CN113769712A - Preparation method and application of covalent organic framework compound and open-cage fullerene composite material - Google Patents
Preparation method and application of covalent organic framework compound and open-cage fullerene composite material Download PDFInfo
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Abstract
The invention discloses a preparation method of a covalent organic framework compound and cage-opening fullerene composite material, which is prepared by mixing fullerene with a common-valence organic framework after chemical cage opening, and then carrying out ultrasonic treatment, stirring, washing, soaking and drying on the mixture; in addition, the adsorbent can be applied to adsorbing carbon dioxide, and compared with the traditional adsorbent, the adsorbent has higher nitrogen element doping rate, larger specific surface area and pore volume, and better adsorptivity, selectivity and repeatability. The method is suitable for preparing the covalent organic framework compound and open-cage fullerene composite material, and the prepared composite material can be further applied to carbon dioxide adsorption and can also be used as an electrocatalyst for efficient hydrogen evolution.
Description
Technical Field
The invention belongs to the technical field of chemical synthesis, and relates to preparation of a multifunctional compound, in particular to a preparation method and application of a composite material of a covalent organic framework compound and cage-opening fullerene.
Background
Along with the rapid development of global industrialization, fossil resources are greatly developed and consumed, and meanwhile, a serious environmental pollution problem comes along, the scarcity and pollution of global fossil resources become topics of urgent attention, and researches on the purposes of replacing fossil energy, reducing carbon emission, relieving increasingly severe environmental pollution and greenhouse effect and obtaining high-value-added chemicals become targets pursued by more and more people.
The covalent organic framework has a stable pi-conjugated stable structure and a large specific surface area, and the adsorption amount of the covalent organic framework can be adjusted by adjusting the size of the pore diameter, so that the covalent organic framework can play a large role in the adsorption process of carbon dioxide gas.
Meanwhile, due to the special spatial structure of the covalent organic framework, the covalent organic framework can be used as a special catalyst for catalyzing water into hydrogen and oxygen, namely an electrocatalyst, the hydrogen is prepared and stored by the electrocatalyst, and the hydrogen can be converted into electric energy at any time, the only byproduct in the whole engineering is water, and the water can be recycled, so that the requirement of green chemical engineering is met. At present, noble metal platinum is an electrochemical hydrogen evolution catalyst with highest catalytic efficiency and best effect in the hydrogen production process, but the expensive price of the noble metal platinum becomes the key for limiting the platinum catalyst, so that the design and development of a novel electrocatalyst with wide sources and low price and the improvement of the electrocatalysis performance are urgent matters of electrocatalysis energy conversion at present.
The cage-opening fullerene can be prepared by using fullerene C60 as a starting material and a chemical cage-opening method, and the carbon dioxide adsorption amount can be increased by introducing an edge strong polar group-C ═ O (hydroxyl) and an electron-rich group-N ═ N- (diazo) into the edge of the cage-opening fullerene. The covalent organic framework is doped into the open-cage fullerene, so that the aperture size can be adjusted, and different requirements can be met by grafting different functional groups.
Disclosure of Invention
The invention aims to provide a preparation method of a covalent organic framework compound and open-cage fullerene composite material
In order to achieve the purpose, the invention adopts the technical scheme that:
a preparation method of a covalent organic framework compound and cage-opening fullerene composite material comprises the following steps of:
s1. preparation of covalent organic framework Compounds
S11, placing 1,3,6, 8-tetra (4-formaldehyde phenyl) pyrene and p-phenylenediamine in a container, adding acetic acid and a solvent X for ultrasonic dissolution, exhausting air from the container, and sealing the container in a degassing state;
s12, heating the sealed container at room temperature and reacting to obtain a reactant A;
s13, washing, soaking and drying the reactant A in sequence to obtain a covalent organic framework compound;
s2, preparation of cage-opening fullerene
S21, taking C60 and 3- (2-pyridyl) -5, 6-diphenyl-1, 2, 4-triazine, adding a solvent Y for dissolving, heating and refluxing, cooling, eluting, purifying and secondarily eluting to obtain a reactant B;
s22, dissolving the reactant B in a solvent Z, and sequentially carrying out high-pressure mercury lamp irradiation, rotary evaporation and elution to obtain cage-opened fullerene;
s3, preparation of covalent organic framework compound and open-cage fullerene composite material
And (3) taking out the cage-opening fullerene, adding a solvent W to dissolve the cage-opening fullerene, adding the covalent organic framework compound, and sequentially performing ultrasonic treatment, stirring, washing, soaking and drying to obtain the covalent organic framework compound and cage-opening fullerene composite material.
