CN114709427A - Preparation method of nitrogen-sulfur co-doped hierarchical porous carbon catalyst with acid-alkali-oxygen-resistant reduction catalysis performance - Google Patents

Preparation method of nitrogen-sulfur co-doped hierarchical porous carbon catalyst with acid-alkali-oxygen-resistant reduction catalysis performance Download PDF

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CN114709427A
CN114709427A CN202210478388.0A CN202210478388A CN114709427A CN 114709427 A CN114709427 A CN 114709427A CN 202210478388 A CN202210478388 A CN 202210478388A CN 114709427 A CN114709427 A CN 114709427A
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sulfur
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高书燕
王首婷
刘旭坡
王奎
王坤
赵亚岭
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Henan Normal University
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    • 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
    • H01M4/8605—Porous electrodes
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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Abstract

The invention discloses a preparation method of a nitrogen-sulfur co-doped hierarchical pore carbon catalyst with acid, alkali, oxygen reduction catalysis resistance, and belongs to the technical field of preparation of heteroatom-doped hierarchical pore carbon-oxygen reduction catalysts. According to the invention, the biomass waste orange leaf powder is used as a carbon precursor, and a strategy of decomposing ammonium chloride by melting zinc oxide is adopted to successfully synthesize the nitrogen-sulfur co-doped hierarchical pore carbon catalyst with acid, alkali, oxygen and reduction catalysis resistance. The preparation method has the outstanding advantages of simplicity, environmental protection, low cost and the like, not only provides an idea for ZABs air electrode research, but also provides a new attempt for the treatment of the byproduct ammonium chloride in the soda industry.

Description

Preparation method of nitrogen-sulfur co-doped hierarchical porous carbon catalyst with acid-alkali-oxygen-resistant reduction catalysis performance
Technical Field
The invention belongs to the technical field of preparation of heteroatom-doped hierarchical pore carbon oxygen reduction catalysts, relates to a cathode catalyst of a zinc-air battery or a fuel cell, and particularly relates to a preparation method of a nitrogen-sulfur co-doped hierarchical pore carbon catalyst with acid, alkali, oxygen reduction catalysis resistance performance.
Background
Currently, China is facing the challenges of unreasonable energy structure, high fossil fuel ratio and the like, and needs to construct a novel energy development pattern with new energy as a main body, firmly anchor the 'double-carbon' target and move a green low-carbon development way. As one of electrochemical energy storage devices, Zinc-Air batteries (ZABs) have the advantages of low cost, environmental protection, high theoretical energy density and the like, and have wide application prospects in the fields of electronic products, new energy power generation and energy storage, electric automobiles, portable power supplies and the like. However, in the case of ZAB, the cathode undergoes Oxygen reduction (ORR), which is a process that has low solubility of Oxygen in water, difficult adsorption on the surface of the air electrode, and large hydrogen-Oxygen bond energy, and is not easily broken, so that the cathode kinetic process is relatively slow. At present, noble metals and alloys thereof are widely applied to ZAB cathodes, but the noble metals and alloys thereof are high in price and scarce in resources, so that the large-scale application is hindered. Therefore, it is necessary to find a catalyst with low cost, wide sources and high catalytic activity.
Heteroatom-doped carbon-based materials are attracting attention because of their excellent electrical conductivity, catalytic activity, and durability. The synergy of heteroatom co-doping and hierarchical structure is considered to be one of the most promising approaches to achieve excellent ORR performance. The hierarchical uniform multi-level pores provide transmission channels for oxygen and water, which are important factors influencing the catalytic activity of oxygen reduction. The most common methods of building pore structures are physical activation, which is partial gasification by oxidation of carbon by an oxidizing gas (e.g., steam and air), and chemical activation, which is often accomplished by a chemical reaction between a carbon precursor and an added chemical reagent. The commonly used chemical pore-forming agents in the present research are KOH and H3PO4、NaNH2And ZnCl2Etc., and what is obtained by activation with the above reagents is microporesThe carbon material with the main structure can provide abundant reaction active sites, contributes to specific surface area, and is not beneficial to the transmission process of substances and ions.
