CN114392761A - Preparation method of M-N-C carbon aerogel electrocatalyst - Google Patents

Preparation method of M-N-C carbon aerogel electrocatalyst Download PDF

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CN114392761A
CN114392761A CN202210020822.0A CN202210020822A CN114392761A CN 114392761 A CN114392761 A CN 114392761A CN 202210020822 A CN202210020822 A CN 202210020822A CN 114392761 A CN114392761 A CN 114392761A
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aerogel
nitrogen
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吴晓栋
卢嘉欣
沈晓冬
崔升
丁洁
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Nanjing Tech University
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    • B01J37/02—Impregnation, coating or precipitation
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Abstract

The invention relates to a preparation method of an M-N-C carbon aerogel electrocatalyst. A sodium carbonate catalyst is introduced to carry out phenolic aldehyde reaction, and a sol-gel method is adopted in combination with a supercritical drying process, an impregnation method and high-temperature heat treatment to prepare the M-N-C aerogel electrocatalyst. The aerogel material prepared by the method has the characteristics of excellent electrocatalysis performance, low density, high specific surface, energy conservation, environmental protection and the like, and has positive production significance for realizing the application of the aerogel material in the fields of water electrolysis, electrocatalysis, fuel cells, energy conservation, environmental protection and the like.

Description

Preparation method of M-N-C carbon aerogel electrocatalyst
Technical Field
The invention belongs to the field of preparation processes of aerogel materials, and particularly relates to a method for preparing an M-N-C carbon aerogel electrocatalyst by combining a sol-gel method and a supercritical drying process.
Background
In order to effectively alleviate the problems of energy crisis and environmental deterioration caused by the combustion of the conventional fossil fuel and meet the energy requirements of modern society, it is important to seek sustainable, clean and efficient energy production, which has prompted the development of sustainable energy conversion and storage technologies such as fuel cells, metal-air batteries, water decomposition, and the like. Electrolysis of water is an efficient and sustainable way to generate hydrogen and is considered an effective method for future renewable energy production, storage and use. The electrolyzed water consists of two half-reactions, the cathodic Hydrogen Evolution Reaction (HER) and the anodic Oxygen Evolution Reaction (OER), respectively. OER is a four-electron transfer process, the mechanism is very complex, the reaction kinetics is slow, and the overpotential is high, which is an important factor for limiting the efficiency of water electrolysis, so that the design and synthesis of the efficient OER catalyst are the key for improving the energy efficiency of water electrolysis. The prior electrocatalysis field is researched more materials such as transition metal oxide, perovskite oxide, layered double hydroxide, spinel type semiconductor oxide and the like, which makes great breakthrough in the aspect of optimizing the composition and structure of the catalyst. Ji and the like use sulfur to modulate NiFe compound to prepare N/S co-doped graphene S-Ni3The catalyst has rich active center and two-dimensional sheet structure, is an excellent bifunctional oxygen electrocatalyst, has a half-wave potential of 0.87V in ORR reaction, and has an OER reaction current density of 10mA cm-2The overpotential in the case of time was 0.26V. (Angewandte Chemie-International edition, 2020.59 (26)). Li and the like doping with cobalt to modify Cu7S4The nano-disc is used for preparing the electrocatalyst with low cost, good stability and environmental friendliness, and the OER reaction is carried out at the current density of 10mA cm-2The overpotential is 0.27V, which is favorable for electron transfer between the active site of the electrocatalyst and the electrode. (ACS Nano,2017,11, (12)). But realize high-efficiency mass transferAnd improving the overall catalytic performance, there are still some disadvantages, such as high price of metal, small specific surface area, few active sites, low mass transfer efficiency, etc.