As one limitation, in step S11, the solvent X is 1,4 dioxane or o-dichlorobenzene;
the ultrasonic time is 0.5-1 h;
the air suction is carried out under the condition of liquid nitrogen;
the molar ratio of the 1,3,6, 8-tetra (4-formaldehyde phenyl) pyrene to the p-phenylenediamine to the acetic acid is 1:1-3: 10-20.
As another limitation, in step S12, the temperature raising rate is 3-5 ℃/h, and the temperature after temperature raising is 200-;
the reaction time is 40-50 h.
As a third limitation, in step S13, the washing is performed by sequentially washing with acetone, methanol, and 1, 4-dioxane;
the soaking is to soak in acetone for 10 to 15 hours;
the drying is carried out at 70-90 ℃ under vacuum condition for 8-15 h.
As a fourth limitation, in step S21, the solvent Y is ortho-dichlorobenzene, toluene or chlorobenzene;
the temperature of the heating reflux is 150-200 ℃, and the time is 20-30 h;
the temperature after cooling is 20-30 ℃;
the elution is carried out by taking carbon disulfide as an eluent;
the purification is carried out by using a silica gel column;
the eluent for secondary elution is formed by mixing ethyl acetate and carbon disulfide in a volume ratio of 1: 40-80;
the molar ratio of the 3- (2-pyridyl) -5, 6-diphenyl-1, 2, 4-triazine to the C60 is 10: 3-8.
As a fifth limitation, in step S22, the solvent Z is carbon tetrachloride, chloroform or carbon disulfide;
the power of the high-pressure mercury lamp is 120-180 watts, and the irradiation time is 60-80 h;
the eluent for elution is formed by mixing ethyl acetate and carbon disulfide in a volume ratio of 1: 40-80.
As a sixth limitation, in step S3, the solvent W is at least one of chloroform, carbon tetrachloride and carbon disulfide;
the ultrasonic temperature is 20-30 deg.C, and the ultrasonic time is 10-15min;
the stirring temperature is 20-30 ℃, the rotating speed is 1000-2000rpm, and the time is 20-30 h;
the washing is carried out by sequentially using acetone, methanol and 1, 4-dioxane;
the soaking is to soak in acetone for 10 to 15 hours;
the drying is carried out at 70-90 ℃ under the vacuum condition for 8-15 h;
the mass ratio of the cage-opening fullerene to the covalent organic framework compound is 1: 0.5-4.
The invention also provides an application of the covalent organic framework compound and the cage-opening fullerene composite material prepared by the preparation method of the covalent organic framework compound and the cage-opening fullerene composite material, and the covalent organic framework compound and the cage-opening fullerene composite material are used for preparing hydrogen in industrial electrocatalytic hydrogen evolution reaction.
The invention also provides another application of the covalent organic framework compound and the open-cage fullerene composite material prepared by the preparation method of the covalent organic framework compound and the open-cage fullerene composite material, and the covalent organic framework compound and the open-cage fullerene composite material are used for adsorbing carbon dioxide.
