阅读说明：本技术 一种聚酯碳化制备而成的氮掺杂碳泡沫及其制备方法 (Nitrogen-doped carbon foam prepared by carbonizing polyester and preparation method thereof ) 是由 龚江 白慧颖 刘宁 郝亮 牛冉 于 2020-12-14 设计创作，主要内容包括：本发明属于氮掺杂碳泡沫技术领域,更具体地,涉及一种聚酯碳化制备而成的氮掺杂碳泡沫及其制备方法。本发明制备方法包括以下步骤：(1)将聚酯材料、交联剂和熔融盐混合均匀获得聚酯-交联剂-熔融盐混合物,所述交联剂为多氨基化合物；(2)将所述聚酯-交联剂-熔融盐混合物加热至碳化温度得到碳化产物,将碳化产物酸洗除去熔融盐,可获得氮掺杂碳泡沫。本发明交联剂的引入促进了聚酯的交联反应,有效地降低碳化温度,而低熔点熔融盐催化剂的存在可以消除交联结构中的部分弱的化学键生成二氧化碳和水蒸气等小分子产物,这些降解产物充当原位发泡剂的效果,从而提高了碳化过程中聚酯的利用率,在废弃聚酯回收利用方面有较大的应用潜力。(The invention belongs to the technical field of nitrogen-doped carbon foam, and particularly relates to nitrogen-doped carbon foam prepared by carbonizing polyester and a preparation method thereof. The preparation method comprises the following steps: (1) uniformly mixing a polyester material, a cross-linking agent and molten salt to obtain a polyester-cross-linking agent-molten salt mixture, wherein the cross-linking agent is a polyamino compound; (2) and heating the polyester-crosslinking agent-molten salt mixture to a carbonization temperature to obtain a carbonized product, and pickling the carbonized product to remove the molten salt to obtain the nitrogen-doped carbon foam. The introduction of the cross-linking agent promotes the cross-linking reaction of the polyester, effectively reduces the carbonization temperature, and the existence of the low-melting-point molten salt catalyst can eliminate partial weak chemical bonds in a cross-linking structure to generate small molecular products such as carbon dioxide, water vapor and the like, and the degradation products have the effect of serving as in-situ foaming agents, so that the utilization rate of the polyester in the carbonization process is improved, and the polyester has great application potential in the aspect of recycling of waste polyester.)

1. The preparation method for preparing nitrogen-doped carbon foam by carbonizing polyester is characterized by comprising the following steps of:

(1) uniformly mixing a polyester material, a cross-linking agent and molten salt to obtain a polyester-cross-linking agent-molten salt mixture, wherein the cross-linking agent is a polyamino compound;

(2) and heating the polyester-crosslinking agent-molten salt mixture to a carbonization temperature to obtain a carbonized product, and pickling the carbonized product to remove the molten salt to obtain the nitrogen-doped carbon foam.

2. The method according to claim 1, wherein the crosslinking agent is one or a mixture of melamine and urea.

3. The method according to claim 1 or 2, wherein the polyester material is one or more of polyethylene terephthalate, polycarbonate, polybutylene terephthalate, polycaprolactone, polydiallyl terephthalate, polyparaxybenzoate, polyvinyl acetate, polymethyl methacrylate, and polyurethane.

4. The method of claim 3, wherein the polyester material is a waste polyester material.

5. The method according to claim 1, wherein the molten salt is any one of a mixed salt of sodium chloride and zinc chloride, a mixed salt of potassium chloride and zinc chloride, and a mixed salt of lithium chloride and zinc chloride.

6. The method of claim 5, wherein the carbonization temperature is 250 ℃ to 400 ℃, preferably 260 ℃ to 380 ℃, and the temperature increase rate is 2 ℃/min to 30 ℃/min, more preferably 5 ℃/min to 20 ℃/min.

7. The production method according to claim 1, wherein the mass fraction of the polyester in the polyester-crosslinking agent-molten salt mixture is 5% to 95%.