The aerogel is a light material with a three-dimensional nano porous structure, and has excellent performances of high specific surface area, high porosity, low density, low dielectric constant and the like. The method has wide application prospect in the fields of thermal, optical, acoustic, microelectronic, catalytic, aerospace, energy-saving building and the like. Therefore, the conductive aerogel is used as an electrocatalytic material, and the high specific surface area of the aerogel material is utilized to improve the electrocatalytic performance. The conductive aerogel is: carbon aerogels, graphene aerogels, and metal aerogels. Among them, carbon aerogel is a network structure with high specific surface area, high porosity, strong corrosion resistance, low density, low resistivity and good stability, and is one of the best material of catalyst carrier and ideal material of high-efficiency and high-energy capacitor. In order to increase the catalytic active sites and further improve the electrocatalytic performance, non-metal nitrogen is selected to be doped into the carbon aerogel, and the doped nitrogen can provide abundant structural defects and active sites and generate local electronic states around carbon atoms to become definite catalytic active sites. Then metal elements are doped, the isolated metal single atom and the surrounding nitrogen atoms form M-N coordination effective electronic coupling, and the electronic coupling can remarkably adjust the adsorption energy of an electronic structure and an intermediate product, so that the kinetics of electrochemical reaction is promoted. Therefore, the M-N-C aerogel formed by doping the non-metal elements and the metal elements into the carbon aerogel greatly improves the electrocatalytic activity of the catalyst and achieves better catalytic effect.
Disclosure of Invention
The invention synthesizes M-N-C aerogel by combining a sol-gel method with a supercritical drying process, a soaking penetration method and high-temperature heat treatment, and aims to overcome the defects in the prior art, provide a preparation method of an M-N-C aerogel electrocatalyst.
The technical scheme of the invention is as follows: a preparation method of an M-N-C aerogel electrocatalyst comprises the following specific steps:
(1) uniformly mixing deionized water, phenol, aldehyde and a nitrogen-containing compound, and stirring to obtain a sol system;
(2) adding sodium carbonate into the sol system obtained in the step (1) and stirring to obtain nitrogen-doped wet gel;
(3) adding an aging liquid into the wet gel obtained in the step (2), and performing replacement in an oven;
(4) performing carbon dioxide supercritical drying treatment on the wet gel obtained in the step (3) to obtain nitrogen-doped organic aerogel;
(5) soaking the nitrogen-doped organic aerogel obtained in the step (4) in a metal salt solution to obtain a metal and nitrogen-doped M-N-C aerogel precursor;
(6) carrying out heat treatment on the metal and nitrogen-doped M-N-C aerogel precursor obtained in the step (5) in a furnace containing a protective gas atmosphere to obtain an M-N-C aerogel electrocatalyst;
wherein: deionized water, phenol, nitrogen-containing compounds and aldehyde in the step (1) are (30-60): 1: (1.0-10.0): (5-20) uniformly mixing in a molar ratio; the sodium carbonate and the phenol in the step (2) are mixed according to a molar ratio (0.04-0.1): 1, mixing.
Preferably, the phenol in the step (1) is one or more of resorcinol, hydroquinone, catechol or phloroglucinol; the aldehyde is one or more of formaldehyde, acetaldehyde, propionaldehyde or benzaldehyde; the nitrogen-containing compound is one or more of melamine, urea, hydrazine hydrate or ethylenediamine.
Preferably, the stirring temperature in the step (1) is 25-40 ℃ and the time is 5-30 min.
Preferably, the stirring temperature in the step (2) is 25-40 ℃ and the time is 0.5-2 h.
Preferably, the aging solution in the step (3) is one or more of methanol, n-amyl alcohol, ethanol or isopropanol.
Preferably, the temperature of the oven in the step (3) is 20-70 ℃, the replacement times are 3-9 times, and each time lasts for 8-24 hours.
Preferably, the carbon dioxide supercritical drying method in the step (4): carbon dioxide is used as a drying medium, the reaction temperature is 40-90 ℃, the pressure in the high-pressure reaction kettle is 8-12 MPa, the drying rate is 5-10L/min, and the drying time is 8-16 h.
Preferably, the metal salt solution in the step (5) is an aqueous solution of a metal salt; the mass concentration of the metal salt solution is 1-10%; wherein the metal salt is one or more of ferric chloride, cobalt chloride, nickel chloride, zinc chloride or manganese chloride.
Preferably, the mass ratio of the nitrogen-doped organic aerogel to the metal salt in the step (5) is 0.02-0.4; the soaking time is 0.5-5 h.
