WO2020024766A1 - 一种杂原子掺杂的聚合物纳米微球/炭纳米微球及其制备方法 - Google Patents

一种杂原子掺杂的聚合物纳米微球/炭纳米微球及其制备方法 Download PDF

Info

Publication number
WO2020024766A1
WO2020024766A1 PCT/CN2019/094807 CN2019094807W WO2020024766A1 WO 2020024766 A1 WO2020024766 A1 WO 2020024766A1 CN 2019094807 W CN2019094807 W CN 2019094807W WO 2020024766 A1 WO2020024766 A1 WO 2020024766A1
Authority
WO
WIPO (PCT)
Prior art keywords
preparation
solution
mol
reaction
microspheres
Prior art date
Application number
PCT/CN2019/094807
Other languages
English (en)
French (fr)
Inventor
吕荣文
刘明辉
刘盈岑
林华
Original Assignee
大连理工大学
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from CN201810857851.6A external-priority patent/CN108822274B/zh
Priority claimed from CN201810858599.0A external-priority patent/CN108862240B/zh
Application filed by 大连理工大学 filed Critical 大连理工大学
Priority to US17/265,199 priority Critical patent/US11919772B2/en
Publication of WO2020024766A1 publication Critical patent/WO2020024766A1/zh

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • 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
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/06—Making microcapsules or microballoons by phase separation
    • B01J13/14—Polymerisation; cross-linking
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
    • C01B21/086—Compounds containing nitrogen and non-metals and optionally metals containing one or more sulfur atoms
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
    • C08G12/04—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
    • C08G12/06—Amines
    • C08G12/08—Amines aromatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
    • C08G12/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
    • C08G12/30—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with substituted triazines
    • C08G12/32—Melamines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
    • C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer

Definitions

  • the invention belongs to the technical field of new nanomaterials, and particularly relates to a heteroatom-doped polymer nanomicrosphere / carbon nanomicrosphere and a preparation method thereof.
  • Heteroatom-doped polymer nanospheres have great advantages in carbon dioxide adsorption and separation, labeling and detection, flame retardancy, removal of metal ions in water, gas storage and separation, and synthesis of hollow nanospheres and porous nanomaterials by hard template method.
  • the application potential has received widespread attention in recent years.
  • Doping non-metallic impurities such as sulfur, nitrogen, boron, phosphorus, or multiple heteroatoms on the carbon atom skeleton can effectively improve its application performance.
  • nitrogen-doped polymer nanospheres have better CO 2 adsorption performance.
  • the current research on non-metal heteroatom doping mainly focuses on single non-metal heteroatom doping. For example, the preparation of nitrogen-containing carbon nanospheres starting from melamine.
  • heteroatom doping Two or more kinds of heteroatom doping involve less, even if it involves It also uses heteroatom-containing amino acids as one of the raw materials to synthesize heteroatom-doped polymer nanomaterials under hydrothermal conditions.
  • the operation is complicated, time-consuming, and energy-consuming.
  • Heteroatom-doped carbon nanospheres have great application potential in energy conversion and storage, carbon dioxide adsorption and separation, metal ion removal in water, gas storage and separation, and catalysis.
  • Doping non-metal heteroatoms on the carbon atom skeleton such as sulfur, nitrogen, boron, phosphorus, or multiple heteroatoms, can effectively improve its application performance.
  • sulfur and nitrogen doped graphene materials due to heteroatom Synergistic effect, better oxygen reduction performance than undoped graphene; the presence of heteroatoms can give carbon materials good electrical conductivity, chemical stability and catalytic performance.
  • the current research on non-metal heteroatom doping also focuses on single non-metal heteroatom doping.
  • Two or more kinds of heteroatom doping are less involved, even if it involves multi-step synthesis and post-doping.
  • elemental sulfur, Na 2 S or urea is used to process nitrogen-containing carbon materials at high temperature to obtain nitrogen and sulfur doped carbon materials, and because it uses post-doping technology, from the perspective of microscopic particle morphology, Atoms are not uniformly doped; or doped polymer nanomaterials are synthesized under hydrothermal conditions, and heteroatom-doped carbon nanospheres are obtained after calcination, which is also complicated, time-consuming, and energy-consuming.
  • the hydrothermal method starting from melamine also first prepares the prepolymer, and then polymerizes the prepolymer under hydrothermal conditions to obtain melamine formaldehyde resin microspheres; the hydrothermal method starting from starch or glucose requires heteroatom-containing amino acids to participate in the microspheres Formation.