In addition, in recent years, the demand of soda ash is continuously and rapidly increased, so that the storage amount of ammonium chloride which is a reaction byproduct is increased, but the application of ammonium chloride is limited, and therefore, a proper treatment mode for changing waste into valuable is urgently needed. The process of generating ammonia gas and hydrogen chloride by thermal decomposition of ammonium chloride is a reversible chemical reaction and can be used for activating carbon materials, but the ammonium chloride is easy to sublimate and is often accompanied with the occurrence of reverse reaction, so that the complete and stepwise decomposition of the ammonium chloride is not facilitated, and the preparation of the hierarchical uniform multi-level pore material is influenced, so that the decomposed ammonia gas or hydrogen chloride can be specially treated by selecting acidic or alkaline substances, and the distribution of the pore structure is contributed. In addition, in the activation of the non-metallic carbon material, based on the particularity of the physical boiling point of zinc metal, it is changed into a gas state at about 900 ℃ to leave a microporous structure, which has been extensively studied by researchers. Therefore, the invention adopts the strategy of decomposing ammonium chloride by melting zinc oxide, and in view of the amphoteric property of nano zinc oxide, the nano zinc oxide can be combined with decomposed hydrogen chloride under high-temperature melting to release ammonia gas, so that the ammonia gas contributes to the hierarchical structure of the carbon material, and the oxygen reduction performance of the carbon material is improved.
Disclosure of Invention
The invention solves the technical problem of providing a preparation method of a nitrogen-sulfur co-doped hierarchical porous carbon catalyst with acid and alkali oxygen reduction catalysis resistance, which has simple process and low cost.
The invention adopts the following technical scheme for solving the technical problems, and the preparation method of the nitrogen-sulfur co-doped hierarchical pore carbon catalyst with the acid-alkali-oxygen reduction catalysis performance is characterized by comprising the following specific steps:
step S1: dissolving ammonium chloride in ultrapure water, sequentially dispersing the tangerine leaf powder and the nano zinc oxide in the ammonium chloride solution, violently stirring for 30min, and drying in an oven at 80 ℃ to obtain a material A;
step S2: fully grinding the material A to uniform powder, collecting the powder, placing the powder in a corundum boat, placing the corundum boat in a tube furnace for high-temperature annealing, and performing high-temperature annealing at 5 ℃ for min in a continuous nitrogen atmosphere-1Heating from 25 deg.C to 400 deg.C for 60min, and heating at 5 deg.C for 5 min-1Heating to 900 ℃ at the heating rate, keeping the temperature for 60min, and naturally cooling to room temperature to obtain a material B;
step S3: transferring the material B into a container, adding an acid solution to soak for 24h, washing with high-purity water until the filtrate is neutral, and then placing the filtrate in a 60 ℃ forced air drying oven to dry for 12h to obtain a target product, namely the nitrogen-sulfur co-doped hierarchical porous carbon catalyst with the acid and alkali oxygen reduction resistance catalytic performance, wherein N, S contents in the nitrogen-sulfur co-doped hierarchical porous carbon catalyst are respectively 4.56at.% and 0.17at.%, and the specific surface area reaches 2332.19m2 g-1And the nitrogen-sulfur co-doped carbon catalyst has excellent acid-base-resistant oxygen reduction catalytic activity, stability and methanol resistance.
Further preferably, the mass ratio of the ammonium chloride to the orange leaf powder to the nano zinc oxide in the step S1 is 0.5-0.6:1: 5-6.
Further preferably, the inert gas in step S2 is one or more of nitrogen or argon.