Preferably, the protective gas in step (6) is one or a mixture of argon, helium and nitrogen. The heat treatment temperature is 300-800 ℃, the heating rate is 1-10 ℃/min, and the heat treatment heat preservation time is 2-8 h.
Has the advantages that:
the method and the M-N-C carbon aerogel electrocatalyst prepared by the method have the following characteristics:
(1) the process has the advantages of simple raw materials and production method, low energy consumption, high efficiency and low cost.
(2) The material has the advantages of excellent catalytic performance, high porosity, large specific surface area and uniform particles.
(3) The non-metal doped carbon aerogel prepared by the method is a complete block material, and has positive significance for realizing the application of the aerogel material in the fields of water electrolysis, fuel cells, metal air cells, energy conservation, environmental protection and the like.
Drawings
FIG. 1 is a photomicrograph of the bulk Fe-N-C aerogel material prepared in example 1.
FIG. 2 is a graph of the nitrogen adsorption desorption of the Co-N-C aerogel material of example 2.
FIG. 3 is a LSV plot of the OER reaction of the Ni-N-C aerogel material of example 3.
Detailed Description
Example 1
Deionized water, resorcinol, melamine and formaldehyde are mixed according to a molar ratio of 30: 1: 1.5: 5, stirring for 5min at 25 ℃, adding sodium carbonate and resorcinol into the obtained sol system according to the molar ratio of 0.05:1, uniformly stirring for 0.5h, pouring into a beaker with a preservative film, putting into a 25 ℃ oven for gelation, adding methanol aging solution, and replacing for 4 times, 8h each time. And then carrying out carbon dioxide supercritical drying treatment on the wet gel, wherein the reaction temperature is 45 ℃, the pressure in a high-pressure reaction kettle is 8MPa, the drying rate is 6L/min, and the drying time is 15h, so as to obtain the nitrogen-doped carbon aerogel. Soaking the aerogel in a 1% ferric chloride solution for 0.5h, wherein the mass ratio of the aerogel to ferric chloride is 0.02, so as to obtain a Fe-N-C aerogel precursor, and carrying out heat treatment at 300 ℃ in an argon atmosphere of a tubular furnace, wherein the heating rate is 3 ℃/min, the heat treatment time is 8h, so as to finally obtain the Fe-N-C aerogel electrocatalyst. A physical photograph of the aerogel material obtained is shown in FIG. 1, and the aerogel appears black and is a block material with a specific surface area of 615.2m2(ii)/g, total micropore volume of 0.21cm3OER at a current density of 10m A/cm-2Then, the overpotential of this sample is 0.31V, and the Tafel slope is 72mV dec-1。
Example 2
Deionized water, resorcinol, urea and acetaldehyde are mixed according to a molar ratio of 40: 1: 3.0: 10, stirring for 10min at 28 ℃, adding sodium carbonate and resorcinol into the obtained sol system according to the molar ratio of 0.05:1, uniformly stirring for 0.8h, pouring into a beaker with a preservative film, putting into a 35 ℃ oven for gelation, adding n-amyl alcohol aging liquid, and replacing for 6 times, each time for 12 h. And then carrying out carbon dioxide supercritical drying treatment on the wet gel, wherein the reaction temperature is 60 ℃, the pressure in a high-pressure reaction kettle is 9MPa, the drying rate is 6L/min, and the drying time is 15h, so as to obtain the nitrogen-doped carbon aerogel. Soaking the aerogel in 3% cobalt chloride solution for 1.0h at a mass ratio of 0.1 to cobalt chloride to obtain Co-N-C aerogel precursor, performing heat treatment at 500 deg.C in a tube furnace under argon atmosphere, and heating to obtain the final productThe temperature speed is 5 ℃/min, the heat treatment time is 4h, and the Co-N-C aerogel electrocatalyst is finally obtained. The nitrogen-desorption adsorption of the prepared aerogel material is shown in FIG. 2, and the specific surface area of the material is 847.6m2(ii)/g, total micropore volume of 0.29cm3(ii) in terms of/g. OER at a current density of 10m A/cm-2When the voltage is high, the overpotential of the prepared aerogel material is 0.33V, and the Tafel slope is 78mV dec-1。