  • the hydrothermal method requires a higher reaction temperature and a longer reaction time, and the yield is low, and it is difficult to achieve large-scale industrial application.
  • the above-mentioned water bath heating method obtains carbon microspheres containing only nitrogen, and after firing, it is only carbon nanospheres containing nitrogen; the reaction temperature is high, the time is long, and the operation is complicated.
  • the purpose of the present invention is to provide a method for preparing heteroatom-doped polymer nano-microspheres with simple process operation, mild conditions, and fast reaction.
  • the method uses a mild reaction temperature (10-50 ° C) under stirring conditions. ), Using arylamine and aldehyde as raw materials, in the presence of the compound represented by the general formula I, in an aqueous solution system, the aldehyde and the compound represented by the general formula I are formed into a Schiff base, and the aromatic amine is added to the generated Schiff base
  • the heteroatom-doped polymer nano-microspheres are prepared.
  • the user can calcine the polymer nano-microspheres in an inert gas atmosphere to prepare carbon nano-microspheres according to different needs.
  • the size and morphology of the nanosphere product prepared by this method are controllable, the particle size is uniform, the yield is large, and the heteroatom is doped uniformly.
  • the method for preparing heteroatom-doped polymer nanomicrospheres according to the present invention includes the following steps:
  • R 1 is selected from H, NH 2 ;
  • R 2 is selected from H, COOH, SO 3 H, B (OH) 2 , OPO (OH) 2 , Cl, OCH 3 , CN, OH, SH, NO 2 ;
  • R 3 is selected from H, SO 3 H;
  • the aromatic amine in step (1) is selected from one or more of the following: melamine, or 1,3-phenylenediamine, 1,4-phenylenediamine, 1,3-xylylenediamine, 1 1,4-xylylenediamine, tris (4-aminophenyl) amine, 2,4,6-triaminopyrimidine, 2,6-diaminopyridine, 1,5-diaminonaphthalene, 1,4-diamino Naphthalene, 2,3-diaminonaphthalene and 1,8-diaminonaphthalene;
  • the concentration of the aromatic amine solution is 0.015 to 1.0 mol / L; wherein the preferred range of the concentration of the aromatic amine solution is 0.02 to 0.5 mol / L; most The optimal arylamine solution concentration is 0.03 to 0.2 mol / L; when a melamine solution is preferred, a concentration of 0.038 mol / L is the best condition.
  • the compound represented by Formula I in the step (1) includes: 2,4-diaminobenzenesulfonic acid, anthranilic acid, and m-aminobenzene Sulfonic acid, p-aminobenzenesulfonic acid, m-phenylenediamine disulfonic acid, 3,5-diaminobenzoic acid, p-aminochlorobenzene, p-aminoanisole, p-aminobenzonitrile, p-aminophenol, anthranilic acid
  • the concentration of the compound-forming solution of the general formula I is 0.015 to 0.2 mol / L; the preferred concentration range is 0.004 to 0.1 mol / L; the optimal solution concentration 0.006 to 0.008 mol / L; when a 2,4-diaminobenzenesulfonic acid solution is preferred, a concentration of 0.0076 g / mL is the best condition.
  • the ammonia solution added in the step (2) is added dropwise, and the stirring time is 1 to 10 minutes to gradually form a clear, transparent solution.
  • the aldehyde used in step (3) includes formaldehyde or fatty dialdehyde; wherein, the formaldehyde is a commercially available formaldehyde aqueous solution product; the Fatty dialdehydes include glyoxal, malonaldehyde, succinaldehyde, glutaraldehyde, adipaldehyde, etc .;
  • the aldehyde described in step (3) is added in a dropwise manner, and the amount of the aldehyde used is 5-12 times the equivalent of the amount of aldehyde groups relative to the aromatic amine.
  • the preferred amount of aldehyde used is 8 to 10 times the equivalent of the amount of aldehyde groups relative to the aromatic amine.
  • the most preferred amount of aldehyde used is 9 times the equivalent of aldehyde group relative to the aromatic amine.
  • step (3) after the aldehyde is added in step (3), the solution is stirred and the solution changes from clarified to turbid with time; keep the reaction stirred for 0.2 to 6 hours, Dry to obtain polymer nano microspheres with uniform particle size, controllable size and morphology, and good dispersibility;
  • the preferred temperature range in the steps (1) to (3) is 20 to 35 ° C; the optimal temperature is 25 ° C.