8. The method according to claim 7, wherein the polyester is 18 to 40 mass%, the crosslinking agent is 8 to 25 mass%, and the molten salt is 40 to 67 mass%.

9. The method for preparing the compound of claim 1, wherein the acid washing is performed by soaking in 0.1-1mol/L hydrochloric acid for 1 hour.

10. A nitrogen-doped carbon foam produced by carbonizing a polyester, which is produced by the production method according to any one of claims 1 to 9.

Technical Field

The invention belongs to the technical field of nitrogen-doped carbon foam, and particularly relates to nitrogen-doped carbon foam prepared by carbonizing polyester and a preparation method thereof.

Background

The carbon foam has the advantages of low density, high strength, high specific modulus, high thermal conductivity, low expansion coefficient, good friction performance, good impact resistance, stable size and the like. The highest theoretical temperature of carbon foam is 2600 ℃, which is one of the most promising high temperature materials. The starting material for the carbon foam is typically polyester. Polyester is used as common plastic in life, and is widely applied to product packaging, such as beverage bottles and the like. The carbon content of polyesters is generally high, easy to recover and extremely inexpensive and readily available. Common methods for preparing carbon foam using polyester as a carbon source include a supercritical method and a template method. For example, Michio Inagaki et al prepared carbon foam using polyurethane foam as a template material and polyimide resin as a carbon precursor. Firstly, carrying out imidization reaction at 200 ℃ to obtain polyurethane/polyimide composite foam, then heating to more than 400 ℃ to obtain polyimide foam, and heating to more than 800 ℃ to obtain carbon foam. At 1000 c, the carbon foam is graphitized and at 3000 c the heat treatment maintains the graphite properties. Such Carbon foams can be applied to adsorb water vapor around the environment or as a substrate for a photocatalyst, anatase titanium dioxide (Michio Inagaki, Jieshan Qiu, Quangui Guo, Carbon foam: Preparation and application, Carbon 2015,87, 128-152). The method has the disadvantages of harsh preparation conditions, high carbonization temperature and complex process.

M. karthik et al prepared interconnected graphitized macroporous carbon foams with uniform mesoporous walls by hydrothermal method, they prepared graphitized structures of carbon foams by using polyurethane foam and Pluronic F127 as sacrificial polymer and mesoporous guide template, respectively, and iron as catalyst, and by using catalytic graphitization method. Carbon foams have been found to have high surface area, high open cell content, low density, good mechanical strength and high electrical conductivity, with many potential applications (m. karthik, a. faik, s. doppeu, v. roddations, b.d' ageno, a single address for the implementation of interconnected patterned macro foams with inorganic pores by using a hydrothermatic method, Carbon 2015,87, 434-. The disadvantages of this process are the need to use high-pressure reactors, the high requirements made of the equipment and the dangers of the experimental process.

CN108400023A discloses a three-dimensional nitrogen-doped carbon foam composite electrode material and a preparation method thereof, firstly, ferric chloride and hydrochloric acid are added into deionized water and fully mixed; then, immersing melamine foam in the melamine foam, adding a certain amount of aniline monomer, stirring for 10-24h at 20-90 ℃, washing and drying to obtain a product; and finally, calcining the obtained product to obtain the three-dimensional nitrogen-doped carbon foam composite electrode material. The preparation method is simple and reliable, has low cost, is not environment-friendly enough, and has an improvement space.