Further preferably, the acidic solution in step S3 is a dilute hydrochloric acid solution with a concentration of 2M.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1. according to the invention, rich trace element N, S in biomass (tangerine leaf powder) is induced to be doped into a carbon skeleton in situ through a high-temperature pyrolysis process, and N element is additionally introduced while ammonium chloride is decomposed to be used as a template agent, so that more active sites are promoted to be formed, and the electrochemical performance of the prepared doped carbon material is enhanced. In addition, the problems that the doping amount of heteroatoms (such as nitrogen and sulfur) is very small, the configuration of the heteroatoms in the material is unstable, the heteroatoms are easy to fall off from a carbon substrate, the preparation process is complex, the cost is high and the like in a carbon material prepared by a post-doping method are avoided to a certain extent.
2. The strategy for the zinc oxide to decompose ammonium chloride in a melting way is characterized in that the specific pyrolysis mechanism is as follows: (1) when the temperature is 220 ℃ from room temperature, the moisture (free water and crystal water) on the surface of the material is mainly reduced, and a little ammonium chloride is decomposed into zinc oxide and ammonium chloride, so that the process provides a microporous structure for the carbon material; (2) at the temperature of 220 ℃ and 648 ℃, zinc oxide is used as amphoteric oxide and is combined with hydrogen chloride decomposed by ammonium chloride under the condition of high-temperature melting to release ammonia gas, the ammonia gas and the hydrogen chloride are prevented from being combined again in a reverse reaction when encountering cold, and in addition, the stage is accompanied with the pyrolysis of carbon precursor lignin, cellulose and hemicellulose; (3) 648 ℃ and 900 ℃, zinc oxide is reduced by carbon to release CO or CO2And (3) bubbling the gas away from the medium and large pores mainly generated in the carbon material, and then enabling the zinc metal to reach the boiling point of the zinc metal at about 900 ℃ and become gaseous to escape, so that a microporous structure is left for the carbon material. The microporous structure can not only contribute to the specific surface area of the carbon material and provide more active sites, but also effectively adsorb oxygen molecules and improve the interaction with catalytic active sites; the meso-macroporous structure and the macroporous structure provide a transmission channel for oxygen reduction reaction. In summary, the pyrolysis process provides a beneficial guarantee for the hierarchical pore structure and accelerates the transport of the substance molecules and electrons, thereby promoting the occurrence of oxygen reduction reactions. The finally formed hierarchical pore structure is beneficial to the mass transfer process in the electrochemical ORR reaction, and meanwhile, the specific surface area of the nitrogen-sulfur co-doped carbon catalyst is increased, so that the exposure of active sites such as N, S is facilitated, and the ORR catalytic performance of the obtained catalyst is further enhanced.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) electron micrograph (a), a Transmission Electron Microscope (TEM) electron micrograph (b-c), and a High Resolution Transmission Electron Microscope (HRTEM) electron micrograph (d) of the nitrogen-sulfur co-doped hierarchical pore carbon catalyst E1 having the acid and alkali oxygen reduction resistance catalytic property prepared in example 1;
FIG. 2 shows N of the nitrogen-sulfur co-doped hierarchical porous carbon catalyst E1 with acid and alkali oxygen reduction resistant catalytic performance prepared in example 12Adsorption and desorption isotherm (N)2an adsorption/desorption isothiazolm) map and a Pore Size Distribution (PSD) map;
FIG. 3 is a thermogravimetric-differential thermogravimetric (TG-DTG) graph of the nitrogen-sulfur co-doped hierarchical porous carbon catalyst E1 with acid and alkali oxygen reduction catalysis resistance prepared in example 1;