Due to the adoption of the technical scheme, compared with the prior art, the invention has the technical progress that:
the preparation method of the invention provides strong electron group by inserting cage-opening fullerene into the hole of the covalent organic framework compound, increases the adsorptivity of the composite material, changes the characteristics of the framework, thereby forming the covalent organic framework compound and cage-opening fullerene composite material for carbon dioxide adsorption;
the preparation method is simple, wide in raw material source and low in cost;
the preparation method of the invention takes a high specific surface area covalent organic framework as a substrate, and is doped with cage-opening fullerene with different mass fractions, and the prepared composite material of the covalent organic framework and the cage-opening fullerene has the characteristics of higher nitrogen element doping, larger specific surface area, higher pore volume, pore diameter concentrated in a micropore area and the like, increases the interaction force of carbon dioxide molecules and a main body material, improves the selectivity and the adsorption capacity of the composite material to carbon dioxide, can be repeatedly used, and has the advantages of environmental protection, convenient recovery and the like;
the preparation method of the invention changes the loading capacity of the cage-opening fullerene by adjusting the mass ratio of the cage-opening fullerene to the common organic frame, and synthesizes the electrocatalyst with high-efficiency hydrogen evolution;
the preparation method of the invention selects covalent organic framework as rigid framework, selects open-cage fullerene with better conductivity, dopes open-cage fullerene on the rigid framework, increases the conductivity of the composite material, changes the characteristics of the framework, and uses-C-N-C-O of the open-cage fullerene as catalytic hydrogen evolution to increase active sites, so that the overpotential is obviously reduced compared with intrinsic material, thereby enhancing the catalytic activity of the catalyst, when the dosage ratio of the covalent organic framework compound to the open-cage fullerene is 1:1, the catalyst is used at 10 mA-cm-2The overpotential is 283mV, and the Tafel slope is 130mV dec-1Under the acidic condition, the catalytic reaction can stably circulate for 2000 circles, noble metal is not used in the composite material, the cost is greatly reduced, and the cost of hydrogen evolution by water electrolysis is reduced while the catalytic efficiency is ensured;
the covalent organic framework compound and open cage fullerene composite material prepared by the preparation method can be used as a carbon dioxide adsorbent and also can be used as a catalyst in industrial electro-catalytic hydrogen evolution reaction.
The preparation method is suitable for preparing the covalent organic framework compound and open-cage fullerene composite material, and the prepared covalent organic framework compound and open-cage fullerene composite material is suitable for preparing hydrogen in industrial electrocatalytic hydrogen evolution reaction and is also suitable for adsorbing carbon dioxide.
Drawings
The invention will be described in more detail with reference to the following figures and embodiments:
FIG. 1 is a scanning electron micrograph of a covalent organic framework compound prepared according to example 1 of the present invention;
FIG. 2 is BET data for a covalent organic framework compound prepared in example 1 of the present invention;
FIG. 3 is a transmission electron micrograph of a covalent organic framework compound prepared according to example 1 of the present invention;
FIG. 4 is an XRD pattern spectrum of a composite material of a covalent organic framework compound and an open cage fullerene prepared in example 13 of the present invention;
FIG. 5 shows the results of the electro-catalytic hydrogen evolution test of the covalent organic framework compound and cage-opened fullerene composite material prepared in example 13 of the present invention;
FIG. 6 is an electrocatalytic process of a covalent organic framework compound and cage-opened fullerene composite prepared in example 13 of the present invention;
fig. 7 is a transmission electron microscope image of the covalent organic framework compound and the cage-opened fullerene composite material prepared in example 13 of the present invention.
Detailed Description
The present invention is further illustrated by the following specific examples, which are to be construed as merely illustrative, and not limitative of the remainder of the disclosure.