Example 3
Deionized water, hydroquinone, hydrazine hydrate and propionaldehyde are mixed according to a molar ratio of 45: 1: 4.0: 13, stirring for 15min at 30 ℃, adding sodium carbonate and hydroquinone into the obtained sol system according to the molar ratio of 0.06:1, uniformly stirring for 1.0h, pouring into a beaker with a preservative film, putting into a 45 ℃ oven for gelation, adding ethanol aging solution, and replacing for 7 times, each time for 18 h. And then carrying out carbon dioxide supercritical drying treatment on the wet gel, wherein the reaction temperature is 70 ℃, the pressure in a high-pressure reaction kettle is 10MPa, the drying rate is 7L/min, and the drying time is 10h, so as to obtain the nitrogen-doped carbon aerogel. Soaking the aerogel in a nickel chloride solution with the concentration of 5% for 2.0h, wherein the mass ratio of the aerogel to nickel chloride is 0.2, so as to obtain a Ni-N-C aerogel precursor, and carrying out heat treatment on the Ni-N-C aerogel precursor at the temperature of 600 ℃ in a tubular furnace in the nitrogen atmosphere, wherein the temperature rise speed is 6 ℃/min, and the heat treatment time is 5h, so as to finally obtain the Ni-N-C doped carbon aerogel electrocatalyst. The OER reaction LSV curve of the aerogel material is shown in FIG. 3 at a current density of 10m A/cm-2Then, the overpotential of this sample is 0.34V, and the Tafel slope is 84mV dec-1The specific surface area of the material is 797.6m2(ii)/g, total micropore volume of 0.32cm3/g。
Example 4
Deionized water, pyrocatechol, ethylenediamine and formaldehyde are mixed according to a molar ratio of 50: 1: 6.5: 15, stirring for 25min at 35 ℃, adding sodium carbonate into the obtained sol system according to the molar ratio of the sodium carbonate to catechol of 0.08:1, uniformly stirring for 1.5h, pouring into a beaker with a preservative film, putting into a 60 ℃ oven for gelation, adding ethanol aging solution for replacing for 8 times, and each time for 20 h. The wet gel is then subjected to a dioxygenationAnd (3) performing carbon supercritical drying treatment, wherein the reaction temperature is 80 ℃, the pressure in the high-pressure reaction kettle is 10MPa, the drying rate is 8L/min, and the drying time is 10h, so that the nitrogen-doped carbon aerogel is obtained. Soaking the aerogel in a manganese chloride solution with the concentration of 8% for 3.5h, wherein the mass ratio of the aerogel to manganese chloride is 0.3, so as to obtain a Mn-N-C aerogel precursor, and carrying out heat treatment on the Mn-N-C aerogel precursor at 700 ℃ in an argon atmosphere of a tubular furnace, wherein the heating rate is 7 ℃/min, and the heat treatment time is 3h, so as to finally obtain the Mn-N-C carbon aerogel electrocatalyst. The specific surface area of the material is 792.2m2(ii)/g, total micropore volume of 0.2cm3In the OER reaction, at a current density of 10m A/cm-2Then, the overpotential of this sample is 0.31V, and the Tafel slope is 68mV dec-1。
Example 5
Deionized water, catechol, melamine and benzaldehyde are mixed according to a molar ratio of 60: 1: 9.0.: 20, stirring for 30min at 40 ℃, adding sodium carbonate and catechol into the obtained sol system according to a molar ratio of 0.08:1, uniformly stirring for 2.0h, pouring into a beaker with a preservative film, putting into a 70 ℃ oven to be gelled, adding methanol aging liquid for replacement for 9 times every 24h, and then performing carbon dioxide supercritical drying treatment on the wet gel, wherein the reaction temperature is 90 ℃, the pressure in a high-pressure reaction kettle is 12MPa, the drying rate is 9L/min, and the drying time is 16h, so as to obtain the nitrogen-doped carbon aerogel. Soaking the aerogel in a zinc chloride solution with the concentration of 10% for 5.0h, wherein the mass ratio of the aerogel to the zinc chloride is 0.4, so as to obtain a Zn-N-C carbon aerogel precursor, and carrying out heat treatment on the precursor at 800 ℃ in a tubular furnace under the nitrogen atmosphere, wherein the heating rate is 10 ℃/min, and the heat treatment time is 2h, so as to finally obtain the Zn-N-C aerogel electrocatalyst. The specific surface area of the material is 789.2m2(ii)/g, total micropore volume of 0.2cm3In the OER reaction, at a current density of 10mA/cm-2Then, the overpotential of this sample is 0.32V, and the Tafel slope is 75mV dec-1。