FIG. 4 is a graph of basic rotating-disk-ring electrode (RRDE) polarization curves/ORR activity for the nitrogen-sulfur co-doped hierarchical porous carbon catalyst E1 with acid and alkali-oxygen reduction catalytic performance and a commercial reference Pt/C prepared in example 1;
FIG. 5 is a graph of basic ORR Cyclic Voltammetry (CV) curves/performance of the nitrogen-sulfur co-doped hierarchical porous carbon catalyst E1 having acid and base oxygen reduction resistant catalytic performance prepared in example 1 and a commercial reference Pt/C;
FIG. 6 is a graph of basic ORR Cyclic Voltammetry (CV) curves/methanol resistance performance of the nitrogen-sulfur co-doped hierarchical porous carbon catalyst E1 having acid and base oxygen reduction resistance catalytic performance prepared in example 1 and a commercial reference Pt/C;
FIG. 7 is a graph of polarization curves/ORR activity of the nitrogen-sulfur co-doped hierarchical porous carbon catalyst E1 with acid and base oxygen reduction catalytic performance prepared in example 1 and a commercially-referenced Pt/C acidic rotating-disc-ring electrode (RRDE);
FIG. 8 is a graph of acidic ORR Cyclic Voltammetry (CV) curves/stabilities of the nitrogen-sulfur co-doped hierarchical porous carbon catalyst E1 having acid and base oxygen reduction catalytic performance prepared in example 1 and a commercial reference Pt/C;
fig. 9 is a graph of acidic ORR Cyclic Voltammetry (CV) curves/methanol resistance performance of the nitrogen-sulfur co-doped hierarchical pore carbon catalyst E1 with acid and base oxygen reduction catalytic performance prepared in example 1 and a commercial reference Pt/C.
Detailed Description
The present invention is described in further detail below with reference to examples, but it should not be construed that the scope of the above subject matter of the present invention is limited to the following examples, and that all the technologies realized based on the above subject matter of the present invention belong to the scope of the present invention.
Example 1
Step S1: dissolving 0.53g of ammonium chloride in 50mL of ultrapure water, sequentially dispersing 1g of the tangerine seed leaf powder and 5.7g of nano zinc oxide in the ammonium chloride solution, violently stirring for 30min, and drying in an oven at 80 ℃ for 12h to obtain a material A1;
step S2: fully grinding the material A1 to uniform powder, collecting the powder, placing the powder in a corundum boat, placing the corundum boat in a tube furnace for high-temperature annealing, and performing high-temperature annealing at 5 ℃ for min in a continuous nitrogen atmosphere-1Heating from 25 deg.C to 400 deg.C at a heating rate of 60min, and maintaining at 5 deg.C for 5 min-1Heating at a heating rate to 900 ℃ and keeping for 60min, then naturally cooling to room temperature to obtain a material B1, wherein amphoteric oxide nano zinc oxide in a high-temperature molten state can be combined with hydrogen chloride released by ammonium chloride decomposition to release ammonia gas, a hierarchical pore structure is provided for the carbon material, meanwhile, heteroatom N is additionally introduced by taking the ammonium chloride as a template agent, so that more catalytic active sites are introduced, the hierarchical porous carbon material with high specific surface area, rich defects and high nitrogen and sulfur doping levels is successfully prepared, and the obtained carbon material has excellent acid and alkali resistance ORR catalytic activity, stability and methanol resistance;
step S3: and transferring the material B1 to a container, adding a dilute hydrochloric acid solution with the concentration of 2M, soaking for 24h, washing with high-purity water until the filtrate is neutral, and then placing the filtrate in a forced air drying oven at 60 ℃ for drying for 12h to obtain the target product, namely the nitrogen-sulfur co-doped hierarchical porous carbon catalyst E1 with the acid and alkali oxygen reduction catalysis resistance performance.