EXAMPLE 1 preparation of a covalent organic framework Compound
The embodiment comprises the following steps which are carried out in sequence:
s11, respectively weighing 3.09kg (5mol) of 1,3,6, 8-tetra (4-formaldehyde phenyl) pyrene and 1.08kg (10mol) of p-phenylenediamine, placing the materials in a container, adding o-dichlorobenzene to perform ultrasonic treatment for 30min, performing auxiliary dissolution to form a uniform solution, adding 4.65kg (77.5mol) of acetic acid in the ultrasonic treatment process, freezing the container under the condition of liquid nitrogen, exhausting air from the container to remove oxygen, and sealing the container in a degassing state;
s12, heating the sealed container to 250 ℃ at the temperature rise rate of 5 ℃/h at the temperature rise rate of 25 ℃, and reacting for 48h to obtain a reactant A;
s13, washing the reactant A with acetone, methanol and dioxane in sequence, soaking the reactant A with acetone for 12 hours, and finally drying the reactant A under vacuum at 80 ℃ for 12 hours to obtain a covalent organic framework compound X1.
The scanning electron micrograph of the covalent organic framework compound X1 prepared in the embodiment is shown in FIG. 1, and it can be seen from FIG. 1 that small particles with the diameter of 100-200 nm are attached to the surface of nanoparticles with the radial size of 10-20 nm; as can be seen from FIG. 1b, the composite material has a rod-like structure with a size of about 100 nm;
the BET data for the covalent organic framework Compound X1 prepared in this example is shown in FIG. 2, and the porosity of the covalent organic framework polymeric network is determined by the N measured at 77K2The adsorption and desorption isotherms were characterized, and in FIG. 2, the covalent organic framework was in the lower relative pressure range (P/P0)<0.01) exhibit stronger N2The adsorption amount indicates that a large amount of microporous structures exist in the void structure, and the nitrogen adsorption amount of the covalent organic framework is also rapidly increased with the increase of the relative pressure. Finally, by calculation of the Brunauer-Emmett-Teller (BET) equation, we can obtain a specific surface area of 2087.251m for the covalent organic framework compound X12g–1；
The transmission electron micrograph of the covalent organic framework compound X1 prepared in this example is shown in FIG. 3.
Examples 2-6 preparation of covalent organic framework Compounds
Examples 2-6 are processes for the preparation of covalent organic framework compounds, respectively, which are essentially the same as example 1 except for the differences in raw material amounts and process parameters, as detailed in table 1:
TABLE 1 summary of the process parameters of examples 2-6
Example 7 preparation method of cage-opened fullerene
The embodiment comprises the following steps which are carried out in sequence:
s21, dissolving 3.1kg (10mol) of 3- (2-pyridyl) -5, 6-diphenyl-1, 2, 4-triazine and 3.6kg (5mol) of C60 in 9L o-dichlorobenzene, heating to reflux for 24h at 150 ℃, cooling to room temperature, and adding CS2Subjecting the eluate to silica gel column chromatography, removing unreacted C60, and adding CS2Carrying out secondary elution with an eluent mixed with ethyl acetate in a volume ratio of 80:1 to obtain a reactant B;
s22, dissolving 10g of reactant B in 10L of CCl4In the middle, a 150 watt high-pressure mercury lamp is used for irradiating for 72 hours in an oxygen atmosphere, and the solution is changed from pink purple to tan; performing rotary evaporation on the solution, performing silica gel column chromatography on the residue, and performing CS2Eluting with solution mixed with ethyl acetate at a volume ratio of 80:1, collecting the second brown band, and evaporating to obtain fullerene product, i.e. open cage fullerene Y1.