Claims (10)

1. A preparation method of an M-N-C aerogel electrocatalyst comprises the following specific steps:
(1) uniformly mixing deionized water, phenol, aldehyde and a nitrogen-containing compound, and stirring to obtain a sol system;
(2) adding sodium carbonate into the sol system obtained in the step (1) and stirring to obtain nitrogen-doped wet gel;
(3) adding an aging liquid into the wet gel obtained in the step (2), and performing replacement in an oven;
(4) performing carbon dioxide supercritical drying treatment on the wet gel obtained in the step (3) to obtain nitrogen-doped organic aerogel;
(5) soaking the nitrogen-doped organic aerogel obtained in the step (4) in a metal salt solution to obtain a metal and nitrogen-doped M-N-C aerogel precursor;
(6) carrying out heat treatment on the metal and nitrogen-doped M-N-C aerogel precursor obtained in the step (5) in a furnace containing a protective gas atmosphere to obtain an M-N-C aerogel electrocatalyst;
wherein: deionized water, phenol, nitrogen-containing compounds and aldehyde in the step (1) are (30-60): 1: (1.0-10.0): (5-20) uniformly mixing in a molar ratio; the sodium carbonate and the phenol in the step (2) are mixed according to a molar ratio (0.04-0.1): 1, mixing.
2. The preparation method according to claim 1, wherein the phenol in the step (1) is one or more of resorcinol, hydroquinone, catechol or phloroglucinol; the aldehyde is one or more of formaldehyde, acetaldehyde, propionaldehyde or benzaldehyde; the nitrogen-containing compound is one or more of melamine, urea, hydrazine hydrate or ethylenediamine.
3. The method according to claim 1, wherein the stirring in step (1) is carried out at a temperature of 25 to 40 ℃ for 5 to 30 min.
4. The method according to claim 1, wherein the stirring in step (2) is carried out at a temperature of 25 to 40 ℃ for 0.5 to 2 hours.
5. The method according to claim 1, wherein the aging solution in step (3) is one or more selected from methanol, n-pentanol, ethanol and isopropanol.
6. The preparation method according to claim 1, wherein the temperature of the oven in the step (3) is 20-70 ℃, and the number of times of replacement is 3-9 times, each time for 8-24 hours.
7. The method according to claim 1, wherein the carbon dioxide supercritical drying method in the step (4): carbon dioxide is used as a drying medium, the reaction temperature is 40-90 ℃, the pressure in the high-pressure reaction kettle is 8-12 MPa, the drying rate is 5-10L/min, and the drying time is 8-16 h.
8. The method according to claim 1, wherein the metal salt solution in the step (5) is an aqueous solution of a metal salt; the mass concentration of the metal salt solution is 1-10%; wherein the metal salt is one or more of ferric chloride, cobalt chloride, nickel chloride, zinc chloride or manganese chloride.
9. The preparation method according to claim 1, wherein the mass ratio of the nitrogen-doped organic aerogel to the metal salt in the step (5) is 0.02 to 0.4; the soaking time is 0.5-5 h.
10. The method according to claim 1, wherein the protective gas in step (6) is one or a mixture of argon, helium and nitrogen. The heat treatment temperature is 300-800 ℃, the heating rate is 1-10 ℃/min, and the heat treatment heat preservation time is 2-8 h.
CN202210020822.0A 2022-01-10 2022-01-10 Preparation method of M-N-C carbon aerogel electrocatalyst Pending CN114392761A (en)

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