CN113594480B - Heteroatom-codoped non-noble metal-based carbon material and preparation method and application thereof - Google Patents
Heteroatom-codoped non-noble metal-based carbon material and preparation method and application thereof Download PDFInfo
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- CN113594480B CN113594480B CN202110804761.2A CN202110804761A CN113594480B CN 113594480 B CN113594480 B CN 113594480B CN 202110804761 A CN202110804761 A CN 202110804761A CN 113594480 B CN113594480 B CN 113594480B
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- H—ELECTRICITY
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Abstract
The invention belongs to the technical field of catalysts, and particularly relates to a heteroatom-codoped non-noble metal-based carbon material, and a preparation method and application thereof. The material is prepared by the following method: ultrasonically dispersing ferric chloride in ethanol uniformly, adding sodium lignosulfonate, stirring, drying and washing to obtain iron chelated lignin; grinding sodium hypophosphite and iron chelated lignin uniformly, and carrying out pyrolysis reaction to obtain the iron chelated lignin. The preparation method of the invention integrates the active sites of Fe-N-C, FeP, realizes the electrocatalytic oxygen reduction, hydrogen evolution and oxygen evolution reaction simultaneously by utilizing the synergistic effect of the two, and realizes the remarkable improvement of the catalytic activity and stability. The invention combines iron chelated lignin and sodium hypophosphite by using a salt auxiliary strategy to prepare the three-functional non-noble metal-based carbon material capable of catalyzing oxygen reduction, hydrogen evolution and oxygen evolution reactions simultaneously, and solves the problems of high cost and low reserve of noble metal catalysts in the prior art.
Description
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a heteroatom-codoped non-noble metal-based carbon material, and a preparation method and application thereof.
Background
The continuous activation and sustainable development of the current energy problem are urgent, so that the development of novel energy conversion devices such as metal-air batteries and proton exchange membrane fuel cells becomes a research hotspot. The electrocatalysis material is used as a key material of the fuel cell, and the development of the low-cost and high-performance three-function electrocatalyst which can be simultaneously applied to catalytic oxygen reduction, hydrogen evolution and oxygen evolution reactions has important significance for energy conversion devices and the like. However, due to the problem of slow reaction kinetics, only low-inventory, high-price noble metal catalysts are currently used as commercial catalysts, thereby limiting the application of commercial fuel cells. Therefore, the development of low-cost and high-performance non-noble metal electrocatalytic materials is a goal of researchers.
In the development process of non-noble metal electrocatalysts, carbon materials have attracted extensive attention due to their high cost performance, good conductivity, high specific surface area, and good stability. The three-function catalyst can not only avoid side reactions caused by the interaction of various catalysts, but also simplify the design and structure of the electrode. The performance in electrocatalytic oxygen reduction, hydrogen evolution and oxygen evolution reactions has a significant impact on carbon materials. Therefore, the development of a three-functional carbon-based electrocatalyst with high performance for the three key reactions is of great significance. Therefore, the heteroatom-codoped non-noble metal-based carbon material with high activity and high stability, which is simultaneously applied to electrocatalytic oxygen reduction, hydrogen evolution and oxygen evolution reactions, is developed, so that the wide application of the non-noble metal electrocatalyst in the commercial fuel cell is realized, and the method has wide economic benefits and social benefits and has important significance.
Disclosure of Invention
In order to obtain a heteroatom-codoped non-noble metal-based carbon material with high activity and high stability, which is simultaneously applied to electrocatalytic oxygen reduction, hydrogen evolution and oxygen evolution reactions, the invention provides a heteroatom-codoped non-noble metal-based carbon material, and the material realizes three-function electrocatalytic performance.
The invention also aims to provide a preparation method of the heteroatom-codoped non-noble metal-based carbon material, which is simple to operate and solves the problems of high cost and low storage capacity of the noble metal catalyst in the prior art.
The invention also aims to provide application of the heteroatom-codoped non-noble metal-based carbon material in electrocatalytic oxygen reduction, hydrogen evolution and oxygen evolution reactions, and the material has excellent electrocatalytic performance.
In order to solve the technical problems, the invention adopts the following technical scheme:
the invention provides a preparation method of a heteroatom-codoped non-noble metal-based carbon material, which comprises the following steps:
(1) ultrasonically dispersing ferric chloride in ethanol uniformly, adding sodium lignosulfonate, stirring, drying and washing to obtain iron chelated lignin;
(2) uniformly grinding sodium hypophosphite and iron chelated lignin, and carrying out pyrolysis reaction to obtain the heteroatom co-doped non-noble metal-based carbon material.
Further, in the step (1), the concentration of the ferric chloride in the ethanol is 0.025-0.1 g/mL; the mass ratio of the ferric chloride to the sodium lignin sulfonate is 1-3: 1-3.
Further, in the step (1), the power of the ultrasonic wave is 220-; the drying is carried out at 70-90 ℃ for 20-24 h.
Further, in the step (2), the mass ratio of the sodium hypophosphite to the sodium lignosulfonate is 1-3: 0.1.
