CN113003560A - Method for hydro-thermal synthesis of 'sea urchin-like' nitrogen-doped hollow carbon microspheres by in-situ self-growth template - Google Patents
Method for hydro-thermal synthesis of 'sea urchin-like' nitrogen-doped hollow carbon microspheres by in-situ self-growth template Download PDFInfo
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- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/22—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains four or more hetero rings
Abstract
A method for synthesizing 'sea urchin-like' nitrogen-doped hollow carbon microspheres by using an in-situ self-growth template hydro-thermal method, belonging to the technical field of material preparation. The method comprises the following specific steps: adding glucose, zinc nitrate, urotropine and trisodium citrate into deionized water according to a certain proportion, uniformly stirring, then transferring the suspension into a self-pressurized kettle for hydro-thermal treatment to obtain brown powder solid, roasting in inert atmosphere, and removing the template by using hydrochloric acid solution to obtain the sea urchin-like nitrogen-doped hollow carbon microsphere material.
Description
Technical Field
The invention relates to a preparation method of 'sea urchin-like' nitrogen-doped hollow carbon microspheres by in-situ self-growth template hydrothermal synthesis, belonging to the technical field of material preparation.
Background
The porous carbon material has the characteristics of large specific surface area, easy regulation and control of aperture and surface chemical properties, good chemical stability, wide raw material source and the like, shows good application prospects in the fields of catalysis, energy storage and conversion, adsorption and the like, and is widely concerned by scientific researchers. Through continuous research and exploration, people can carry out effective structural design and physicochemical modification on the porous carbon material, and realize aperture regulation and heteroatom doping modification of the porous carbon material. There are various methods for producing porous carbon materials, such as: the hard template method (Puthusseri D., et al., Energy & Environmental Science,2014,7(2):728-735) using clay, zeolite, mesoporous silicon, etc. as templates; "Soft template method" (Meng Y., et al., Chemistry of Materials,2006,18(18): 4447-. These methods are difficult to industrialize because the preparation process is complicated or the precursor of carbon is expensive.
The surface chemical property of the porous carbon material has a remarkable influence on the application performance of the porous carbon material, and chemical doping modification of the porous carbon material is a common surface modification method. The effects of heteroatom doping on porous carbon materials are mainly as follows: 1) the introduction of the heteroatom can increase the surface hydrophilicity of the porous carbon material and improve the wetting capacity; 2) the introduction of the hetero atoms can influence the surface electronic structure of the porous carbon material, so that the conductivity and the electrochemical property of the porous carbon material are improved; 3) the hetero atoms can act with the metal active components to improve the dispersion degree and the catalytic performance of the active components. Common doping atoms are: nitrogen, sulfur, boron, and the like. Such as: zuo et al (Zuo S, et al, Carbon,2018,129: 199-; yeh et al (Yeh M.H., et al., Energy Procedia,2014,61: 1764-; liu et al (Liu S., et al, Journal of Power Sources,2017,360:373-382) prepared sulfur-doped porous carbon nanospheres by using glucose as a carbon source and elemental sulfur as a sulfur source through processes such as high-temperature hydrothermal carbonization. These heteroatom-doped carbon materials all exhibit excellent properties.
The invention takes glucose as a carbon source to collectThe nitrogen-doped hollow carbon microsphere material is prepared by one-step hydrothermal synthesis by using an in-situ self-growth template method, and has a typical mesoporous structure. In addition, compared with the traditional silicon-based template method, the method avoids using a strong corrosive hydrofluoric acid solution. Pd (OH) prepared by using carbon material as carrier2the/C catalyst shows excellent activity in the hydrogenolysis debenzylation of Hexabenzylhexaazaisowurtzitane (HBIW).
Disclosure of Invention
The invention aims to provide a preparation method for synthesizing 'sea urchin-like' nitrogen-doped hollow carbon microspheres by using an in-situ self-growth template hydro-thermal method.
