CN113398967B - Preparation method of sulfur-nitrogen double-doped oxygen modified carbon cloth material - Google Patents
Preparation method of sulfur-nitrogen double-doped oxygen modified carbon cloth material Download PDFInfo
- Publication number
- CN113398967B CN113398967B CN202110557907.8A CN202110557907A CN113398967B CN 113398967 B CN113398967 B CN 113398967B CN 202110557907 A CN202110557907 A CN 202110557907A CN 113398967 B CN113398967 B CN 113398967B
- Authority
- CN
- China
- Prior art keywords
- carbon cloth
- sulfur
- nitrogen
- modified carbon
- oxygen
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
Abstract
The invention discloses a method for preparing a sulfur-nitrogen double-doped oxygen modified carbon cloth material by a microwave coupling hydrothermal method. Compared with the original untreated carbon cloth, the surface appearance of the material subjected to microwave treatment is obviously improved in roughness and disorder degree, and the surface is effectively grafted with rich oxygen-containing functional groups, so that the hydrophobic surface is changed into a hydrophilic surface. The defect degree of the surface of the carbon cloth is changed, the doping of subsequent sulfur and nitrogen species is facilitated, the oxygen content of the finally prepared material is 5-20%, the elemental content of sulfur is 1-10%, and the elemental content of nitrogen is 1-10%. The heteroatom doped oxygen modified carbon cloth prepared by the method has the advantages of easily available raw materials, simple process, convenient control of conditions and higher heteroatom doping amount.
Description
Technical Field
The invention relates to the field of functional materials, in particular to a preparation method of a sulfur-nitrogen double-doped oxygen modified carbon cloth material.
Background
The proportion of the oxidation reaction in the whole organic chemical production is more than 30%, and most of the existing catalysts are metal catalysts. Leading-edge scientific and technological research in the catalytic and environmentally friendly energy fields to alleviate pollution problems has recently attracted considerable attention. However, the large-scale use of metal-based catalysts in industry is subject to various limitations or challenges due to limited reserves and environmental pollution. More efficient catalysis and new catalytic technologies are critical to minimizing environmental pollution, and great demands have prompted researchers to develop catalysts with advanced properties of high activity, high selectivity, excellent stability, and easy recovery. Carbon materials, particularly nanocarbon materials, have received considerable attention from researchers due to their unique properties of large specific surface area, acid and alkali resistance, wide sources, and adjustable surface groups. The carbon-based metal-free nano material is found to be applicable to various processes requiring metal catalysis, is expected to replace the traditional metal-based catalyst, and has important significance in saving metal resources and improving the sustainability of chemical processes. However, when using the carbon nano catalytic material, the catalyst in the form of ultrafine powder needs to be recovered by a solid-liquid separation device to avoid loss of the catalyst, which increases complexity and cost of the process flow. Thus, there is a need to produce monolithic carbon-based catalysts that are more suitable for use in reactors.
Commercial carbon cloths are woven from thin, continuous, free-standing, relatively smooth carbon fibers (about 10 μm in diameter). The carbon cloth is a three-dimensional structure on a microscopic scale, and weaves the space and the gap generated by the structure, so that in practical application, particularly in a liquid environment, the carbon cloth is favorable for quality permeation and exchange, and has become a substrate with development potential in the fields of energy storage devices, photocatalysis, electrocatalytic and the like due to excellent thermal stability, high conductivity, excellent acid and alkali resistance and mechanical stability. However, the carbon cloth has fewer surface defects, so that the active material loading is low. Therefore, it is necessary to modify and functionalize the surface functional groups of the carbon cloth. The skeleton structure of the carbon cloth is easily damaged by common methods such as gas phase oxidation, liquid phase oxidation, plasma oxidation and the like, so that how to modify the carbon cloth on the basis of not damaging the structure of the carbon cloth to increase the active material loading capacity of the carbon cloth and prepare a structured carbon catalytic material become the key for solving the problem.
Disclosure of Invention
The invention aims to provide a simple and effective preparation method of a sulfur-nitrogen double-doped oxygen modified carbon cloth material. The preparation method adopts a microwave coupling hydrothermal treatment method, namely, firstly, the carbon cloth is pretreated, and the microwave method is used for carrying out oxygen modification on the carbon cloth, so that the surface defects and the number of functional groups of the carbon cloth are increased, and the subsequent doping is facilitated. And then adopting proper sulfur-nitrogen precursors as sulfur and nitrogen sources, adopting a one-step hydrothermal method to realize co-doping of sulfur-nitrogen species on the surface of the modified carbon cloth, and drying to obtain the heteroatom doped carbon cloth-based material.