ORR activity test procedure: weighing a certain amount of nitrogen-sulfur co-doped hierarchical pore carbon catalyst E1 which is ground into powder and has the catalytic performance of acid-base-oxygen reduction by using an electronic balance, uniformly mixing the nitrogen-sulfur co-doped hierarchical pore carbon catalyst E1 with Nafion and high-purity water with the mass fraction of 0.1wt%, and performing ultrasonic treatment for several minutes to finally obtain a uniform ink-like solution. Polishing with 0.05 μm alumina in an ultrasonic processThe method comprises the following steps of grinding the surface of the glassy carbon electrode to be bright and free of any stain and scratch, placing the electrode in an ultrasonic instrument for ultrasonic treatment for a few minutes, and finally drying the surface of the electrode with air for later use. And transferring a proper amount of ultrasonically-good ink-like active substances to the glassy carbon electrode by using a liquid transfer gun, and then airing at room temperature to finish the preparation of the working electrode. All electrochemical tests used a three-electrode system. In the test of the rotating disk-ring disk electrode (RRDE), the working electrode is a 5mm diameter glassy carbon electrode with a platinum ring coated with a certain volume and a certain concentration of active substance (the prepared ink-like active substance), the reference electrode is an Hg/HgO and saturated calomel electrode, and the counter electrode is a platinum sheet (1 cm)2) The electrolyte of the electrode is 0.1M KOH aqueous solution or 0.5M H2SO4The aqueous solution is used for the ORR catalytic activity test, and the scanning speed is 10mV s when the aqueous solution is tested in a saturated nitrogen/oxygen atmosphere-1The rotation speed was 1600rpm, and the scanning ranges were 0.07-1.07V (vs. RHE) and 0.17-1.27V (vs. RHE). In the Cyclic Voltammetry (CV) test, the working electrode was a 3mm diameter glassy carbon electrode coated with a volume of active material (prepared as described above in the form of an ink) at a concentration, the reference electrode was again a Hg/HgO and saturated calomel electrode, the counter electrode was again a platinum plate electrode, and the electrolyte was 0.1M KOH in water and 0.5M H M KOH in water2SO4The aqueous solution is saturated with oxygen or nitrogen in advance, and the scanning speed is still 10mV s when testing-1The scanning ranges are 0.07-1.07V (vs. RHE, basic) and 0.17-1.27V (vs. RHE, acidic).
The basic ORR catalytic performance of the E1 sample prepared in example 1 was as follows: as shown in FIG. 4, the half-wave potentials of the E1 sample and the commercial reference Pt/C were 0.85V (vs. RHE) and 0.86V (vs. RHE), respectively, at 1600rpm, indicating that the half-wave potential of the E1 sample is equivalent to that of the commercial reference Pt/C, and it is fully demonstrated that the E1 sample has ORR activity equivalent to that of the commercial Pt/C; the limiting current densities of the E1 sample and the commercial reference Pt/C were 5.2mA cm-2And 6.5mA cm-2The E1 sample was shown to have a conductivity comparable to commercial Pt/C.
The electrochemical basic CV performance of the E1 sample prepared in example 1 was as follows: as shown in fig. 5, with the stability plots of the E1 sample and the commercial reference Pt/C, it can be seen that the performance of the E1 sample is more stable after 5000 cycles; as shown in FIG. 6, from the graphs of the methanol resistance of the E1 sample and the commercial reference Pt/C, it can be seen that the performance of the E1 sample is hardly disturbed after the addition of the methanol solution, while the peak potential and the peak current of the commercial reference Pt/C are reversed, and it is known that the methanol oxidation reaction occurs, whereby the stability and the methanol resistance of the E1 sample are superior to those of the commercial reference Pt/C.
The acidic ORR catalytic performance of the E1 sample prepared in example 1 was as follows: as shown in FIG. 7, the half-wave potentials of the E1 sample and the commercial reference Pt/C were 0.67V (vs. RHE) and 0.76V (vs. RHE), respectively, at 1600rpm, indicating that the E1 sample had a slightly inferior half-wave potential to the commercial reference Pt/C; whereas the limiting current densities of the Pt/C of the E1 sample and the commercial reference were 6.6mA cm-2And 5.8mA cm-2Indicating that the E1 sample had good conductivity.