  • the above-mentioned method of the present invention uses aromatic amines and aldehydes as basic raw materials, the reaction system is water, and the addition of ammonia water to adjust the pH of the reaction is beneficial to the regulation of the uniformity and morphology of polymer nanospheres.
  • the addition of the compound is beneficial to the rapid formation and morphology control of the nanospheres.
  • the concentration of the basic raw materials in the system, the concentration of the compound shown by the general formula I, and the amount of ammonia water are mutually restricted.
  • the polymer nano By changing the ratio of the compound represented by the general formula I to the aromatic amine, the ratio of the aromatic amine to the aldehyde, the concentration of the aromatic amine, different amounts of ammonia water added, and different reaction temperatures (10-50 ° C), the polymer nano The particle size of the microspheres is well regulated.
  • Nanometer microspheres have a diameter of 30nm ⁇ 3 ⁇ m, and have uniform particle size, uniform heteroatom distribution, adjustable particle size, and good dispersibility.
  • the invention discloses a method for preparing nitrogen-containing sulfur carbon nano-microspheres, that is, the heteroatom-doped polymer nano-microspheres described above are prepared by baking under an inert gas atmosphere.
  • the specific method is as follows: On the basis of the above method for preparing polymer nanospheres, the method further includes step (4): the polymer nanospheres obtained in step (3) are centrifuged, dried, and then calcined in an inert gas atmosphere. A heteroatom-doped carbon nanosphere was obtained.
  • the product is centrifuged at 6000 rpm and then washed with a 20% ethanol solution. This process is repeated three times (or directly dried without washing), and then centrifuged and dried. To obtain nanometer microspheres with uniform particle size, controllable morphology, and good dispersibility.
  • the firing conditions described in step (4) are 300 to 800 ° C, preferably 400 to 600 ° C, and more preferably 500 ° C.
  • the roasting conditions described in step (4) are based on room temperature as the starting temperature, the roasting temperature rise rate is the same at 2.5 ° C / min, the constant temperature is maintained at 100 ° C for 30 minutes, the intermediate program temperature is maintained at constant temperature for 60 minutes, and the final roasting temperature is maintained at 120 Minutes, then cool down naturally.
  • the roasting conditions used in the examples of the present invention are: starting at room temperature, increasing to 2.5 ° C / min to 100 ° C, maintaining a constant temperature for 30 minutes, and then increasing to 2.5 ° C / min to 300 ° C. The temperature was kept constant for 60 minutes, and then raised to 500 ° C at 2.5 ° C / min. The temperature was kept constant for 120 minutes. Finally, the temperature was naturally reduced to obtain carbon nanospheres.
  • the nitrogen content of the nitrogen-containing sulfur carbon nanospheres described in the present application is 1% to 60%, preferably 20 to 60%, and the sulfur content is 0.1% to 8%, and the content is adjustable.
  • Nanometer microspheres have a diameter of 30nm ⁇ 2 ⁇ m, and have uniform particle size, uniform heteroatom distribution, adjustable size, and good dispersibility.
  • the method of the present invention adopts a new process route, which can be produced at a mild operating temperature (10-50 ° C); avoiding the relatively harsh 70-100 ° C or hydrothermal reaction conditions used in traditional processes; It is especially suitable for rapid operation at normal temperature (20 ⁇ 35 ° C), which is more conducive to popularization and application.
  • the process adopted by the present invention is simple, easy to operate, large in output, and can be used to control the ratio of the compound shown by general formula I to the aromatic amine, the ratio of the aromatic amine to the aldehyde, the concentration of the aromatic amine, and the Polymer nano-microspheres / carbon nano-microspheres with controllable size and morphology were obtained by adding ammonia water and different reaction temperatures (10-50 ° C).
  • step (3) a product is formed within a few minutes after the aldehyde is added dropwise. Under stirring conditions, the solution changes from clarified to cloudy with time, and the product gradually increases, and After the reaction is completed, the remaining reaction solution after centrifugal removal of all polymer nanospheres need not be discarded, and can be recycled for recycling.
  • the method of the present invention can expand the use of fatty dialdehydes with high carbon numbers, and can avoid the use of formaldehyde, a harmful substance.