Compared with the original untreated carbon cloth, the surface appearance of the material is obviously improved in roughness and disorder degree, the carbon cloth surface is grafted with rich oxygen-containing functional groups, the hydrophobic surface is changed into a hydrophilic surface, sulfur and nitrogen species are successfully doped, the content of oxygen is 5-20%, the content of sulfur is 1-10%, and the content of nitrogen is 1-10%. The heteroatom doped oxygen modified carbon cloth prepared by the method has the advantages of easily available raw materials, simple process, convenient control of conditions and higher heteroatom doping amount. No strong acid or alkali is needed, no pollution to the environment is caused, no harm is caused to human body, and the cost is lower.
In order to solve the technical problems, the technical scheme adopted by the invention is to provide a simple and effective preparation method of sulfur-nitrogen double-doped oxygen modified carbon cloth material, which comprises the following steps:
step 1) pretreating carbon cloth with a certain size by using ethanol and deionized water;
step 2) putting the pretreated carbon cloth with certain water content into a microwave oven, and controlling the microwave treatment time to fully modify the carbon cloth;
step 3) rapidly cooling the carbon cloth obtained in the previous step by deionized water with a certain temperature;
step 4) forming a solution from sulfur-nitrogen precursor and proper amount of water in a certain proportion with the mass of the carbon cloth;
step 5) adding the cooled carbon cloth into a sulfur-nitrogen precursor solution, transferring to a hydrothermal kettle, controlling the temperature, and controlling the proper reaction time to enable the carbon cloth to fully react in the hydrothermal kettle;
and 6) washing the carbon cloth subjected to the hydrothermal treatment by deionized water, and drying to obtain the final product of the sulfur-nitrogen double-doped oxygen modified carbon cloth.
Preferably, the water content of the pretreated carbon cloth used in the step 2) is 10-50%.
Preferably, the microwave treatment time in the step 2) is 10-60 s.
Preferably, the microwave treatment atmosphere in step 2) is selected from one or more of the following: air, oxygen, argon.
Preferably, the temperature of the water in step 3) is 2-6 ℃.
Preferably, the carbon cloth in step 4): the mass ratio of the sulfur-nitrogen precursor is 1:20 to 70. The ratio of the mass of the sulfur-nitrogen precursor to the mass of the water is 1:1-50.
Preferably, the sulfur nitrogen precursor salt of step 4) is selected from one or more of the following: thiourea, dithizone, dimethyl sulfoxide and thioacetamide.
Preferably, in step 5), the reaction temperature is 100 to 250 ℃, more preferably, the reaction temperature is 120 to 200 ℃; most preferably, the reaction time is 180 ℃.
Preferably, in step 5), the reaction time is 5 to 60 hours, more preferably, the reaction time is 8 to 24 hours; most preferably, the reaction time is 12 hours.
The beneficial effects of the invention are as follows:
1. the sulfur-nitrogen double-doped oxygen modified carbon cloth material prepared by the invention has various functional groups and hydrophilicity. No strong acid or alkali is needed, no pollution to the environment is caused, no harm is caused to human body, and the cost is lower.
2. The invention has the advantages of easily available raw materials, simple process, convenient control of conditions and higher doping amount of hetero atoms.
3. The material prepared by the invention has high-efficiency oxidizing property and can be applied to catalyzing alcohol liquid-phase oxidation reaction.
Drawings
FIG. 1 is a schematic diagram of a sulfur-nitrogen double-doped oxygen modified carbon cloth material in example 1.
FIG. 2 is an SEM image of a sulfur nitrogen double doped oxygen modified carbon cloth material of example 3.
FIG. 3 is an XPS spectrum of a sulfur-nitrogen double doped oxygen modified carbon cloth material in example 5.
FIG. 4 is an AFM roughness data graph of sulfur-nitrogen double doped oxygen modified carbon cloth material of example 5.
Detailed Description
In order to more clearly illustrate the present invention, the present invention will be further described with reference to preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and that this invention is not limited to the details given herein.
Example 1:
1) The size is 1 x 2cm 2 Washing the carbon cloth with ethanol and deionized water;
2) Putting the pretreated carbon cloth (with the water content of 0%) into a household microwave oven (700W), and carrying out pulse heating treatment on the carbon cloth for 5s in an air atmosphere to fully modify the carbon cloth;
3) Adding the carbon cloth obtained in the previous step into deionized water (1 ℃) and rapidly cooling;
4) Thiourea powder with the mass of 1:10 with carbon cloth is dispersed in 25mL of deionized water to form thiourea solution;
5) Adding the cooled carbon cloth into thiourea solution, transferring to a hydrothermal kettle, controlling the temperature to be 100 ℃, and controlling the reaction time to be 4 hours to enable the solution to fully react in the hydrothermal kettle;
6) Washing the carbon cloth subjected to the hydrothermal treatment by deionized water, and drying to obtain the final product of the sulfur-nitrogen double-doped oxygen modified carbon cloth.