CN111977656A discloses an MXene/nitrogen-doped carbon foam composite material with a 3D porous neuron-like structure and a preparation method thereof, specifically 1) preparing an MXene colloidal dispersion liquid by a chemical liquid phase etching method: dissolving lithium fluoride in hydrochloric acid to obtain a lithium fluoride solution, uniformly stirring, and slowly adding Ti₃AlC₂Stirring for 24h at 45 ℃, washing and centrifuging by using deionized water, collecting precipitates, ultrasonically dispersing the obtained precipitates in water, centrifuging the obtained dispersion liquid, and taking supernatant liquid to obtain MXene colloid dispersion liquid; 2) preparing MXene/nitrogen-doped carbon foam composite material: completely soaking the melamine formaldehyde resin foam in the MXene colloidal dispersion liquid obtained in the step 1), then freeze-drying the soaked melamine formaldehyde resin foam, putting the melamine formaldehyde resin foam in a tubular furnace for pyrolysis, and naturally cooling to room temperature to obtain the MXene/nitrogen-doped carbon foam composite material with the 3D porous neuron structure. The nitrogen-doped carbon foam obtained by the technical scheme has more contact sites, promotes the permeation of electrolyte, provides an effective channel for the transmission of ions in the electrode,the transfer of ions is accelerated, but the method is complicated and the production efficiency is not high enough.

In conclusion, the prior art still lacks a preparation method of nitrogen-doped carbon foam with the advantages of simple process, low energy consumption, high production efficiency, greenness, sustainability and the like.

Disclosure of Invention

In view of the above drawbacks of the prior art, the present invention provides a simple, effective and inexpensive method for preparing nitrogen-doped carbon foam by low-temperature carbonization of polyester. Firstly, polyester is mixed with a crosslinking agent containing a polyamino compound and a low-melting-point molten salt, and then the mixture is heated and carbonized, so that the carbonization temperature of the polyester is reduced, and the utilization rate of the polyester in the carbonization process is improved. When the cross-linking agent exists, the cross-linking agent can generate chemical bonds with linear polyester molecules generated by breakage, so that the linear molecules are connected with each other to form a network structure. The molten salt with low melting point is used for dehydration and foaming. Therefore, the technical problems of high energy consumption, complex preparation process and the like caused by high carbonization temperature in the conventional preparation of nitrogen-doped carbon foam by polyester carbonization are solved.

In order to achieve the above objects, according to one aspect of the present invention, there is provided a method for preparing nitrogen-doped carbon foam by carbonizing polyester, comprising the steps of:

(1) uniformly mixing a polyester material, a cross-linking agent and molten salt to obtain a polyester-cross-linking agent-molten salt mixture, wherein the cross-linking agent is a polyamino compound;

(2) and heating the polyester-crosslinking agent-molten salt mixture to a carbonization temperature to obtain a carbonized product, and pickling the carbonized product to remove the molten salt to obtain the nitrogen-doped carbon foam.

The polyester material is firstly cracked and then has crosslinking reaction with the crosslinking agent of the polyamino compound. Typically, when polyethylene terephthalate (PET) is used as the polyester starting material and melamine is used as the crosslinking agent, the crosslinking reaction route is as follows.

And (3) performing a crosslinking reaction to generate a formula (4), taking water and carbon dioxide as byproducts to serve as a foaming agent, and changing the formula (4) into a formula (5) under the action of molten salt to obtain the nitrogen-doped carbon foam. According to the invention, the nitrogen-doped carbon foam with high added value is obtained by simultaneously carbonizing the polyester, the cross-linking agent and the molten salt. The introduction of the cross-linking agent promotes the cross-linking reaction of the polyester, the carbonization temperature is effectively reduced, the existence of the low-melting-point molten salt catalyst can eliminate partial weak chemical bonds in a cross-linking structure to generate micromolecule products such as carbon dioxide, water vapor and the like, and the micromolecule products can serve as the effect of an in-situ foaming agent.

Preferably, the cross-linking agent is one or a mixture of melamine and urea.

Preferably, the polyester material is one or a mixture of polyethylene terephthalate, polycarbonate, polybutylene terephthalate, polycaprolactone, polydiallyl terephthalate, poly-p-hydroxybenzoate, polyvinyl acetate, polymethyl methacrylate and polyurethane.

Preferably, the polyester material is a waste polyester material.