  • Figure 1 SEM image of 10 g of melamine reacted with 2,4-diaminobenzenesulfonic acid nanospheres
  • Figure 2 SEM images of 2,4-diaminobenzenesulfonic acid participating in the reaction at different temperatures
  • Figure 3 SEM images of different concentrations of 2,4-diaminobenzenesulfonic acid participating in the reaction microspheres;
  • Figure 4 SEM images of 2,4-diaminobenzenesulfonic acid participating in the reaction of nanospheres under different amounts of melamine;
  • Figure 5 SEM images of 2,4-diaminobenzenesulfonic acid participating in the reaction of nano-microspheres under different amounts of ammonia water;
  • Figure 6 SEM images of 2,4-diaminobenzenesulfonic acid participating in the reaction of nanospheres under different amounts of formaldehyde;
  • Figure 7 SEM image of anthranilic acid participating in the reaction nanospheres
  • Figure 8 SEM image of m-aminobenzenesulfonic acid participating in the reaction nanospheres
  • Figure 10 SEM image of p-aminochlorobenzene in the reaction nanospheres
  • Figure 11 SEM image of melamine, m-phenylenediamine, and m-phenylenediamine disulfonic acid participating in the reaction of nanospheres;
  • Figure 12 SEM image of p-aminoanisole participating in the reaction microspheres
  • Figure 13 SEM image of para-aminobenzonitrile participating in the reaction microspheres
  • FIG. 14 SEM image of p-aminophenol participating in the reaction microspheres
  • Figure 15 SEM image of anthranilic acid participating in the reaction microspheres
  • Figure 16 SEM image of meta-aminobenzoic acid participating in the reaction microspheres
  • Figure 17 SEM image of the para-aminobenzoic acid participating in the reaction microspheres
  • Figure 18 SEM image of aniline participating in the reaction nanospheres
  • Figure 19 SEM image of o-phenylenediamine participating in the reaction nanospheres
  • Fig. 21 SEM image of p-phenylenediamine participating in the reaction nanospheres
  • Figure 22 SEM image of 2,4-diaminobenzenesulfonic acid participating in the reaction nanospheres
  • FIG. 24 SEM image of 2,4-diaminobenzenesulfonic acid-containing nanospheres prepared using glyoxal as a raw material
  • FIG. 25 SEM image of 2,4-diaminobenzenesulfonic acid-containing nanospheres prepared using glutaraldehyde as a raw material;
  • Figure 26 SEM image of nano-microspheres prepared from 2,4,6-triaminopyrimidine, 2,4-diaminobenzenesulfonic acid, and formaldehyde;
  • Figure 27 SEM image of nanomicrospheres prepared from 2,6-diaminopyridine, 2,4-diaminobenzenesulfonic acid, and formaldehyde;
  • Figure 28 SEM image of nano-microspheres prepared from 1,5-diaminonaphthalene, 2,4-diaminobenzenesulfonic acid, and formaldehyde;
  • Figure 29 SEM image of 3.78 g of m-phenylenediamine and 2,4-diaminobenzenesulfonic acid participating in the reaction of nanospheres;
  • Figure 30 SEM images of 2,4-diaminobenzenesulfonic acid participating in the reaction of microspheres under different amounts of m-phenylenediamine;
  • Figure 31 SEM images of m-phenylenediamine and 2,4-diaminobenzenesulfonic acid participating in the reaction at different temperatures;
  • Figure 32 SEM images of melamine and 2,4-diaminobenzenesulfonic acid reaction nanospheres under different m-phenylenediamine dosage conditions
  • FIG. 33 STEM image of nanospheres obtained in Example 39;
  • Figure 34 Scanning element surface of nanospheres obtained in Example 39; where abcd corresponds to elements C, N, S, and O, respectively;
  • FIG. 35 is an X-ray energy spectrum analysis chart of nanospheres obtained in Example 39.
  • FIG. 35 is an X-ray energy spectrum analysis chart of nanospheres obtained in Example 39.
  • test methods described in the following examples are conventional methods; the reagents and materials can be obtained from commercial sources unless otherwise specified.
  • the microspheres were obtained by centrifugation, washing, drying and observation under an electron microscope.
  • the temperature conditions of a to e are 5 ° C., 15 ° C., 25 ° C., 35 ° C., and 45 ° C.
  • the nano-microspheres are uniform, and the average particle diameter is 148 nm, 257 nm, 513 nm, 627 nm, and 845 nm.
  • the microspheres were obtained by centrifugation, washing, drying and observation under an electron microscope.
