon catalyst and the commercial platinum carbon have similar initial potential, half-wave potential and ultimate diffusion current of the oxygen reduction reaction. When the rotating speed of the rotating disc electrode is 1600rpm, the initial potential relative to the reversible hydrogen electrode is 0.92V, the half-wave potential is 0.86V, and the limiting diffusion current is 5.0mA cm-2And the stability and the methanol resistance are better than those of the commercial platinum-carbon catalyst.
The above examples are given by way of reference only, and it is within the scope of the present patent to have a method for preparing a non-metal redox catalyst from glucose-polymerizing polysaccharide and zinc salt similar to or extended from the teachings of the present patent.
Claims (6)
1. A nitrogen-doped porous carbon non-metal catalyst is characterized in that: the catalyst has a three-dimensional hierarchical pore structure, the hierarchical pore structure comprises mesopores formed between glucose carbon spheres which are mutually adhered and micropores on the carbon spheres, and the size of the glucose carbon spheres is 100-300 nm; the preparation method of the nitrogen-doped porous carbon nonmetal catalyst comprises the following steps:
(1) hydrothermal polymerization: preparing a glucose solution, and carrying out hydrothermal polymerization reaction at the temperature of 120-250 ℃ and the pressure of 0.5-3MPa for 4-24 h; obtaining precursor carbon spheres after centrifugation, washing and drying;
(2) high-temperature carbonization: grinding and mixing the precursor carbon spheres obtained in the step (1), a nitrogen source and zinc salt, putting the mixture into a tube furnace, protecting the mixture for 1 to 3 hours in advance in an inert atmosphere, heating the mixture to the temperature of 800-1000 ℃, preserving the heat for 0.5 to 4 hours, and cooling the mixture along with the furnace to obtain the nitrogen-doped porous carbon non-metal catalyst;
in the step (2), the weight ratio of the precursor carbon spheres, the nitrogen source and the zinc salt is (1-2): (10-20): (1-4); the nitrogen source is urea, melamine or ammonium chloride, the zinc salt is zinc chloride, zinc nitrate, zinc acetate or zinc sulfate, and the inert atmosphere is helium, argon or nitrogen.
2. The nitrogen-doped porous carbon non-metallic catalyst of claim 1, wherein: the hierarchical pore structure comprises pores having different pore diameters, including pore diameters in the range of 0.1-1nm, 2-5nm, and 50-100 nm.
3. The nitrogen-doped porous carbon non-metallic catalyst of claim 1, wherein: the X-ray diffraction pattern of the catalyst has a wide diffraction peak in the range of 10-30 degrees, and a diffraction peak at 55 degrees.
4. The nitrogen-doped porous carbon non-metallic catalyst of claim 1, wherein: in the step (1), the solvent of the glucose solution is water, and the concentration of the glucose solution is 0.01-2.0 mol/L.
5. The nitrogen-doped porous carbon non-metallic catalyst of claim 1, wherein: in the step (1), the drying temperature is 50-100 ℃, and the drying time is 5-30 h.
6. Use of a nitrogen doped porous carbon non-metallic catalyst according to any one of claims 1 to 3 in a redox reaction, characterized in that: the catalyst is applied to catalytic reduction of oxygen in alkaline electrolyte, and the initial potential, half-wave potential and limiting current density of the catalyst relative to a reversible hydrogen electrode are respectively 0.6-1.0V, 0.5-0.9V and 3.0-6.0mA cm-2。
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| CN112221530A (en) * | 2020-11-13 | 2021-01-15 | 青岛科技大学 | Preparation method and application of non-noble metal single-atom dual-function electrocatalyst |
| CN113013391A (en) * | 2021-02-23 | 2021-06-22 | 北京工业大学 | Method for preparing nitrogen-doped multidimensional and hierarchical porous carbon material adaptive to sulfur anode carrier of aluminum-sulfur battery |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106185918A (en) * | 2016-07-19 | 2016-12-07 | 句容市百诚活性炭有限公司 | A kind of preparation method of the activated carbon of hierarchical porous structure |
| CN107572523A (en) * | 2017-09-11 | 2018-01-12 | 桂林电子科技大学 | A kind of classifying porous carbosphere of N doping and its preparation method and application |
| CN108295832A (en) * | 2018-02-06 | 2018-07-20 | 淮北师范大学 | A kind of porous ZnO composite hollow sphere catalyst and preparation method thereof |
| CN110124721A (en) * | 2019-05-24 | 2019-08-16 | 桂林电子科技大学 | A kind of nitrogen-doped porous carbon material and its preparation method and application of load C oB nanoparticle |
-
2019
- 2019-10-12 CN CN201910967519.XA patent/CN110993975B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106185918A (en) * | 2016-07-19 | 2016-12-07 | 句容市百诚活性炭有限公司 | A kind of preparation method of the activated carbon of hierarchical porous structure |
| CN107572523A (en) * | 2017-09-11 | 2018-01-12 | 桂林电子科技大学 | A kind of classifying porous carbosphere of N doping and its preparation method and application |
| CN108295832A (en) * | 2018-02-06 | 2018-07-20 | 淮北师范大学 | A kind of porous ZnO composite hollow sphere catalyst and preparation method thereof |
| CN110124721A (en) * | 2019-05-24 | 2019-08-16 | 桂林电子科技大学 | A kind of nitrogen-doped porous carbon material and its preparation method and application of load C oB nanoparticle |
Non-Patent Citations (2)
| Title |
|---|
| "Hierarchically porous nitrogen一doped carbon as cathode for lithium-sulfur batteries"，;Wu Rui et al.;《Journal of Energy Chemistry》;20180216;第27卷;第1661-1667页 * |
| "Synthesis of Nitrogen-Doped Porous Carbon Spheres with Improved Porosity toward the Electrocatalytic Oxygen Reduction";Gu Daguo et al.;《ACS Sustainable Chemistry&Engineering》;20171003;第5卷;第11105-11116页 * |
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