Example 2:
1) The size is 1 x 2cm 2 Washing the carbon cloth with ethanol and deionized water;
2) Putting the pretreated carbon cloth (with the water content of 10%) into a household microwave oven (700W), and carrying out pulse heating treatment on the carbon cloth for 15s in an oxygen atmosphere to fully modify the carbon cloth;
3) Adding the carbon cloth obtained in the previous step into deionized water (4 ℃) and rapidly cooling;
4) Dispersing thioacetamide with the mass of the carbon cloth being 1:20 in 25mL of deionized water to form a thioacetamide solution;
5) Adding the cooled carbon cloth into thioacetamide solution, transferring to a hydrothermal kettle, controlling the temperature to be 120 ℃, and controlling the reaction time to be 8 hours, so that the solution fully reacts in the hydrothermal kettle;
6) Washing the carbon cloth subjected to the hydrothermal treatment by deionized water, and drying to obtain the final product of the sulfur-nitrogen double-doped oxygen modified carbon cloth.
Example 3:
1) The size is 1 x 2cm 2 Washing the carbon cloth with ethanol and deionized water;
2) Putting the pretreated carbon cloth (with the water content of 20%) into a household microwave oven (700W), and performing pulse heating treatment on the carbon cloth for 30s in an air atmosphere to fully modify the carbon cloth;
3) Adding the carbon cloth obtained in the previous step into deionized water (6 ℃) and rapidly cooling;
4) Thiourea powder with the mass of 1:20 with carbon cloth is dispersed in 50mL of deionized water to form thiourea solution;
5) Adding the cooled carbon cloth into thiourea solution, transferring to a hydrothermal kettle, controlling the temperature to 120 ℃, and controlling the reaction time to 12 hours to enable the solution to fully react in the hydrothermal kettle;
6) Washing the carbon cloth subjected to the hydrothermal treatment by deionized water, and drying to obtain the final product of the sulfur-nitrogen double-doped oxygen modified carbon cloth.
Example 4:
1) The size is 1 x 2cm 2 Washing the carbon cloth with ethanol and deionized water;
2) Putting the pretreated carbon cloth (with the water content of 40%) into a household microwave oven (700W), and carrying out pulse heating treatment on the carbon cloth for 20s in an argon atmosphere to fully modify the carbon cloth;
3) Adding the carbon cloth obtained in the previous step into deionized water (4 ℃) and rapidly cooling;
4) Dispersing dithizone with the mass of 1:30 with carbon cloth in 25mL of deionized water to form dithizone solution;
5) Adding the cooled carbon cloth into a dithizone solution, transferring to a hydrothermal kettle, controlling the temperature to be 150 ℃, and controlling the reaction time to be 6 hours, so that the solution fully reacts in the hydrothermal kettle;
6) Washing the carbon cloth subjected to the hydrothermal treatment by deionized water, and drying to obtain the final product of the sulfur-nitrogen double-doped oxygen modified carbon cloth.
Example 5:
1) The size is 1 x 2cm 2 Washing the carbon cloth with ethanol and deionized water;
2) Putting the pretreated carbon cloth (with the water content of 50%) into a household microwave oven (700W), and carrying out pulse heating treatment on the carbon cloth for 20s in an air atmosphere to fully modify the carbon cloth;
3) Adding the carbon cloth obtained in the previous step into deionized water (4 ℃) and rapidly cooling;
4) Thiourea powder with the mass of 1:50 with carbon cloth is dispersed in 25mL of deionized water to form thiourea solution;
5) Adding the cooled carbon cloth into thiourea solution, transferring to a hydrothermal kettle, controlling the temperature to 180 ℃, and controlling the reaction time to be 12 hours to enable the solution to fully react in the hydrothermal kettle;
6) Washing the carbon cloth subjected to the hydrothermal treatment by deionized water, and drying to obtain the final product of the sulfur-nitrogen double-doped oxygen modified carbon cloth.