  • the amount of a to e 2,4-diaminobenzenesulfonic acid is 0.0145 g (0.000075 mol), 0.029 g (0.00015 mol), 0.058 g (0.0003 mol), 0.116 g (0.0006 mol), 0.174 g (0.0009mol)
  • the nanospheres are uniform, and the average particle diameter is 793nm, 624nm, 496nm, 307nm, 169nm.
  • sulfonic acid was dissolved in 50 mL of water, 0.1 mL of ammonia water was added dropwise, and the solution was stirred at a temperature of 25 ° C and a stirring speed of 500 rpm until the solution became uniform and transparent. After adding 1.2 mL of an aqueous formaldehyde solution, the liquid changed from clear to cloudy after about 45 seconds. The temperature was kept at 25 ° C and the mixture was stirred at 500 rpm for 2 hours.
  • the microspheres were obtained by centrifugation, washing, drying and observation under an electron microscope.
  • the amount of a to e melamine is 0.1g (0.0008mol), 0.125g (0.001mol), 0.25g (0.002mol), 0.33g (0.0026mol), 0.5g (0.004mol), and
  • the spheres are uniform and the average particle diameter is 753nm, 607nm, 531nm, 130nm, 70nm.
  • 0.19 g (0.0015 mol) of melamine and 0.058 g (0.0003 mol) of 2,4-diaminobenzenesulfonic acid were dissolved in 50 mL of water, and 0.01 mL, 0.05 mL, 0.1 mL, 0.2 mL, 0.3 mL of ammonia water was added dropwise, and the temperature was 25 ° C. At 500 rpm, the solution was stirred until the solution was uniform and transparent. After adding 1.2 mL of an aqueous formaldehyde solution, the liquid changed from clear to cloudy after about 45 seconds. The temperature was kept at 25 ° C and the mixture was stirred at 500 rpm for 2 hours.
  • the microspheres were obtained by centrifugation, washing, drying and observation under an electron microscope.
  • the amount of a to e ammonia water was 0.01 mL, 0.05 mL, 0.1 mL, 0.2 mL, and 0.3 mL, and the nanospheres were uniform, and the average particle diameter was 163 nm, 203 nm, 537 nm, 607 nm, and 715 nm.
  • the microspheres were obtained by centrifugation, washing, drying and observation under an electron microscope.
  • the amount of formaldehyde a to e is 0.337 mL, 0.5 mL, 0.675 mL, 1 mL, and 1.35 mL.
  • the nanospheres are uniform, and the average particle diameter is 245 nm, 470 nm, 600 nm, 624 nm, and 624 nm.
  • the microspheres were obtained by centrifugation, washing, drying and observation under an electron microscope.
  • the amount of a-c m-phenylenediamine is 0.378 g (0.0035 mol), 0.351 g (0.00325 mol), and 0.324 g (0.003 mol) in this order.
  • the nanospheres are uniform, and the average particle size is 353nm, 259nm, 240nm.
  • the microspheres were obtained by centrifugation, washing, drying and observation under an electron microscope. As shown in Figure 32, the amount of a-c m-phenylenediamine is 0.252 g (0.002 mol), 0.189 g (0.0015 mol), and 0.126 g (0.001 mol) in this order.
  • the nanospheres are uniform, and the average particle size is 62nm, 56nm, 47nm.
  • nitrogen-containing sulfur polymer nano-microspheres were obtained.
  • the temperature was calcined using a DTL 1200 tube furnace program, room temperature was the initial temperature, and the temperature was increased from 2.5 ° C / min to 100 ° C. The temperature was kept constant for 30 minutes, and then 2.5 ° C / The temperature was raised to 300 ° C for 60 minutes, and then kept at 2.5 ° C / min to 500 ° C for 120 minutes. Finally, the temperature was naturally lowered to obtain carbonized nanospheres.
  • the heating rate of other products is the same at 2.5 ° C / min.