Example 8-12 preparation of cage-opening Fullerene
Examples 8 to 12 are methods of producing an open-cage fullerene, respectively, and the steps are substantially the same as in example 7, except for the differences in the amounts of the raw materials and the process parameters, as detailed in table 2:
TABLE 2 summary of the process parameters of examples 8-12
Example 13 preparation method of a covalent organic framework compound and cage-opened fullerene composite
The embodiment comprises the following steps which are carried out in sequence:
dissolving 10kg of cage-opening fullerene in chloroform to form a uniform solution, weighing 10kg of covalent compound X1, adding into the solution, carrying out ultrasound for 15min at 20 ℃, stirring for 24h at the rotation speed of 1500rpm, sequentially washing with acetone, methanol and dioxane, soaking in acetone for 12h, and finally carrying out vacuum drying at 80 ℃ for 12h to obtain a covalent organic framework compound and cage-opening fullerene composite material Z1;
the XRD pattern of the covalent organic framework compound prepared in this example and the open-cage fullerene composite material Z1 is shown in fig. 4, and it can be seen from fig. 4 that diffraction peaks appear when 2 θ is 3.7 °, 7.5 °, 11.1 ° and 23.58 °, corresponding to the (110), (220), (330) and (001) crystal planes, respectively, wherein the diffraction peak when 2 θ is 23.58 ° proves that the polymer is formed by two-dimensional blocky stacking, and the structure is favorable for increasing the migration rate of electrons;
the transmission electron micrograph of the covalent organic framework compound and the open cage fullerene composite material prepared in the example is shown in FIG. 7.
Examples 14-18 preparation of composite of covalent organic framework Compounds and cage-opening Fullerene
Examples 14 to 18 are methods of preparing a covalent organic framework compound and a caged fullerene composite, respectively, which have substantially the same steps as in example 13, except for the amount of raw materials and the process parameters, as detailed in table 2:
TABLE 3 summary of the process parameters of examples 14-18
EXAMPLE 19 electrocatalytic testing of covalent organic framework Compounds with cage-opened Fullerene composites
The embodiment provides an application of a covalent organic framework compound and open-cage fullerene composite material prepared by the preparation method of any one of the covalent organic framework compounds and open-cage fullerene composite materials in embodiments 13-18, and the application is used for preparing hydrogen by a catalyst in an industrial electro-catalytic hydrogen evolution reaction.
The mass ratio of the open-cage fullerene to the covalent organic framework compound of the composite material of the covalent organic framework compound and the open-cage fullerene obtained in the embodiments 13 to 18 is 1:0.5-4, and when the open-cage fullerene and the covalent organic framework compound are applied to the electrocatalytic hydrogen evolution reaction, the linear scanning curve of the performance is shown in fig. 5:
FIG. 5a is a polarization curve of hydrogen evolution reaction of a covalent organic framework compound and an open-cage fullerene composite material prepared from COFs (covalent organic framework compound), mC60 (open-cage fullerene), Pt/C (platinum-carbon ratio) of 20%, and COFs and MC60 with different doping ratios, and it can be seen from the polarization curve that only 283mV of voltage is needed to drive 10mAcm cm when hydrogen evolution reaction occurs between the covalent organic framework compound and the open-cage fullerene composite material under acidic conditions-2The current density of the composite material is shown in the specification, the conjugated framework formed by the conjugated framework of the IL-COFs can enhance the delocalization effect of electrons, improve the rapid migration of the electrons on the surface of the conjugated framework, and simultaneously, the impedance of a reaction system can be reduced by doping cage-opening fullerene, so that the electrocatalytic composite material is proved to have higher catalytic activity;
FIG. 5b is a comparison of the Tafel slope of a covalent organic framework compound versus an open cage fullerene composite, as can be seen, 130mV dec-1The tafel slope of the compound proves that the compound has higher intrinsic reaction activity;
fig. 5c is a measurement result of impedance performance of a covalent organic framework compound and open-cage fullerene composite material, from which it can be known that the impedance of the whole composite material can be reduced by doping open-cage fullerene into IL-COFs, when IL-COFs @ mC60 is 3:1, the radius is minimum, the electron transfer resistance on the surface of the composite material is minimum, and the reaction rate is faster;
FIG. 5d is a measurement result of the stability of the covalent organic framework compound and the open-cage fullerene composite material in the electrocatalysis process, and it can be known that the covalent organic framework compound and the open-cage fullerene composite material have higher stability in the electrocatalysis process and still have activity after 2000 cycles of the cycle test;
the reaction scheme of catalyzing hydrogen evolution by using the covalent organic framework compound prepared in examples 8-13 and the cage-opening fullerene composite material is shown in fig. 6;
in conclusion, the covalent organic framework compound and the open cage fullerene composite material are most suitable for industrial electro-catalytic hydrogen evolution production under the acidic condition.