Preferably, the molten salt is any one of a mixed salt of sodium chloride and zinc chloride, a mixed salt of potassium chloride and zinc chloride, and a mixed salt of lithium chloride and zinc chloride.

Preferably, the carbonization temperature is 250-400 ℃, preferably 260-380 ℃, and the heating rate is 2-30 ℃/min, more preferably 5-20 ℃/min.

Preferably, the mass fraction of the polyester in the polyester-crosslinking agent-molten salt mixture is 5% to 95%.

Preferably, the polyester accounts for 18-40% by mass, the crosslinking agent accounts for 8-25% by mass, and the molten salt accounts for 40-67% by mass.

Preferably, the acid washing refers to soaking in 0.1-1mol/L hydrochloric acid for washing for 1 h.

According to another aspect of the present invention, there is provided a nitrogen-doped carbon foam produced by carbonizing polyester, the nitrogen-doped carbon foam produced according to the above-described production method.

The invention has the following beneficial effects:

(1) according to the invention, the nitrogen-doped carbon foam with high added value is obtained by simultaneously carbonizing the polyester, the cross-linking agent and the molten salt. The introduction of the cross-linking agent promotes the cross-linking reaction of the polyester, the carbonization temperature is effectively reduced, the existence of the low-melting-point molten salt catalyst can eliminate partial weak chemical bonds in a cross-linking structure to generate micromolecule products such as carbon dioxide, water vapor and the like, and the micromolecule products can serve as the effect of an in-situ foaming agent. The application of the carbonization method has great guiding significance for large-scale treatment of waste polyester to prepare nitrogen-doped carbon foam. In addition, the preparation process is simple, a better solution is provided for solving the problems in the preparation of nitrogen-doped carbon foam by the controllable carbonization of polyester, and the method has industrial potential. The method promotes the polyester carbonization to prepare the nitrogen-doped carbon foam at a lower temperature, effectively solves the problems of high carbonization temperature, harsh carbonization reaction conditions, complex carbonization process and the like in the preparation process of the nitrogen-doped carbon foam, improves the utilization rate of the polyester in the carbonization process, is simple and effective, and has great application potential in the technical field of preparing the nitrogen-doped carbon foam by recycling the waste polyester.

(2) The heating temperature in the invention is 250-400 ℃, preferably 260-380 ℃, and the heating rate is preferably 2-30 ℃/min, more preferably 5-20 ℃/min. Compared with the prior art, the carbonization temperature is over 600 ℃, the carbonization temperature in the technology is reduced by over 220 ℃, and the effect is obvious. The reduction of the carbonization temperature not only reduces the energy consumption required by the process, thereby reducing the cost, but also avoids harsh reaction conditions at high temperature, so that the technology is easier to popularize and apply on a large scale. In addition, the temperature rise rate is selected moderately, the temperature rise rate selected in the technology can ensure that enough time can be provided for full reaction and synergistic effect between polyester degradation products in the carbonization process, so that the nitrogen-doped carbon foam structure is more uniform, the whole carbonization time can be within an acceptable range, and the method is favorable for practical popularization and application.

(3) The polyester material in the present invention is preferably one of polyethylene terephthalate, polycarbonate, polybutylene terephthalate, polycaprolactone, polydiallyl terephthalate, polyparaxybenzoate, polyvinyl acetate, polymethyl methacrylate, polyurethane, and waste polyester materials corresponding thereto. These polyester materials are all carbon-forming polymers, and the carbonization process can be regarded as a process of forming a carbon material skeleton by crosslinking. In the carbonization process, the polyester materials are heated and decomposed into a large number of molecular chains with carboxyl end groups, and although the decomposition products are difficult to perform cross-linking reaction at low temperature, the cross-linking agent generates a large number of cross-linked structures, which is beneficial to forming carbon foam with interconnected network structures. Meanwhile, the molten salt catalyst can eliminate partial weak chemical bonds in a cross-linked structure to generate micromolecule products such as carbon dioxide, water vapor and the like; these small molecule products can act as an in situ blowing agent. Thus, the in situ generated cross-linked structure and the generation of small molecule blowing agents are key to the conversion of polyesters to nitrogen-doped carbon foams.