  • the temperature is kept constant at 100 ° C for 30 minutes, the intermediate program temperature is kept constant for 60 minutes, and the final baking temperature is maintained for 120 minutes, and then the temperature is naturally lowered.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • Dispersion Chemistry (AREA)
  • Phenolic Resins Or Amino Resins (AREA)
  • Manufacturing Of Micro-Capsules (AREA)

Abstract

本发明公开一种杂原子掺杂的聚合物纳米微球/炭纳米微球及其制备方法；所述方法是在搅拌条件下，采用温和的反应温度(10～50℃)，以芳胺、醛为原料，在下述通式（I）所示化合物的存在下，在水溶液体系中，经过醛与通式I所示化合物生成席夫碱，芳胺再与生成的席夫碱加成制得。上述聚合物纳米微球再经离心、干燥后，在惰性气体气氛下焙烧后可制得炭纳米微球。本发明所述工艺方法的操作简单、条件温和、反应快速；利用此方法制备所得的纳米微球产物的大小及形貌可控、粒度均匀、产量大、且杂原子掺杂均匀，具有很好的应用前景。

Description

一种杂原子掺杂的聚合物纳米微球/炭纳米微球及其制备方法 技术领域
本发明属于纳米新材料技术领域，具体涉及一种杂原子掺杂的聚合物纳米微球/炭纳米微球及其制备方法。
背景技术
杂原子掺杂的聚合物纳米微球在二氧化碳吸附与分离、标记与检测、阻燃、水中金属离子去除、气体存储与分离、硬模板法合成空心纳米微球及多孔纳米材料等方面具有很大的应用潜力，近年来受到了广泛关注。在碳原子骨架上掺杂非金属杂，例如硫、氮、硼、磷或多杂原子，可有效提升其应用性能，如氮掺杂的聚合物纳米微球具有更好的CO 2吸附性能。而目前对于非金属杂原子掺杂的研究主要集中在单一非金属杂原子掺杂，如从三聚氰胺出发制备含氮碳纳米微球，两种及三种以上杂原子掺杂涉及较少，即使涉及也是采用含杂原子的氨基酸作为原料之一在水热条件进行杂原子掺杂聚合物纳米材料的合成，操作复杂、耗时、耗能。
杂原子掺杂的炭纳米微球在能量转换与存储、二氧化碳吸附与分离、水中金属离子去除、气体存储与分离、催化等方面具有很大的应用潜力。在碳原子骨架上掺杂非金属杂原子，例如硫、氮、硼、磷或多杂原子，可有效提升其应用性能，如人们已经发现硫、氮双掺杂的石墨烯材料由于杂原子的协同作用，比未掺杂的石墨烯具有更好的氧还原性能；杂原子的存在可赋予炭材料良好的导电性、化学稳定性及催化性能。而目前对于非金属杂原子掺杂的研究同样主要集中在单一非金属杂原子掺杂，两种及三种以上杂原子掺杂涉及较少，即使涉及也是采用多步合成及后掺杂的方式进行，如采用元素硫、Na 2S或尿素在高温下处理含氮碳材料来获得氮、硫双掺杂炭材料，且由于其采用后掺杂的工艺方法，从微观粒子形貌来看，原子掺杂不均匀；或是采用水热条件进行掺杂聚合物纳米材料的合成，经焙烧后得到杂原子掺杂炭纳米微球，同样操作复杂、耗时、耗能。
目前已有从三聚氰胺或三聚氰胺与间苯二酚混合物出发制备含氮纳米微球的方法，进一步焙烧可得到含氮纳米炭球；也有氨基酸参与合成杂原子掺杂碳纳米微球的方法。具体方法有水浴加热法和水热法。水浴加热法首先制备预聚物，即三聚氰胺与甲醛发生N-羟甲基化的产物，被称为预聚物，再将预聚物进一步在酸性条件下缩聚，制备三聚氰胺甲醛树脂微球。从三聚氰胺出发的水热法同样首先制备预聚物，然后在水热条件下将预聚物聚合得到三聚氰胺甲醛树脂微球；从淀粉或葡萄糖出发的水热法需要含杂原子的氨基酸参与微球的形成。水热法需要较高的反应温度和较长的反应时间且产率低、难以实现大批量产业化应用。上述水浴加热法得到的是仅含氮的碳微球，其焙烧后也仅是含氮的炭纳米微球；反应温度高、时间长、操作复杂。