In order to achieve the purpose of the invention, the technical scheme adopted by the experiment is as follows:
a preparation method of 'sea urchin-like' nitrogen-doped hollow carbon microspheres by in-situ self-growth template hydrothermal synthesis is characterized by comprising the following steps:
(1) adding zinc nitrate, urotropine, trisodium citrate and a carbon precursor into deionized water, and stirring to form a suspension;
(2) adding the suspension obtained in the step (1) into a polytetrafluoroethylene lining, putting the lining into a stainless steel self-pressure kettle, and carrying out hydrothermal synthesis at a certain temperature to obtain brown powder solid;
(3) roasting the brown powder obtained in the step (2) in a tube furnace under inert gas for a certain time;
(4) and (4) putting the product obtained in the step (3) into a hydrochloric acid solution, and stirring for 3-6h to remove the template agent. And then filtering, washing and drying to obtain the expected carbon material.
The concentration of the carbon precursor in the step (1) is 0.1-0.4 mol/L; the molar ratio of the zinc nitrate to the urotropine is 1: 5-5: 1; the amount of the trisodium citrate is 0.01-0.20 times of the mass of the zinc nitrate.
The carbon precursor is at least one of monosaccharide such as glucose, fructose and galactose, and disaccharide such as sucrose, trehalose, maltose and lactose.
The hydrothermal synthesis temperature in the step (2) is 140-240 ℃, wherein the preferable temperature is 150-200 ℃, and the time is 12-24 h.
In the step (3), the roasting temperature is 600-800 ℃, the heating rate is 2-10 ℃/min, the roasting time is 2-10 h, and the inert gas is selected from one of nitrogen, helium and argon.
In the step (4), the mass concentration of the hydrochloric acid is 5-37%.
The obtained material can be used as a catalyst carrier for hydrogenolysis debenzylation, especially for hydrogenolysis debenzylation of HBIW.
The diameter of the 'sea urchin-like' nitrogen-doped hollow carbon microsphere prepared by the method is about 2-5 mu m (shown in figures 1, 2 and 3), and the nitrogen-doped hollow carbon microsphere has a typical mesoporous structure (shown in figure 4) and micropores, wherein the volume of the micropores accounts for less than 20% of the total volume.
The invention has the innovation points that the sea urchin-like nitrogen-doped hollow carbon microsphere material is prepared by taking cheap saccharides as a carbon source, urotropine as a nitrogen source and trisodium citrate as a structure directing agent through one-step hydrothermal synthesis by adopting an in-situ self-growth template method, and has simple preparation process and unique product structure.
Drawings
Fig. 1 is a Transmission Electron Microscope (TEM) photograph of a single hollow carbon microsphere.
Fig. 2 is a Transmission Electron Microscope (TEM) photograph of # 1, 2 samples prepared in examples 1, 2.
Fig. 3 is a Scanning Electron Microscope (SEM) photograph of # 1, # 2, and # 3 samples prepared in examples 1, 2, and 3.
Fig. 4 is a nitrogen adsorption and desorption curve (a) and a pore size distribution curve (b) of sample # 1 prepared in example 1.
FIG. 5 shows the hydrogenolysis debenzylation reaction formula of HBIW.
Figure 6 is a hydrogenolysis debenzylation hydrogen sorption curve.
Detailed Description
The present invention will be further described with reference to the following examples, but the present invention is not limited to the following examples.
Example 1
2.23g (0.25mol/L) of zinc nitrate hexahydrate, 1.04g (0.25mol/L) of urotropine and 1.08g of glucose are weighed and dissolved in 30ml of deionized water, 2ml (0.25mol/L) of trisodium citrate is added under magnetic stirring, stirring is continued for 1h, the suspension is transferred into a polytetrafluoroethylene lining, the lining is placed into a stainless steel self-pressure kettle, and the reaction is carried out for 18h at 150 ℃. Filtering to obtain brown solid, roasting the brown solid in a tubular furnace at 700 ℃ for 2h, cooling to room temperature, removing the template by using 20 wt% hydrochloric acid, washing by using deionized water, and drying to obtain a sample No. 1.