Claims (10)
1. A preparation method of a covalent organic framework compound and cage-opening fullerene composite material is characterized by comprising the following steps of:
s1. preparation of covalent organic framework Compounds
S11, placing 1,3,6, 8-tetra (4-formaldehyde phenyl) pyrene and p-phenylenediamine in a container, adding acetic acid and a solvent X for ultrasonic dissolution, performing air suction on the container to a degassing state, and then sealing;
s12, heating the sealed container at room temperature and reacting to obtain a reactant A;
s13, washing, soaking and drying the reactant A in sequence to obtain a covalent organic framework compound;
s2, preparation of cage-opening fullerene
S21, taking C60 and 3- (2-pyridyl) -5, 6-diphenyl-1, 2, 4-triazine, adding a solvent Y for dissolving, heating and refluxing, cooling, eluting, purifying and secondarily eluting to obtain a reactant B;
s22, dissolving the reactant B in a solvent Z, and sequentially carrying out high-pressure mercury lamp irradiation, rotary evaporation and elution to obtain cage-opened fullerene;
s3, preparation of covalent organic framework compound and open-cage fullerene composite material
And (3) taking out the cage-opening fullerene, adding a solvent W to dissolve the cage-opening fullerene, adding the covalent organic framework compound, and sequentially performing ultrasonic treatment, stirring, washing, soaking and drying to obtain the covalent organic framework compound and cage-opening fullerene composite material.
2. The method of claim 1, wherein in step S11, the solvent X is 1,4 dioxane or o-dichlorobenzene;
the ultrasonic time is 0.5-1 h;
the air suction is carried out under the condition of liquid nitrogen;
the molar ratio of the 1,3,6, 8-tetra (4-formaldehyde phenyl) pyrene to the p-phenylenediamine to the acetic acid is 1:1-3: 10-20.
3. The method for preparing a covalent organic framework compound and caged fullerene composite material according to claim 1 or 2, wherein in step S12, the temperature rise rate is 3-5 ℃/h, and the temperature after temperature rise is 200-300 ℃;
the reaction time is 40-50 h.
4. The method for preparing a covalent organic framework compound and caged fullerene composite material according to claim 1 or 2, wherein in step S13, the washing is performed by sequentially washing with acetone, methanol and 1, 4-dioxane;
the soaking is to soak in acetone for 10 to 15 hours;
the drying is carried out at 70-90 ℃ under vacuum condition for 8-15 h.
5. The method for preparing a composite material of a covalent organic framework compound and a cage-opened fullerene according to claim 1 or 2, wherein in step S21, the solvent Y is o-dichlorobenzene, toluene or chlorobenzene;
the temperature of the heating reflux is 150-200 ℃, and the time is 20-30 h;
the temperature after cooling is 20-30 ℃;
the elution is carried out by taking carbon disulfide as an eluent;
the purification is carried out by using a silica gel column;
the eluent for secondary elution is formed by mixing ethyl acetate and carbon disulfide in a volume ratio of 1: 40-80;
the molar ratio of the 3- (2-pyridyl) -5, 6-diphenyl-1, 2, 4-triazine to the C60 is 10: 3-8.
6. The method for preparing a covalent organic framework compound and cage-opened fullerene composite material according to claim 1 or 2, wherein in step S22, the solvent Z is carbon tetrachloride, chloroform or carbon disulfide;
the power of the high-pressure mercury lamp is 120-180 watts, and the irradiation time is 60-80 h;
the eluent for elution is formed by mixing ethyl acetate and carbon disulfide in a volume ratio of 1: 40-80.