Example 6:
1) The size is 1 x 2cm 2 Washing the carbon cloth with ethanol and deionized water;
2) Putting the pretreated carbon cloth (with the water content of 50%) into a household microwave oven (700W), and carrying out pulse heating treatment on the carbon cloth for 40s in an air atmosphere to fully modify the carbon cloth;
3) Adding the carbon cloth obtained in the previous step into deionized water (10 ℃) and rapidly cooling;
4) Dispersing thioacetamide with the mass of the carbon cloth being 1:70 in 25mL of deionized water to form a thioacetamide solution;
5) Adding the cooled carbon cloth into thioacetamide solution, transferring to a hydrothermal kettle, controlling the temperature to be 200 ℃, and controlling the reaction time to be 20 hours, so that the solution fully reacts in the hydrothermal kettle;
6) Washing the carbon cloth subjected to the hydrothermal treatment by deionized water, and drying to obtain the final product of the sulfur-nitrogen double-doped oxygen modified carbon cloth.
The scope of the present invention includes, but is not limited to, the above embodiments, and any alterations, modifications, and improvements made by those skilled in the art are within the scope of the invention as defined in the claims.
Claims (3)
1. A preparation method of a sulfur-nitrogen double-doped oxygen modified carbon cloth material is characterized by comprising the following steps of: the material is based on oxygen modification of carbon cloth by using a microwave method, and is coupled with a one-step hydrothermal treatment method, so that two nonmetallic elements of sulfur and nitrogen are doped on an oxygen modified carbon cloth substrate together;
step 1), pretreating carbon cloth by using ethanol and deionized water;
step 2) putting the pretreated carbon cloth into a microwave oven, and controlling the microwave treatment time to fully modify the carbon cloth; the water content of the carbon cloth after pretreatment is 10-50%;
step 3) the modified carbon cloth obtained in the previous step is rapidly cooled by deionized water with a certain temperature; the water temperature for rapid cooling is 1-10 ℃;
step 4) forming a solution from sulfur-nitrogen precursor and proper amount of water in a certain proportion with the mass of the carbon cloth;
step 5) adding the cooled carbon cloth into a sulfur-nitrogen precursor solution, transferring to a hydrothermal kettle, controlling the temperature and the reaction time, and fully reacting the carbon cloth in the hydrothermal kettle;
step 6), washing the carbon cloth subjected to the hydrothermal treatment by deionized water, and drying to obtain a final product of sulfur-nitrogen double-doped oxygen modified carbon cloth;
the sulfur-nitrogen double-doped oxygen modified carbon cloth material obtained after the hydrothermal treatment has the oxygen element content of 5-20%, the sulfur element content of 1-10% and the nitrogen element content of 1-10%.
2. The method for preparing the sulfur-nitrogen double-doped oxygen modified carbon cloth material according to claim 1, which is characterized in that: the preparation method comprises the following steps:
the microwave treatment time in the step 2) is 6-60 s;
the microwave treatment atmosphere in the step 2) is selected from one or more of the following substances: air, oxygen or argon;
step 4) the carbon cloth: the mass ratio of the sulfur-nitrogen precursor is 1: 20-1: 70; the mass ratio of the sulfur-nitrogen precursor to water is 1:1-1: 50;
in the step 5), the reaction temperature is 100-250 ℃;
in the step 5), the reaction time is 5-60 h.
3. The method for preparing the sulfur-nitrogen double-doped oxygen modified carbon cloth material according to claim 1, which is characterized in that: step 4) the sulfur nitrogen precursor is selected from one or more of the following substances: thiourea, dithizone, ammonium thiocyanate, 1-ethyl-3-methylimidazole bistrifluoromethanesulfonimide salt and thioacetamide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110557907.8A CN113398967B (en) | 2021-05-21 | 2021-05-21 | Preparation method of sulfur-nitrogen double-doped oxygen modified carbon cloth material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110557907.8A CN113398967B (en) | 2021-05-21 | 2021-05-21 | Preparation method of sulfur-nitrogen double-doped oxygen modified carbon cloth material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113398967A CN113398967A (en) | 2021-09-17 |
| CN113398967B true CN113398967B (en) | 2023-07-25 |
Family
ID=77679247
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110557907.8A Active CN113398967B (en) | 2021-05-21 | 2021-05-21 | Preparation method of sulfur-nitrogen double-doped oxygen modified carbon cloth material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113398967B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108439372A (en) * | 2018-02-07 | 2018-08-24 | 山东大学 | Sulfur and nitrogen co-doped graphene-based aeroge of one kind and preparation method thereof |