The electrochemical acidic CV performance of the E1 sample prepared in example 1 was as follows: as shown in fig. 8, with the acidic ORR cycle stability plots for the E1 sample and the commercial reference Pt/C, it can be seen that the performance of the E1 sample is more stable after 5000 cycles; as shown in fig. 9, from the methanol durability graphs of the E1 sample and the commercial reference Pt/C, it can be seen that the performance of the E1 sample is hardly disturbed after the addition of the methanol solution, and thus it can be obtained that the stability and methanol resistance of the E1 sample are superior to the commercial reference Pt/C.
While the foregoing embodiments have described the general principles, features and advantages of the present invention, it will be understood by those skilled in the art that the present invention is not limited thereto, and that the foregoing embodiments and descriptions are only illustrative of the principles of the present invention, and various changes and modifications can be made without departing from the scope of the principles of the present invention, and these changes and modifications are within the scope of the present invention.

Claims (4)

1. A preparation method of a nitrogen-sulfur co-doped hierarchical pore carbon catalyst with acid-base-oxygen resistant reduction catalysis performance is characterized by comprising the following specific steps:
step S1: dissolving ammonium chloride in ultrapure water, sequentially dispersing the tangerine leaf powder and the nano zinc oxide in the ammonium chloride solution, violently stirring for 30min, and drying in an oven at 80 ℃ to obtain a material A;
step S2: fully grinding the material A to uniform powder, collecting the powder, placing the powder in a corundum boat, placing the corundum boat in the corundum boat for high-temperature annealing, and performing high-temperature annealing at 5 ℃ for min in a continuous nitrogen atmosphere-1Heating from 25 deg.C to 400 deg.C for 60min, and heating at 5 deg.C for 5 min-1Heating to 900 ℃ at the heating rate, keeping the temperature for 60min, and naturally cooling to room temperature to obtain a material B;
step S3: transferring the material B into a container, adding an acid solution to soak for 24h, washing with high-purity water until the filtrate is neutral, and then placing the filtrate in a 60 ℃ forced air drying oven to dry for 12h to obtain a target product, namely the nitrogen-sulfur co-doped hierarchical porous carbon catalyst with the acid and alkali oxygen reduction resistance catalytic performance, wherein N, S contents in the nitrogen-sulfur co-doped hierarchical porous carbon catalyst are respectively 4.56at.% and 0.17at.%, and the specific surface area reaches 2332.19m2 g-1And the nitrogen-sulfur co-doped carbon catalyst has excellent acid-base-oxygen-resistant reduction catalytic activity, stability and methanol resistance.
2. The preparation method of the nitrogen-sulfur co-doped hierarchical porous carbon catalyst with the catalytic performance of acid-base-oxygen reduction according to claim 1, characterized in that: in the step S1, the mass ratio of the ammonium chloride to the orange leaf powder to the nano zinc oxide is 0.5-0.6:1: 5-6.
3. The preparation method of the nitrogen-sulfur co-doped hierarchical porous carbon catalyst with the catalytic performance of acid-base-oxygen reduction according to claim 1, characterized in that: in step S2, the inert gas is one or more of nitrogen or argon.
4. The preparation method of the nitrogen-sulfur co-doped hierarchical porous carbon catalyst with the catalytic performance of acid-base-oxygen reduction according to claim 1, characterized in that: the acidic solution in step S3 is a dilute hydrochloric acid solution with a concentration of 2M.
CN202210478388.0A 2022-05-05 2022-05-05 Preparation method of nitrogen-sulfur co-doped hierarchical porous carbon catalyst with acid-alkali-oxygen-resistant reduction catalysis performance Pending CN114709427A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116190686A (en) * 2023-03-21 2023-05-30 常州大学 Preparation method and application of in-situ activated furfural residue and nitrogen-sulfur co-doped porous carbon catalyst

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116190686A (en) * 2023-03-21 2023-05-30 常州大学 Preparation method and application of in-situ activated furfural residue and nitrogen-sulfur co-doped porous carbon catalyst
CN116190686B (en) * 2023-03-21 2024-03-26 常州大学 Preparation method and application of in-situ activated furfural residue and nitrogen-sulfur co-doped porous carbon catalyst

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