Example 2
2.23g (0.25mol/L) of zinc nitrate hexahydrate, 1.04g (0.25mol/L) of urotropine and 1.08g of glucose are weighed and dissolved in 30ml of deionized water, 1ml (0.25mol/L) of trisodium citrate is added under magnetic stirring, stirring is continued for 1h, the suspension is transferred into a polytetrafluoroethylene lining, the lining is placed into a stainless steel self-pressure kettle, and reaction is carried out for 18h at 150 ℃. Filtering to obtain brown solid, roasting the brown solid in a tubular furnace at 700 ℃ for 2h, cooling to room temperature, removing the template by using 20 wt% hydrochloric acid, washing by using deionized water, and drying to obtain a No. 2 sample.
Embodiment 3
2.23g (0.25mol/L) of zinc nitrate hexahydrate, 1.04g (0.25mol/L) of urotropine and 1.08g of glucose are weighed and dissolved in 30ml of deionized water, 4ml (0.25mol/L) of trisodium citrate is added under magnetic stirring, stirring is continued for 1h, the suspension is transferred into a polytetrafluoroethylene lining, the lining is placed into a stainless steel self-pressure kettle, and the reaction is carried out for 18h at 150 ℃. Filtering to obtain brown solid, roasting the brown solid in a tubular furnace at 700 ℃ for 2h, cooling to room temperature, removing the template by using 20 wt% hydrochloric acid, washing by using deionized water, and drying to obtain a No. 3 sample.
Application example:
pd (OH) with the load of 8 percent is prepared by an impregnation method by taking a sample No. 1 and commercial carbon (Macklin) as a carrier2the/C catalyst was used in the hydrogenolysis debenzylation of HBIW (FIG. 5) under the following reaction conditions: HBIW: 50g of the total weight of the mixture; pd (OH)2/C：0.625g，DMF:100mL；Ac2O: 50 mL; PhBr: 0.9 mL. The 1# catalyst yield was 91%; the Macklin sample yield was 58%; the hydrogen absorption curve is shown in figure 6.
Claims (8)
1. A preparation method of 'sea urchin-like' nitrogen-doped hollow carbon microspheres by in-situ self-growth template hydrothermal synthesis is characterized by comprising the following steps:
(1) adding glucose, zinc nitrate, urotropine and trisodium citrate into a certain amount of deionized water, and uniformly stirring;
(2) adding the suspension obtained in the step (1) into a polytetrafluoroethylene lining, putting the lining into a stainless steel self-pressing kettle, and carrying out hydrothermal treatment at a certain temperature to obtain brown powdery solid;
(3) placing the powder in the step (2) into a tube furnace, and roasting in an inert atmosphere to obtain black powder solid;
(4) and (4) placing the black powder solid in the step (3) into a hydrochloric acid solution with a certain concentration, stirring for 3-6h, removing the template, filtering, washing and drying to obtain the sea urchin-like nitrogen-doped hollow carbon microsphere material.
2. The method according to claim 1, wherein the molar ratio of zinc nitrate to urotropin in step (1) is 1:5 to 5: 1; the weight of the trisodium citrate is 0.01-0.20 times of the weight of the zinc nitrate; the concentration of the carbon precursor is 0.1-0.4 mol/L.
3. The method according to claim 1, wherein the carbon precursor in step (1) is at least one of monosaccharides such as glucose, fructose and galactose and disaccharides such as sucrose, trehalose, maltose and lactose.
4. The method according to claim 1, wherein the hydrothermal temperature in the step (2) is 140-240 ℃ and the reaction time is 12-24 h.
5. The method as claimed in claim 1, wherein the calcination temperature in step (3) is 600-800 ℃. The inert gas is selected from at least one of nitrogen, helium or argon.
6. The method according to claim 1, wherein the prepared 'sea urchin-like' nitrogen-doped hollow carbon microsphere has a diameter of 2-5 μm and a typical mesoporous structure and micropores, and the volume of the micropores accounts for less than 20% of the total volume.
7. The 'sea urchin-like' nitrogen-doped hollow carbon microspheres prepared by the method according to any one of claims 1 to 6.