| CN111509235A (en) * | 2020-04-29 | 2020-08-07 | 沈阳建筑大学 | Sulfur-nitrogen co-doped graphene modified graphite felt composite electrode and preparation method thereof |
| CN112735858A (en) * | 2020-12-24 | 2021-04-30 | 上海应用技术大学 | Preparation method of nitrogen and sulfur co-doped layered porous carbon hybrid material for super capacitor |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10422054B2 (en) * | 2015-09-22 | 2019-09-24 | Board Of Regents Of The University Of Texas System | Method of preparing doped and/or composite carbon fibers |
-
2021
- 2021-05-21 CN CN202110557907.8A patent/CN113398967B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108439372A (en) * | 2018-02-07 | 2018-08-24 | 山东大学 | Sulfur and nitrogen co-doped graphene-based aeroge of one kind and preparation method thereof |
| CN111509235A (en) * | 2020-04-29 | 2020-08-07 | 沈阳建筑大学 | Sulfur-nitrogen co-doped graphene modified graphite felt composite electrode and preparation method thereof |
| CN112735858A (en) * | 2020-12-24 | 2021-04-30 | 上海应用技术大学 | Preparation method of nitrogen and sulfur co-doped layered porous carbon hybrid material for super capacitor |
Non-Patent Citations (3)
| Title |
|---|
| Hyeonyeol Jeon et al..Facile and fast microwave-assisted fabrication of activated and porous carbon cloth composites with graphene and MnO2 for flexible asymmetric supercapacitors.《Electrochimica Acta》.2018,第280卷9-16. * |
| Jing Luo et al..TiNb2O7 nano-particle decorated carbon cloth as flexible self-support anode material in lithium-ion batteries.《Electrochimica Acta》.2019,第332卷135469：1-11. * |
| Masaharu Nakayama et al..Nitrogen-Doped Carbon Cloth for Supercapacitors Prepared via a Hydrothermal Process.《Journal of The Electrochemical Society》.2016,第163卷(第10期),A2428-A2434. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113398967A (en) | 2021-09-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111558391A (en) | Heteroatom-doped cobalt metal catalyst and preparation method thereof | |
| CN111617771B (en) | Preparation method of composite metal material catalyst and application of composite metal material catalyst in preparation of 5-HMF | |
| CN105776181B (en) | A kind of preparation method of flake nano porous carbon and carbon nano tube compound material | |
| CN108816234B (en) | Preparation method and application of derivative catalyst based on LDH (layered double hydroxide) immobilized transition metal MOF (Metal organic framework) | |
| CN105271217A (en) | Method for preparing nitrogen-doped three-dimensional graphene | |
| CN105271203A (en) | Porous co-doped graphene and preparation method thereof | |
| CN109046423B (en) | Three-dimensional grading composite material and preparation method and application thereof | |
| CN103908979A (en) | Supported nano TiO2 catalyst and preparation method thereof | |
| CN109126846B (en) | Silicon carbide nanowire/carbon fiber cloth composite material and preparation method and application thereof | |
| CN111905767B (en) | Nano pompon-shaped molybdenum sulfide/wood-based carbon porous electrode material and preparation method and application thereof | |
| CN109665525B (en) | Preparation method of dumbbell-shaped iron-nitrogen double-doped porous carbon | |
| CN111282588A (en) | Catalyst for hydrogen evolution by electrolyzing water and preparation method and application thereof | |
| CN112609197A (en) | Preparation method of two-dimensional lamellar carbon-based molybdenum carbide composite material | |
| CN113772656B (en) | Method for preparing porous carbon material with assistance of metal salt and application of porous carbon material | |
| CN111822014A (en) | Titanium foil loaded Fe-CoP nano-array structure catalyst and preparation method and application thereof | |
| CN111068717A (en) | Ruthenium simple substance modified sulfur-doped graphene two-dimensional material and preparation and application thereof | |
| CN113398967B (en) | Preparation method of sulfur-nitrogen double-doped oxygen modified carbon cloth material | |
| CN110745801B (en) | Surface sulfur-doped cobalt phosphide nano material and preparation method thereof | |
| CN110773220B (en) | Preparation method and application of porous two-dimensional carbon nitride @ graphene @ carbon nitride sandwich structure photocatalytic material | |
| CN111804317A (en) | Method for directly growing high-density cobalt phosphide nano-wire electrocatalyst on conductive substrate and application thereof | |
| CN110385135B (en) | Method for coating transition metal oxide self-assembly carbon | |
| CN111285349B (en) | Highly graphitized boron-doped carbon nanocapsule and preparation method thereof | |
| CN107857250B (en) | Melamine foam in-situ growth carbon nanotube composite super-hydrophobic material and preparation method thereof | |
| CN116354338A (en) | Method for short-time rapid high-temperature thermal shock treatment of MOF surface growth CNTs | |
| CN107754782B (en) | Self-supporting VO2Preparation method and product of Fenton-like catalytic material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |