CN111977648A - Silk fibroin source nitrogen-doped porous carbon material and preparation method thereof - Google Patents
Silk fibroin source nitrogen-doped porous carbon material and preparation method thereof Download PDFInfo
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- C07K14/435—Peptides having more than 20 amino acids; Gastrins; Somatostatins; Melanotropins; Derivatives thereof from animals; from humans
- C07K14/43504—Peptides having more than 20 amino acids; Gastrins; Somatostatins; Melanotropins; Derivatives thereof from animals; from humans from invertebrates
- C07K14/43563—Peptides having more than 20 amino acids; Gastrins; Somatostatins; Melanotropins; Derivatives thereof from animals; from humans from invertebrates from insects
- C07K14/43586—Peptides having more than 20 amino acids; Gastrins; Somatostatins; Melanotropins; Derivatives thereof from animals; from humans from invertebrates from insects from silkworms
Abstract
The invention discloses a fibroin source nitrogen-doped porous carbon material and a preparation method thereof, wherein the fibroin source nitrogen-doped porous carbon material is prepared by the following steps: and (3) soaking the fibroin protein in 0.1-0.45 mol/L potassium chloride solution, taking out and drying after the soaking is finished, and obtaining the potassium-doped fibroin protein. And (2) carrying out high-temperature treatment on the silk fibroin doped with the potassium element to carbonize the silk fibroin into a carbon material, and simultaneously combining the potassium element, the carbon element and the oxygen element in the silk fibroin to form potassium carbonate and then decomposing the potassium carbonate to generate escaped carbon dioxide so as to form holes on the carbon material, thereby obtaining the fibroin source nitrogen-doped porous carbon material. Wherein the temperature of the high-temperature treatment is 700-900 ℃. The preparation method is simple and easy to operate, and the prepared silk fibroin source nitrogen-doped porous carbon material has high nitrogen content, so that the material has good surface chemical activity and electrochemical performance.
Description
Technical Field
The invention relates to a fibroin source nitrogen-doped porous carbon material and a preparation method thereof.
Background
Porous carbon materials refer to porous structural materials having carbon as their basic skeleton, usually possessing closed or interconnected pores and constituting a network structure. The porous carbon material has the characteristics of low price and good stability of the carbon material, has the performances of high specific surface area and high porosity of the porous material, and is widely applied to the fields of energy storage, gas adsorption and catalysis.
The pure carbon porous material has poor hydrophilicity and poor chemical activity, and is limited in application. Researches show that nitrogen doping is adopted to introduce nitrogen heteroatoms into the carbon material, so that the surface chemical properties of the carbon material can be effectively changed.
After nitrogen doping, active sites on the surface of the material are increased, which is beneficial to the application of the porous carbon material in catalysis. Meanwhile, the introduction of nitrogen atoms can also improve the hydrophilic performance and the pore structure of the material, and even change the selective adsorption of the material to gas.
In the prior art, methods generally used for preparing nitrogen-doped porous carbon materials include a post-treatment synthesis method, a Chemical Vapor Deposition (CVD) method and an in-situ synthesis method.
The post-treatment synthesis method is used for carrying out nitrogen-doped functional modification treatment on the pre-synthesized porous carbon. The post-treatment synthesis method is simple in nitrogen doping process, but the most common post-treatment method needs ammonia gas, so that the cost is increased, and the post-treatment synthesis method is toxic and has risks.
The CVD method can be used for preparing the nitrogen-doped porous carbon material with higher nitrogen content, but the CVD method needs to be carried out at higher temperature, and has rigorous preparation conditions and high cost.
The direct synthesis method mainly refers to a method of directly doping nitrogen atoms into the framework or surface of a carbon material by adopting a carbon precursor rich in nitrogen elements through processes of polymerization, carbonization and the like, and is also called as an in-situ nitrogen doping method. The nitrogen element obtained by the method is mainly structural nitrogen, is more stable, is easy to control the nitrogen content, and can prepare the nitrogen-doped porous carbon material with high specific surface area and high nitrogen content. Meanwhile, other chemical additives are not required to be added in the in-situ method, so that the method is more green and environment-friendly. However, in the prior art, the most commonly used precursors for the direct synthesis method include aminosugars, melamine, benzylamine, nitrogen-containing heterocyclic compounds, phthalocyanines and the like, and the precursors need to be attached to a supporting material and further carbonized to form a nitrogen-doped material.
Therefore, the preparation of the nitrogen-doped porous carbon material in the prior art needs to be improved from the precursor material and the preparation method, so that the application value of the nitrogen-doped porous carbon material can be improved.
Disclosure of Invention
In order to overcome the defects in the prior art, the embodiment of the invention provides the fibroin source nitrogen-doped porous carbon material and the preparation method thereof, the preparation method is simple and easy to operate, and the prepared fibroin source nitrogen-doped porous carbon material has high nitrogen content, so that the material has good surface chemical activity and electrochemical performance.
The invention discloses a preparation method of a fibroin source nitrogen-doped porous carbon material, which comprises the following steps:
soaking fibroin protein in 0.1-0.45 mol/L potassium chloride solution, taking out and drying after soaking is finished, and obtaining potassium-doped fibroin protein;
carrying out high-temperature treatment on the silk fibroin doped with the potassium element to carbonize the silk fibroin into a carbon material, and simultaneously combining the potassium element, the carbon element and the oxygen element in the silk fibroin to form potassium carbonate and then decomposing the potassium carbonate to generate escaped carbon dioxide so as to form holes on the carbon material, thereby obtaining the fibroin source nitrogen-doped porous carbon material;
wherein the temperature of the high-temperature treatment is 700-900 ℃.
Preferably, the step of soaking the fibroin protein in 0.1-0.45 mol/L potassium chloride solution is carried out, the concentration of the potassium chloride solution is 0.45mol/L, and the soaking treatment time is 22-26 h.
Preferably, the temperature of the high-temperature treatment is 900 ℃, the heat preservation time is 2-4 h, and the heating rate is 5 ℃/min.
Preferably, the preparation method of the silk fibroin comprises the following steps:
cleaning the silkworm cocoons to remove impurities, and putting the cleaned silkworm cocoons into a sodium carbonate solution to remove sericin in the silkworm cocoons;
preparing calcium chloride, ethanol and deionized water into a ternary system solution according to the weight ratio of 1:2: 8;
dissolving the silk cocoons without sericin in a ternary system solution to obtain a silk fibroin solution;
putting the silk fibroin solution into a dialysis bag with the molecular weight of 8000-14000 for dialysis so as to remove calcium chloride and ethanol;
and drying the dialyzed silk fibroin solution to obtain the silk fibroin.
Preferably, the step of washing the silkworm cocoons to remove impurities comprises the steps of putting the washed silkworm cocoons into a sodium carbonate solution to remove sericin in the silkworm cocoons, putting the washed silkworm cocoons into the sodium carbonate solution, and carrying out water bath treatment at 100 ℃ for 0.8-1.2 h.
Further preferably, the step of "dissolving the sericin-removed silkworm cocoon in the ternary system solution" includes washing the sericin-removed silkworm cocoon with deionized water for at least 2 times, and then dissolving the silk cocoon in the ternary system solution.
Preferably, the silk cocoon without sericin is dissolved in a ternary system solution to obtain a silk fibroin solution, the silk cocoon without sericin is soaked in the ternary system solution, and the silk fibroin solution is obtained by performing water bath treatment at 75 ℃ for 5-7 h to dissolve the silk cocoon in the ternary system solution.
The fibroin source nitrogen-doped porous carbon material contains nitrogen elements, and the content of the nitrogen elements is 10-13% by weight.
The invention has the following beneficial effects:
the invention successfully synthesizes the silk fibroin source nitrogen-doped porous carbon material with high nitrogen content by carbonizing silk fibroin, activates the silk fibroin through potassium chloride, successfully enables the carbon material to have porous appearance, and improves the nitrogen content of the material after activation. According to the invention, the carbonization temperature and the potassium chloride content are optimized, so that the nitrogen content of the fibroin source nitrogen-doped porous carbon material is increased, the surface chemical activity of the fibroin source nitrogen-doped porous carbon material can be further improved, the conductivity and the electrochemical performance are improved, and the fibroin source nitrogen-doped porous carbon material has higher use value.
The silk fibroin source nitrogen-doped porous carbon material prepared by the invention has the advantages of simple structure, easy operation of the preparation method, easy control of the preparation process and short process flow.
In order to make the aforementioned and other objects, features and advantages of the invention comprehensible, preferred embodiments accompanied with figures are described in detail below.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a scanning electron microscope image of a silk fibroin source nitrogen-doped porous carbon material with a resolution of 2 μm in example 1 of the present invention;
FIG. 2 is a scanning electron microscope image of a silk fibroin source nitrogen-doped porous carbon material with a resolution of 500nm in example 2 of the present invention;
FIG. 3 is a scanning electron microscope image of a silk fibroin source nitrogen-doped porous carbon material with a resolution of 5 μm in example 3 of the present invention;
FIG. 4 is a scanning electron microscope image of a silk fibroin source nitrogen-doped porous carbon material with a resolution of 500nm in example 3 of the present invention;
FIG. 5 is a scanning electron microscope image of a silk fibroin source nitrogen-doped porous carbon material with a resolution of 1 μm in example 4 of the present invention;
FIG. 6 is a scanning electron microscope image of the silk fibroin source nitrogen-doped carbon material of comparative example 1 according to the present invention with a resolution of 100 μm.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Preparing silk fibroin:
calcium chloride, ethanol and deionized water are prepared into a ternary system solution according to the weight ratio of 1:2: 8.
Cleaning the silkworm cocoon to remove impurities, placing the cleaned silkworm cocoon in a sodium carbonate solution, and carrying out water bath treatment at 100 ℃ for 1h to remove sericin in the silkworm cocoon.
And (3) cleaning the silk cocoons without sericin for three times by using deionized water, then soaking the silk cocoons in the ternary system solution, and treating the silk cocoons in a 75 ℃ water bath for 6 hours to dissolve the silk cocoons in the ternary system solution to obtain the silk fibroin solution.
And (2) putting the silk fibroin solution into a dialysis bag with the molecular weight of 8000-14000 for dialysis for 72 hours to remove calcium chloride and ethanol, and drying the dialyzed silk fibroin solution at 25 ℃ to obtain the silk fibroin.
Preparing a fibroin source nitrogen-doped porous carbon material:
soaking fibroin protein in 0.45mol/L potassium chloride solution for treatment for 24h, taking out and drying after soaking is finished, and obtaining potassium-doped fibroin protein;
and (3) carrying out high-temperature carbonization treatment on the silk fibroin doped with the potassium element, wherein the temperature of the high-temperature carbonization treatment is 700 ℃, the heat preservation time is 4h, and the temperature rise rate is 5 ℃/min. In the high-temperature carbonization treatment process, the silk fibroin is carbonized into a carbon material, and simultaneously potassium element, carbon element and oxygen element in the silk fibroin are combined to form potassium carbonate, and then carbon dioxide generated by decomposition escapes to form holes on the carbon material, so that the silk fibroin source nitrogen-doped porous carbon material is obtained.
Example 2
Preparing silk fibroin:
the procedure for preparing silk fibroin in this example was the same as in example 1.
Preparing a fibroin source nitrogen-doped porous carbon material:
soaking fibroin protein in 0.45mol/L potassium chloride solution for treatment for 24h, taking out and drying after soaking is finished, and obtaining potassium-doped fibroin protein;
carrying out high-temperature carbonization treatment on the silk fibroin doped with the potassium element, wherein the temperature of the high-temperature carbonization treatment is 800 ℃, the heat preservation time is 4h, and the temperature rise rate is 5 ℃/min. In the high-temperature carbonization treatment process, the silk fibroin is carbonized into a carbon material, and simultaneously potassium element, carbon element and oxygen element in the silk fibroin are combined to form potassium carbonate, and then carbon dioxide generated by decomposition escapes to form holes on the carbon material, so that the silk fibroin source nitrogen-doped porous carbon material is obtained.