8. Use of the "echinoid-like" nitrogen-doped hollow carbon microspheres prepared according to the process of any one of claims 1 to 6 as catalyst supports for the hydrogenolysis debenzylation, in particular for the hydrogenolysis debenzylation of HBIW.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113680362A (en) * | 2021-08-18 | 2021-11-23 | 北京工业大学 | Preparation method of palladium hydroxide carbon catalyst for removing N-benzyl |
| CN113912099A (en) * | 2021-11-23 | 2022-01-11 | 新乡学院 | Multilayer calcium carbonate hollow microsphere for drug loading and preparation method and application thereof |
| CN114436239A (en) * | 2021-12-29 | 2022-05-06 | 西安理工大学 | Preparation method of mesoporous carbon microspheres |
| CN114735672A (en) * | 2022-04-24 | 2022-07-12 | 深圳市科信通信技术股份有限公司 | Boron-nitrogen co-doped hard carbon material and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101948130A (en) * | 2010-10-11 | 2011-01-19 | 厦门大学 | Zinc oxide hollow microspheres and preparation method thereof |
| CN103183341A (en) * | 2013-04-02 | 2013-07-03 | 中国矿业大学 | Controllable synthesis method of N-doped graphitized carbon ball with hollow structures |
| CN105152167A (en) * | 2015-10-16 | 2015-12-16 | 合肥工业大学 | Large-scale synthesis method of two-dimensional graphene-like carbon material by using sodium citrate |
| CN109775710A (en) * | 2019-03-16 | 2019-05-21 | 南昌大学 | A kind of preparation method of nitrogen-doped porous carbon material and the application in supercapacitor |
| CN110526228A (en) * | 2019-09-12 | 2019-12-03 | 北京工业大学 | The preparation method of one type petal-shaped carbon nanosheet |
-
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- 2021-03-30 CN CN202110344391.9A patent/CN113003560A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101948130A (en) * | 2010-10-11 | 2011-01-19 | 厦门大学 | Zinc oxide hollow microspheres and preparation method thereof |
| CN103183341A (en) * | 2013-04-02 | 2013-07-03 | 中国矿业大学 | Controllable synthesis method of N-doped graphitized carbon ball with hollow structures |
| CN105152167A (en) * | 2015-10-16 | 2015-12-16 | 合肥工业大学 | Large-scale synthesis method of two-dimensional graphene-like carbon material by using sodium citrate |
| CN109775710A (en) * | 2019-03-16 | 2019-05-21 | 南昌大学 | A kind of preparation method of nitrogen-doped porous carbon material and the application in supercapacitor |
| CN110526228A (en) * | 2019-09-12 | 2019-12-03 | 北京工业大学 | The preparation method of one type petal-shaped carbon nanosheet |
Non-Patent Citations (2)
| Title |
|---|
| JI-YUAN LIANG ET AL.: "Glucose-derived nitrogen-doped hierarchical hollow nest-like carbon nanostructures from a novel template-free method as an outstanding electrode material for supercapacitors", 《JOURNAL OF MATERIALS CHEMISTRY A》 * |
| YAN BAO ET AL.: "Trisodium citrate as bridging and suppressing agent to control synthesis of ZnO hollow hierarchical microspheres and their photocatalytic properties", 《CERAMICS INTERNATIONAL》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113680362A (en) * | 2021-08-18 | 2021-11-23 | 北京工业大学 | Preparation method of palladium hydroxide carbon catalyst for removing N-benzyl |
| CN113912099A (en) * | 2021-11-23 | 2022-01-11 | 新乡学院 | Multilayer calcium carbonate hollow microsphere for drug loading and preparation method and application thereof |
| CN114436239A (en) * | 2021-12-29 | 2022-05-06 | 西安理工大学 | Preparation method of mesoporous carbon microspheres |
| CN114735672A (en) * | 2022-04-24 | 2022-07-12 | 深圳市科信通信技术股份有限公司 | Boron-nitrogen co-doped hard carbon material and preparation method thereof |
| CN114735672B (en) * | 2022-04-24 | 2023-08-25 | 深圳市科信通信技术股份有限公司 | Boron-nitrogen co-doped hard carbon material and preparation method thereof |
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Application publication date: 20210622 |