Drawings

FIG. 1 is a photograph of carbonized products of examples 1 to 3 and comparative example 3, wherein (a) in FIG. 1 is a photograph of example 1, (b) is a photograph of example 2, (c) is a photograph of example 3, and (d) is a photograph of comparative example 3.

FIG. 2 is a photograph of carbonized products of examples 4 to 6, wherein (a) in FIG. 2 is example 4, (b) is example 5, and (c) is example 6.

FIG. 3 is a photograph of the carbonized product of examples 7 to 11, wherein FIG. 3(a) is a photograph of example 7, (b) is a photograph of example 8, (c) is a photograph of example 9, (d) is a photograph of example 10, and (e) is a photograph of example 11.

FIG. 4 is photographs showing carbonized products of comparative examples 1-2 and examples 12-13, and FIG. 4 is (a) a photograph showing comparative example 1, (b) a photograph showing comparative example 2, (c) a photograph showing example 12, and (d) a photograph showing comparative example 13.

FIG. 5 is an XRD pattern of the polyethylene terephthalate prepared in examples 1 to 3 and comparative example 3 together with melamine and molten salt carbonized products.

FIG. 6 is an XRD pattern of the polyethylene terephthalate and melamine and molten salt carbonized products prepared in examples 4 to 6.

Fig. 7 is a scanning electron microscope image of nitrogen-doped carbon foam prepared in example 3.

FIG. 8 is an X-ray photoelectron spectrum of a product obtained by carbonizing polyethylene terephthalate with melamine and a molten salt prepared in example 1

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.

Example 1

A nitrogen-doped carbon foam prepared by carbonizing polyester is prepared by the following method:

(1) 1.5g of polyethylene terephthalate (manufactured by Shandong Youyou chemical Co., Ltd.), 0.75g of melamine (chemical reagents of national drug group Co., Ltd.), 1.26g of sodium chloride (chemical reagents of national drug group Co., Ltd.) and 1.74g of zinc chloride (chemical reagents of Shanghai Linfeng Co., Ltd.) were weighed and stirred in a ball mill until they were mixed uniformly.

(2) And (2) putting the mixture obtained in the step (1) into a crucible, putting the crucible into a muffle furnace, heating the crucible to a temperature, setting the muffle furnace to a carbonization temperature of 340 ℃ at a heating rate of 10 ℃/min to obtain a carbonized product, and separating molten salt to obtain the carbonized product.

The carbonized product prepared is shown in FIG. 1 (a). The product appeared to be carbon black, indicating that the polyethylene terephthalate was fully carbonized with melamine, molten salt at 340 ℃.

Example 2

The amount of melamine (0.75 g) in example 1 was changed to 1.125g, and the other steps were not changed to obtain a carbonized product of polyethylene terephthalate, melamine and molten salt.

The carbonized product prepared is shown in FIG. 1 (b). The product appeared to be a carbon black indicating that the polyethylene terephthalate with melamine and molten salt had fully carbonized under these conditions.

Example 3

The amount of melamine (0.75 g) in example 1 was changed to 1.5g, and the other steps were not changed to obtain a carbonized product of polyethylene terephthalate, melamine and molten salt.

The carbonized product prepared is shown in FIG. 1 (c). The product appeared to be a carbon black indicating that the polyethylene terephthalate with melamine and molten salt had fully carbonized under these conditions.

Example 4

1.26g of sodium chloride and 1.74g of zinc chloride in example 1 were changed to 0.63g of sodium chloride and 0.87g of zinc chloride, and the other steps were not changed to obtain a carbonized product of polyethylene terephthalate with melamine and molten salt.

The carbonized product prepared is shown in FIG. 2 (a). The product appeared to be a carbon black indicating that the polyethylene terephthalate with melamine and molten salt had fully carbonized under these conditions.

Example 5

1.26g of sodium chloride and 1.74g of zinc chloride in example 1 were changed to 1.89g of sodium chloride and 2.61g of zinc chloride, and the other steps were not changed to obtain a carbonized product of polyethylene terephthalate with melamine and molten salt.

The carbonized product prepared is shown in FIG. 2 (b). The product appeared to be a carbon black indicating that the polyethylene terephthalate with melamine and molten salt had fully carbonized under these conditions.

Example 6

1.26g of sodium chloride and 1.74g of zinc chloride in example 1 were changed to 2.52g of sodium chloride and 3.48g of zinc chloride, and the other steps were not changed to obtain a carbonized product of polyethylene terephthalate with melamine and molten salt.

The carbonized product prepared is shown in FIG. 2 (c). The product appeared to be a carbon black indicating that the polyethylene terephthalate with melamine and molten salt had fully carbonized under these conditions.

Example 7

The polyethylene terephthalate in example 1 was changed to polycarbonate, the carbonization temperature was changed to 370 ℃, and the other steps were not changed to obtain a carbonized product of polycarbonate with melamine and molten salt.

The carbonized product was prepared as shown in FIG. 3(a), and the product exhibited a carbon black color, indicating that the mixture of polycarbonate with melamine and molten salt had been completely carbonized under this condition.

Example 8

The polyethylene terephthalate in example 1 was changed to polybutylene terephthalate, and the other steps were not changed to obtain a carbonized product of polybutylene terephthalate with melamine and molten salt.

The carbonized product was prepared as shown in FIG. 3(b), and the product exhibited a carbon black color, indicating that the mixture of polybutylene terephthalate with melamine and molten salt had been completely carbonized under this condition.

Example 9

The polyethylene terephthalate in example 1 was changed to waste polyethylene terephthalate, and the other steps were not changed to obtain a carbonized product of waste polyethylene terephthalate, melamine and molten salt.

The carbonized product was prepared as shown in FIG. 3(c), and the product exhibited a carbon black color, indicating that the mixture of waste polyethylene terephthalate with melamine and molten salt had been completely carbonized under this condition.

Example 10

The melamine in example 1 was changed to urea (national chemical group chemical Co., Ltd.), and the other steps were not changed to obtain a carbonized product of polyethylene terephthalate, urea and molten salt.

The carbonized product was prepared as shown in FIG. 3(d), and the product exhibited a carbon black color, indicating that the mixture of polyethylene terephthalate with urea and molten salt had been completely carbonized under this condition.

Example 11

The sodium chloride in example 1 was changed to potassium chloride (national chemical group chemical Co., Ltd.), and the other steps were not changed to obtain a carbonized product of polyethylene terephthalate, melamine and molten salt.

The carbonized product was prepared as shown in FIG. 3(e), and the product exhibited a carbon black color, indicating that the mixture of polyethylene terephthalate with melamine and molten salt had been completely carbonized under this condition.

Example 12

The carbonization temperature in the above example 1 was changed to 320 ℃ and the other steps were not changed to obtain a carbonized product of polyethylene terephthalate with melamine and molten salt.

The resulting carbonized product is shown in FIG. 4 (c). The product was a carbon black color indicating that the polyethylene terephthalate with melamine and molten salt had fully carbonized under these conditions.

Example 13

The carbonization temperature in example 1 was changed to 360 ℃ and the other steps were not changed to obtain a carbonized product of polyethylene terephthalate with melamine and molten salt.

The resulting carbonized product is shown in FIG. 4 (d). The product was a carbon black color indicating that the polyethylene terephthalate with melamine and molten salt had fully carbonized under these conditions. Although the carbonization is completed at the temperature, the carbonization temperature is relatively high and the energy consumption is relatively large.