Example 3
Preparing silk fibroin:
the procedure for preparing silk fibroin in this example was the same as in example 1.
Preparing a fibroin source nitrogen-doped porous carbon material:
soaking fibroin protein in 0.45mol/L potassium chloride solution for treatment for 24h, taking out and drying after soaking is finished, and obtaining potassium-doped fibroin protein;
and (3) carrying out high-temperature carbonization treatment on the silk fibroin doped with the potassium element, wherein the temperature of the high-temperature carbonization treatment is 900 ℃, the heat preservation time is 4h, and the temperature rise rate is 5 ℃/min. In the high-temperature carbonization treatment process, the silk fibroin is carbonized into a carbon material, and simultaneously potassium element, carbon element and oxygen element in the silk fibroin are combined to form potassium carbonate, and then carbon dioxide generated by decomposition escapes to form holes on the carbon material, so that the silk fibroin source nitrogen-doped porous carbon material is obtained.
Example 4
Preparing silk fibroin:
the procedure for preparing silk fibroin in this example was the same as in example 1.
Preparing a fibroin source nitrogen-doped porous carbon material:
soaking fibroin protein in 0.3mol/L potassium chloride solution for treatment for 24h, taking out and drying after soaking is finished, and obtaining potassium-doped fibroin protein;
and (3) carrying out high-temperature carbonization treatment on the silk fibroin doped with the potassium element, wherein the temperature of the high-temperature carbonization treatment is 900 ℃, the heat preservation time is 4h, and the temperature rise rate is 5 ℃/min. In the high-temperature carbonization treatment process, the silk fibroin is carbonized into a carbon material, and simultaneously potassium element, carbon element and oxygen element in the silk fibroin are combined to form potassium carbonate, and then carbon dioxide generated by decomposition escapes to form holes on the carbon material, so that the silk fibroin source nitrogen-doped porous carbon material is obtained.
Comparative example 1
Preparing silk fibroin:
the procedure for preparing silk fibroin in this example was the same as in example 1.
Preparing a fibroin source nitrogen-doped carbon material:
and (3) carrying out high-temperature carbonization treatment on the silk fibroin to obtain the nitrogen-doped carbon material of the silk fibroin source, wherein the temperature of the high-temperature carbonization treatment is 800 ℃, the heat preservation time is 4 hours, and the temperature rise rate is 5 ℃/min.
The materials prepared in examples 1 to 4 and comparative example 1 were subjected to analysis of carbon, nitrogen and oxygen by EDS spectroscopy, and the results are shown in the following table:
EDS (electron-dispersive spectroscopy) energy spectrum analysis shows that the nitrogen-doped porous carbon material can be successfully synthesized by carbonizing silk fibroin.
In examples 1 to 4, after carbonization, the nitrogen content of the silk fibroin activated by potassium chloride was 10.586 wt% (700 ℃), 11.402 wt% (800 ℃), 11.023 wt% (900 ℃), and 12.113 wt% (900 ℃). Comparative example 1 differs from example 2 in that in comparative example 1 where non-potassium chloride activated silk fibroin was used, the nitrogen content of the material was only 5.597% wt. It is seen that the nitrogen content (> 10% wt) of the material activated with potassium chloride and carbonized at different temperatures is significantly increased compared to the nitrogen content of the material that was not activated (5.597% wt).
In examples 1 to 3, the carbonization temperatures were 700 ℃, 800 ℃ and 900 ℃, respectively, and the nitrogen contents of the materials in examples 2 and 3 were significantly higher than those in example 1, indicating that the temperature has an important influence on the nitrogen content of the material. In example 3, the carbonization temperature was 900 ℃ to obtain a material having the highest nitrogen content, which indicates that 900 ℃ is the most suitable carbonization temperature.
The difference between example 4 and example 3 is that potassium chloride with a concentration of 0.3mol/L is used in example 4, and the nitrogen content of the material in example 4 is improved compared with that of the material in example 3, but referring to FIG. 5, it can be observed that the shape of the pores of the material in example 4 is irregular, and the distribution of the pores is not uniform, so that the material in example 3 is the best solution.
Referring to the attached drawings 1-5, and combining the carbon nitrogen oxygen element analysis results, the method shows that a nitrogen-doped carbon material with high nitrogen content is successfully synthesized by carbonizing silk fibroin, the silk fibroin is activated by potassium chloride, the carbon material is successfully made to have a porous appearance, and the nitrogen content of the material is also improved after activation. By improving the nitrogen content of the material, the surface chemical activity of the material can be improved, the conductivity and the electrochemical performance of the material are improved, and the material has higher use value.
As can be seen from the attached drawings 1-4, the sample surface activated by potassium chloride has obvious porous appearance, and the surface pore appearance of the activated sample treated at 900 ℃ is ideal. Referring to the attached figure 5, the final morphology of the material is greatly influenced by the concentration of potassium chloride, and the material can reach more ideal surface holes by selecting 0.45mol/L potassium chloride for activation.
Referring to fig. 6, it can be seen that the surface of the silk fibroin without activation is difficult to form pores, thereby resulting in poor overall performance of the material.
The principle and the implementation mode of the invention are explained by applying specific embodiments in the invention, and the description of the embodiments is only used for helping to understand the method and the core idea of the invention; meanwhile, for a person skilled in the art, according to the idea of the present invention, there may be variations in the specific embodiments and the application scope, and in summary, the content of the present specification should not be construed as a limitation to the present invention.
Claims (8)
1. A preparation method of a fibroin source nitrogen-doped porous carbon material is characterized by comprising the following steps:
soaking fibroin protein in 0.1-0.45 mol/L potassium chloride solution, taking out and drying after soaking is finished, and obtaining potassium-doped fibroin protein;
carrying out high-temperature treatment on the silk fibroin doped with the potassium element to carbonize the silk fibroin into a carbon material, and simultaneously combining the potassium element, the carbon element and the oxygen element in the silk fibroin to form potassium carbonate and then decomposing the potassium carbonate to generate escaped carbon dioxide so as to form holes on the carbon material, thereby obtaining the fibroin source nitrogen-doped porous carbon material;
wherein the temperature of the high-temperature treatment is 700-900 ℃.
2. The preparation method of the nitrogen-doped porous carbon material with the silk fibroin source according to claim 1, wherein the step of soaking the silk fibroin protein in 0.1-0.45 mol/L potassium chloride solution is carried out, the concentration of the potassium chloride solution is 0.45mol/L, and the soaking treatment time is 22-26 h.
3. The preparation method of the nitrogen-doped porous carbon material as claimed in claim 1, wherein the temperature of the high-temperature treatment is 900 ℃, the heat preservation time is 2-4 h, and the temperature rise rate is 5 ℃/min.
4. The preparation method of the nitrogen-doped porous carbon material with silk fibroin as claimed in claim 1, wherein the preparation method of the silk fibroin comprises the following steps:
cleaning the silkworm cocoons to remove impurities, and putting the cleaned silkworm cocoons into a sodium carbonate solution to remove sericin in the silkworm cocoons;
preparing calcium chloride, ethanol and deionized water into a ternary system solution according to the weight ratio of 1:2: 8;
dissolving the silk cocoons without sericin in a ternary system solution to obtain a silk fibroin solution;
putting the silk fibroin solution into a dialysis bag with the molecular weight of 8000-14000 for dialysis so as to remove calcium chloride and ethanol;
and drying the dialyzed silk fibroin solution to obtain the silk fibroin.
5. The preparation method of the silk fibroin source nitrogen-doped porous carbon material according to claim 4, wherein the silk cocoons are washed to remove impurities, the washed silk cocoons are placed in a sodium carbonate solution to remove sericin in the silk cocoons, the washed silk cocoons are placed in the sodium carbonate solution, and the water bath treatment at 100 ℃ is carried out for 0.8-1.2 h.
6. The method for preparing the nitrogen-doped porous carbon material as claimed in claim 4, wherein the silk fibroin source solution is prepared by dissolving the silk cocoon without sericin in the ternary system solution, and the silk cocoon without sericin is washed with deionized water for at least 2 times and then dissolved in the ternary system solution.
7. The preparation method of the silk fibroin-derived nitrogen-doped porous carbon material according to claim 4, wherein in the step of dissolving the sericin-removed silkworm cocoons in the ternary system solution to obtain the silk fibroin solution, the sericin-removed silkworm cocoons are soaked in the ternary system solution, and are subjected to water bath treatment at 75 ℃ for 5-7 hours to dissolve the silkworm cocoons in the ternary system solution, so that the silk fibroin solution is obtained.
8. The fibroin-source nitrogen-doped porous carbon material is prepared by the preparation method according to any one of claims 1-7, and is characterized in that the fibroin-source nitrogen-doped porous carbon material contains nitrogen elements, and the content of the nitrogen elements is 10-13% by weight.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113201754A (en) * | 2021-05-10 | 2021-08-03 | 苏州大学 | Electrocatalyst material for hydrogen evolution and oxygen evolution reaction, and preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103361885A (en) * | 2013-06-28 | 2013-10-23 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of antibacterial silk fibroin fibrous membrane |
| CN105336930A (en) * | 2015-10-16 | 2016-02-17 | 浙江理工大学 | Nitrogen-enriched carbon based/sulfur composite cathode material used for lithium sulphur batteries, and preparation method thereof |
| CN105845954A (en) * | 2016-04-01 | 2016-08-10 | 浙江理工大学 | Silk-derived nitrogen-doped graphene fibers |
| CN107170994A (en) * | 2017-04-14 | 2017-09-15 | 首都师范大学 | A kind of Fe N doping porous carbon oxygen reduction catalyst |
| CN110371970A (en) * | 2019-08-12 | 2019-10-25 | 四川轻化工大学 | A kind of preparation method of the rich nitrogen grading porous carbon material of high-specific surface area |
| CN111533124A (en) * | 2020-05-12 | 2020-08-14 | 湖南鑫恒环境科技有限公司 | Two-dimensional nitrogen-doped nano porous carbon material and preparation method thereof |
-
2020
- 2020-08-19 CN CN202010835632.5A patent/CN111977648A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103361885A (en) * | 2013-06-28 | 2013-10-23 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of antibacterial silk fibroin fibrous membrane |
| CN105336930A (en) * | 2015-10-16 | 2016-02-17 | 浙江理工大学 | Nitrogen-enriched carbon based/sulfur composite cathode material used for lithium sulphur batteries, and preparation method thereof |
| CN105845954A (en) * | 2016-04-01 | 2016-08-10 | 浙江理工大学 | Silk-derived nitrogen-doped graphene fibers |
| CN107170994A (en) * | 2017-04-14 | 2017-09-15 | 首都师范大学 | A kind of Fe N doping porous carbon oxygen reduction catalyst |
| CN110371970A (en) * | 2019-08-12 | 2019-10-25 | 四川轻化工大学 | A kind of preparation method of the rich nitrogen grading porous carbon material of high-specific surface area |
| CN111533124A (en) * | 2020-05-12 | 2020-08-14 | 湖南鑫恒环境科技有限公司 | Two-dimensional nitrogen-doped nano porous carbon material and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113201754A (en) * | 2021-05-10 | 2021-08-03 | 苏州大学 | Electrocatalyst material for hydrogen evolution and oxygen evolution reaction, and preparation method and application thereof |
| CN113201754B (en) * | 2021-05-10 | 2022-04-22 | 苏州大学 | Electrocatalyst material for hydrogen evolution and oxygen evolution reaction, and preparation method and application thereof |
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