Further, in the step (2), the sodium hypophosphite is added and then dissolved, and ultrasonic treatment is adopted, wherein the ultrasonic power is 220-280W, and the ultrasonic time is 10-20 min.
The pyrolysis reaction conditions provided by the invention are as follows: raising the temperature to 850-950 ℃ at the heating rate of 5 ℃/min for 2.5-3.5h in the nitrogen atmosphere, reducing the temperature, carrying out acid cleaning for 22-26h by using 1.5-2.5M HCl solution at the temperature of 85-95 ℃, then maintaining for 0.5-1.5h at the temperature of 750-850 ℃ in the ammonia atmosphere, and reducing the temperature to finally obtain the heteroatom-codoped non-noble metal-based carbon material.
The invention provides a heteroatom-codoped non-noble metal-based carbon material prepared by the preparation method.
The invention also provides application of the heteroatom-codoped non-noble metal-based carbon material in the field of electrocatalysis.
The invention has the beneficial effects that:
(1) the preparation method of the invention integrates the active sites of Fe-N-C, FeP, realizes the electrocatalytic oxygen reduction, hydrogen evolution and oxygen evolution reaction simultaneously by utilizing the synergistic effect of the two, and realizes the remarkable improvement of the catalytic activity and stability.
(2) The invention combines iron chelated lignin and sodium hypophosphite by using a salt auxiliary strategy to prepare the three-functional non-noble metal-based carbon material capable of catalyzing oxygen reduction, hydrogen evolution and oxygen evolution reactions simultaneously, and solves the problems of high cost and low reserve of noble metal catalysts in the prior art.
Drawings
Fig. 1 is a scanning electron microscope image of the non-metal-based carbon material prepared in example 1.
FIG. 2 shows ORR (a), OER (b), 0.5M H of examples 1 to 32SO4Linear scan polarization plots of HER at 1M KOH and HER (c).
FIG. 3 is an ORR (a), OER (b), 0.5M H of example 1, comparative examples 1-22SO4Linear scan polarization plots of HER at 1M KOH and HER (c).
Detailed Description
Exemplary embodiments of the present disclosure will be described in more detail below with reference to the accompanying drawings, in order that the present disclosure may be more fully understood and fully conveyed to those skilled in the art. While the exemplary embodiments of the present disclosure are shown in the drawings, it should be understood that the invention is not limited to the embodiments set forth herein.
Example 1
(1) Adding 1.4g of ferric chloride into 20mL of ethanol, performing ultrasonic treatment for 10min under the condition that the power is 280W, uniformly dispersing, adding 2g of sodium lignosulfonate, stirring, drying for 24h at 80 ℃, and washing to obtain iron chelated lignin;
(2) grinding 1.5g of sodium hypophosphite and 0.1g of iron chelated lignin uniformly, heating to 800 ℃ at a heating rate of 5 ℃/min for 2h in a nitrogen atmosphere, cooling, carrying out acid washing with 2M HCl solution at 90 ℃ for 24h, then keeping at 800 ℃ for 1h in an ammonia atmosphere, and cooling to finally obtain the heteroatom co-doped non-noble metal based carbon material.
Scanning electron microscopy of the heteroatom-co-doped non-noble metal-based carbon material prepared in this example is shown in fig. 1, and the results show that the material contains a large number of pores with a diameter of 1 μm, which may be due to the removal of sodium hypophosphite at high temperature, and the porous structure is beneficial to the electrocatalytic performance of the material.
Example 2
(1) Adding 1.4g of ferric chloride into 20mL of ethanol, performing ultrasonic treatment for 10min under the condition that the power is 280W, uniformly dispersing, adding 2g of sodium lignosulfonate, stirring, drying for 24h at 80 ℃, and washing to obtain iron chelated lignin;
(2) grinding 1.0g of sodium hypophosphite and 0.1g of iron chelated lignin uniformly, heating to 800 ℃ at a heating rate of 5 ℃/min for 2h in a nitrogen atmosphere, cooling, carrying out acid washing with 2M HCl solution at 90 ℃ for 24h, then keeping at 800 ℃ for 1h in an ammonia atmosphere, and cooling to finally obtain the heteroatom co-doped non-noble metal based carbon material.
Example 3
(1) Adding 1.4g of ferric chloride into 20mL of ethanol, performing ultrasonic treatment for 10min under the condition that the power is 280W, uniformly dispersing, adding 2g of sodium lignosulfonate, stirring, drying for 24h at 80 ℃, and washing to obtain iron chelated lignin;
(2) grinding 2.0g of sodium hypophosphite and 0.1g of iron chelated lignin uniformly, heating to 800 ℃ at a heating rate of 5 ℃/min for 2h in a nitrogen atmosphere, cooling, carrying out acid washing with 2M HCl solution at 90 ℃ for 24h, then keeping at 800 ℃ for 1h in an ammonia atmosphere, and cooling to finally obtain the heteroatom co-doped non-noble metal based carbon material.
Comparative example 1
(1) Adding 1.4g of ferric chloride into 20mL of ethanol, performing ultrasonic treatment for 10min under the condition that the power is 280W, uniformly dispersing, adding 2g of sodium lignosulfonate, stirring, drying for 24h at 80 ℃, and washing to obtain iron chelated lignin;
(2) raising the temperature of 0.1g of iron-chelated lignin to 800 ℃ at a heating rate of 5 ℃/min for 2h in a nitrogen atmosphere, cooling, carrying out acid washing with 2M HCl solution at 90 ℃ for 24h, then maintaining at 800 ℃ for 1h in an ammonia atmosphere, and cooling to finally obtain the heteroatom-codoped non-noble metal-based carbon material.
Comparative example 2
(1) Adding 1.4g of ferric chloride into 20mL of ethanol, performing ultrasonic treatment for 10min under the condition that the power is 280W, uniformly dispersing, adding 2g of sodium lignosulfonate, stirring, drying for 24h at 80 ℃, and washing to obtain iron chelated lignin;
(2) grinding 1.5g of sodium hypophosphite and 0.1g of iron chelated lignin uniformly, heating to 800 ℃ at a heating rate of 5 ℃/min for 2h in a nitrogen atmosphere, cooling, carrying out acid washing with 2M HCl solution at 90 ℃ for 24h, then keeping at 750 ℃ for 1h in an ammonia atmosphere, and cooling to finally obtain the heteroatom co-doped non-noble metal based carbon material.
Effects of the embodiment
ORR, OER and HER electrocatalytic performance tests were performed on examples 1,2, 3 and comparative examples 1,2 using a three-electrode test system in electrolyte solutions of 0.1M KOH, 1M KOH, 0.5M H2SO4 and 1M KOH, respectively, via Chenghua CHI760E electrochemical workstation.
(one) ORR (FIG. 2a), OER (FIG. 2b), 0.5M H by examples 1-32SO4The linear scanning polarization curves of the lower HER (fig. 2 c) and the HER (fig. 2 d) under 1M KOH show that example 1 shows higher catalytic activity, indicating that the amount of sodium hypophosphite has a significant effect on the catalytic performance of the material.
(II) ORR (FIG. 3a), OER (FIG. 3b), 0.5M H by example 1 and comparative examples 1,22SO4The linear scanning polarization curves of the lower HER (fig. 3 c) and the HER (fig. 3 d) under 1M KOH show that the example 1 still shows the optimal catalytic activity, which indicates that the doping of phosphorus element and the pyrolysis temperature of 800 ℃ have stronger influence on the performance of the material.
Claims (7)
1. A preparation method of a heteroatom-codoped non-noble metal-based carbon material is characterized by comprising the following steps:
(1) ultrasonically dispersing ferric chloride in ethanol uniformly, adding sodium lignosulfonate, stirring, drying and washing to obtain iron chelated lignin;
(2) uniformly grinding sodium hypophosphite and iron chelated lignin, and obtaining a heteroatom co-doped non-noble metal-based carbon material through a pyrolysis reaction;
the pyrolysis reaction conditions are as follows: heating to 850-class 950 ℃ at the heating rate of 5 ℃/min for 2.5-3.5h in the nitrogen atmosphere, cooling, performing acid cleaning with 1.5-2.5M HCl solution at the temperature of 85-95 ℃ for 22-26h, then maintaining at the temperature of 750-class 850 ℃ for 0.5-1.5h in the ammonia atmosphere, and cooling to finally obtain the heteroatom-codoped non-noble metal-based carbon material with the porous structure;
the non-noble metal-based carbon material has Fe-N-C, FeP active sites, and electrocatalytic oxygen reduction, hydrogen evolution and oxygen evolution reactions are simultaneously realized by utilizing the synergistic effect of the Fe-N-C, FeP active sites.
2. The method according to claim 1, wherein in the step (1), the concentration of the ferric chloride in the ethanol is 0.025 to 0.1 g/mL; the mass ratio of the ferric chloride to the sodium lignin sulfonate is 1-3: 1-3.
3. The preparation method according to claim 1 or 2, wherein in the step (1), the power of the ultrasound is 220- & 280W, and the ultrasound time is 10-20 min; the drying is carried out at 70-90 ℃ for 20-24 h.
4. The preparation method according to claim 1, wherein in the step (2), the mass ratio of the sodium hypophosphite to the sodium lignosulfonate is 1-3: 0.1.
5. The preparation method according to claim 1, wherein in the step (2), the sodium hypophosphite is added and then dissolved, and ultrasonic treatment is adopted, wherein the power of ultrasonic treatment is 220-280W, and the ultrasonic time is 10-20 min.
6. A heteroatom-codoped non-noble metal-based carbon material prepared by the preparation method as set forth in any one of claims 1 to 5.
7. Use of the heteroatom co-doped non-noble metal-based carbon material according to claim 6 in the field of electrocatalysis.
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| CN110433846A (en) * | 2019-08-22 | 2019-11-12 | 浙江工业大学 | A kind of phosphorus doping nitridation cobalt nanowire elctro-catalyst and its preparation method and application |
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