Comparative examples

Comparative example 1

The carbonization temperature in the above example 1 was changed to 280 ℃ and the other steps were not changed to obtain a carbonized product of polyethylene terephthalate with melamine and molten salt.

The resulting carbonized product is shown in FIG. 4 (a). The product was brown, indicating that the polyethylene terephthalate with melamine and molten salt did not carbonize completely under these conditions.

Comparative example 2

The carbonization temperature in the above example 1 was changed to 300 ℃ and the other steps were not changed to obtain a carbonized product of polyethylene terephthalate with melamine and molten salt.

The resulting carbonized product is shown in FIG. 4 (b). The product was dark brown, indicating that the polyethylene terephthalate with melamine and molten salt did not carbonize completely under these conditions.

Comparative example 3

The amount of melamine used in example 1 was changed from 0.75g to 0.375g, and the other steps were not changed to obtain a carbonized product of polyethylene terephthalate and melamine and molten salt.

The resulting carbonized product is shown in FIG. 1 (d). The product appeared dark gray, indicating that the polyethylene terephthalate and melamine and molten salts were not fully carbonized under this condition.

Comparative example 4

The molten salt in example 1 was removed, and the volume of the obtained polymer was not expanded and carbon foam was not formed without changing the other steps.

From this, it was found that the molten salt catalyst can eliminate partially weak chemical bonds in the crosslinked structure to produce small molecular products such as carbon dioxide and water vapor; these small molecule products can act as an in situ blowing agent. Thus, the in situ generated cross-linked structure and the generation of small molecule blowing agents are key to the conversion of polyesters to nitrogen-doped carbon foams.

1. And (4) testing an X-ray diffraction spectrum of the carbonized product.

The products of co-carbonization of polyethylene terephthalate prepared in examples 1 to 3 and comparative example 3 with melamine and molten salt were characterized for their crystal structures by X-ray diffraction. The results are shown in fig. 5, from which it is apparent that the carbonized products of examples 1, 2 and 3 have diffraction characteristic peaks at 20 ° to 30 ° positions corresponding to (002) crystal planes, indicating that the material has amorphous carbon and partially graphitized characteristics, indicating that the prepared co-carbonized product has a standard carbon material crystal structure. In contrast, the carbonized product of comparative example 3 had characteristic diffraction peaks of the residual polyethylene terephthalate, indicating that the polyethylene terephthalate was not completely carbonized.

The polyethylene terephthalate of examples 4 to 6 was carbonized with melamine and molten salt, and its crystal structure was characterized by X-ray diffraction. The results are shown in fig. 6, from which it is apparent that the carbonized products of examples 4, 5 and 6 have diffraction characteristic peaks at 20 ° to 30 ° positions corresponding to (002) crystal planes, indicating that the material has amorphous carbon and partially graphitized characteristics, indicating that the prepared co-carbonized product has a standard carbon material crystal structure.

2. Scanning electron microscopy testing.

The scanning electron microscope photograph of the carbonized product of polyethylene terephthalate with melamine and molten salt in example 3 is shown in FIG. 7. It can be seen that the micro-morphology of the prepared nitrogen-doped porous carbon foam presents a porous structure, and the pore size is mainly distributed between 0.5 and 2 microns. The introduction of the cross-linking agent promotes the cross-linking reaction of the polyester, the carbonization temperature is effectively reduced, and the existence of the low-melting-point molten salt catalyst can eliminate partial weak chemical bonds in a cross-linking structure to generate micromolecule products such as carbon dioxide, water vapor and the like, and the micromolecule products can serve as the in-situ foaming agent.

X-ray photoelectron spectroscopy.

The X-ray photoelectron spectrum of the carbonized product of polyethylene terephthalate and melamine and molten salt is shown in FIG. 8. It can be seen that the carbonized product contains C, N, O three elements, the contents of which are 72.85%, 17.98% and 9.17% respectively. The content of N element in the carbonized product is very high, and the carbon foam generated by the reaction is nitrogen-doped carbon foam.

It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.