7. The method for preparing a covalent organic framework compound and cage-opened fullerene composite material according to claim 1 or 2, wherein in step S3, the solvent W is at least one of chloroform, carbon tetrachloride and carbon disulfide;
the ultrasonic temperature is 20-30 deg.C, and the ultrasonic time is 10-15min;
the stirring temperature is 20-30 ℃, the rotating speed is 1000-2000rpm, and the time is 20-30 h;
the washing is carried out by sequentially using acetone, methanol and 1, 4-dioxane;
the soaking is to soak in acetone for 10 to 15 hours;
the drying is carried out at 70-90 ℃ under the vacuum condition for 8-15 h;
the mass ratio of the cage-opening fullerene to the covalent organic framework compound is 1: 0.5-2.
8. The method of claim 3, wherein in step S3, the solvent W is at least one of chloroform, carbon tetrachloride and carbon disulfide;
the ultrasonic temperature is 20-30 deg.C, and the ultrasonic time is 10-15min;
the stirring temperature is 20-30 ℃, the rotating speed is 1000-2000rpm, and the time is 20-30 h;
the washing is carried out by sequentially using acetone, methanol and 1, 4-dioxane;
the soaking is to soak in acetone for 10 to 15 hours;
the drying is carried out at 70-90 ℃ under the vacuum condition for 8-15 h;
the mass ratio of the cage-opening fullerene to the covalent organic framework compound is 1: 0.5-2.
9. Use of a covalent organic framework compound and open-cage fullerene composite prepared by the method according to any one of claims 1-8 for the preparation of a covalent organic framework compound and open-cage fullerene composite for the preparation of hydrogen in an industrial electrocatalytic hydrogen evolution reaction.
10. Another use of a covalent organic framework compound and open-cage fullerene composite prepared by the method of preparing a covalent organic framework compound and open-cage fullerene composite according to any one of claims 1-8, wherein the covalent organic framework compound and open-cage fullerene composite is used for carbon dioxide adsorption.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1718538A (en) * | 2004-07-08 | 2006-01-11 | 北京化工大学 | Method of perforating on fullerene ball surface |
| WO2013131521A1 (en) * | 2012-03-05 | 2013-09-12 | Kyoto University | Open-cage fullerenes and a method for preparing the same |
| CN110116025A (en) * | 2019-05-30 | 2019-08-13 | 河北科技大学 | Covalent triazine class framework compound and MoS2The preparation method of compound liberation of hydrogen catalyst and the application of liberation of hydrogen catalyst |
| CN110483797A (en) * | 2019-08-28 | 2019-11-22 | 南京大学 | The method of carbon material surface in-situ preparation polyimide type covalent organic frame material |
-
2021
- 2021-07-27 CN CN202110852606.8A patent/CN113769712B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1718538A (en) * | 2004-07-08 | 2006-01-11 | 北京化工大学 | Method of perforating on fullerene ball surface |
| WO2013131521A1 (en) * | 2012-03-05 | 2013-09-12 | Kyoto University | Open-cage fullerenes and a method for preparing the same |
| CN110116025A (en) * | 2019-05-30 | 2019-08-13 | 河北科技大学 | Covalent triazine class framework compound and MoS2The preparation method of compound liberation of hydrogen catalyst and the application of liberation of hydrogen catalyst |
| CN110483797A (en) * | 2019-08-28 | 2019-11-22 | 南京大学 | The method of carbon material surface in-situ preparation polyimide type covalent organic frame material |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114520325A (en) * | 2022-01-07 | 2022-05-20 | 惠州锂威新能源科技有限公司 | Preparation method of nitrogen-doped carbon material, product, negative plate and secondary battery |
| CN114520325B (en) * | 2022-01-07 | 2023-07-04 | 惠州锂威新能源科技有限公司 | Preparation method of nitrogen-doped carbon material, product, negative electrode plate and secondary battery |
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