发明内容
本发明的目的在于提供一种工艺操作简单、条件温和、反应快速的杂原子掺杂的聚合物纳米微球的制备方法；该方法是在搅拌条件下，采用温和的反应温度(10～50℃)，以芳胺、 醛为原料，在通式I所示化合物的存在下，在水溶液体系中，经过醛与通式I所示化合物生成席夫碱，芳胺再与生成的席夫碱加成制得杂原子掺杂的聚合物纳米微球，在其应用过程中，使用者可以根据不同需求，将聚合物纳米微球在惰性气体气氛下焙烧制备炭纳米微球使用。利用此方法制备所得的纳米微球产物的大小及形貌可控、粒度均匀、产量大、且杂原子掺杂均匀。
具体的，本发明所述的杂原子掺杂的聚合物纳米微球的制备方法，包括以下步骤：
(1)在10～50℃条件下，将芳胺、通式I所示化合物溶解于水中为澄清体系，其中通式I所示化合物为：
Figure PCTCN2019094807-appb-000001
R 1选自H,NH 2；
R 2选自H,COOH,SO 3H,B(OH) 2,OPO(OH) 2,Cl,OCH 3,CN,OH,SH,NO 2；
R 3选自H,SO 3H；
(2)向上述体系中加入氨水，搅拌均匀；
(3)在10～50℃条件下，向上述溶液中加入醛，搅拌反应，得到聚合物纳米微球；
其中，步骤(1)所述芳胺选自下述的一种或几种：三聚氰胺，或1,3-苯二胺、1,4-苯二胺、1,3-苯二甲胺、1,4-苯二甲胺、三(4-氨基苯基)胺、2,4,6-三氨基嘧啶、2,6-二氨基吡啶、1,5-二氨基萘、1,4-二氨基萘、2,3-二氨基萘和1,8-二氨基萘；
对于上文所述的技术方案中，进一步优选的情况下，所述芳胺溶液浓度为0.015～1.0mol/L；其中，所述芳胺溶液浓度的优选范围为0.02～0.5mol/L；最优芳胺溶液浓度为0.03～0.2mol/L；当优选为三聚氰胺溶液时，浓度0.038mol/L为最佳条件。
对于上文所述的技术方案中，进一步优选的情况下，所述步骤(1)中通式I所示化合物包括：2,4-二氨基苯磺酸、邻氨基苯磺酸、间氨基苯磺酸、对氨基苯磺酸、间苯二胺双磺酸、3,5-二氨基苯甲酸、对氨基氯苯、对氨基苯甲醚、对氨基苯甲腈、对氨基苯酚、邻氨基苯甲酸、间氨基苯甲酸、对氨基苯甲酸、苯胺、邻苯二胺、间苯二胺、对苯二胺、对氨基苯硫酚、对硝基苯胺、邻(间、对)氨基苯硼酸、对氨基酚磷酸单酯；
对于上文所述的技术方案中，进一步优选的情况下，通式I所示化合物形成溶液的浓度为0.015～0.2mol/L；优选的浓度范围为0.004～0.1mol/L；最优溶液浓度为0.006～0.008mol/L；当优选为2,4-二氨基苯磺酸溶液时，浓度0.0076g/mL为最佳条件。
对于上文所述的技术方案中，进一步优选的情况下，所述步骤(2)所述的加入氨水溶液采用滴加的方式，搅拌时间为1～10分钟逐渐形成澄清、透明溶液。
对于上文所述的技术方案中，进一步优选的情况下，所述步骤(3)中使用的醛包括：甲醛或脂肪二醛；其中，所述的甲醛为市售的甲醛水溶液产品；所述的脂肪二醛包括乙二醛、丙二醛、丁二醛、戊二醛、己二醛等；
对于上文所述的技术方案中，进一步优选的情况下，步骤(3)所述醛采用滴加的方式添加，其使用量为醛基量相对于芳胺5～12倍当量。优选的醛使用量为醛基量相对于芳胺8～10倍当量。最优选的醛使用量为醛基量相对于芳胺9倍当量。
对于上文所述的技术方案中，进一步优选的情况下，步骤(3)中，加入醛后，搅拌，溶液随着时间延长由澄清变浑浊；保持搅拌反应0.2～6小时，将产物离心、干燥，得到粒径均匀、大小及形貌可控、分散性好的聚合物纳米微球；
对于上文所述的技术方案中，进一步优选的情况下，所述步骤(1)～(3)中优选的温度范围是20～35℃；最优温度为25℃。
本发明上文所述的方法采用芳胺和醛为基本原料，反应体系为水，加入氨水调节反应的pH，有利于对聚合物纳米微球均匀性及形貌的调控，通式I所示化合物的加入利于纳米微球的快速形成及形貌控制。体系中基本原料的浓度、通式I所示化合物的浓度、氨水用量是相互制约的。通过改变体系中通式I所示化合物与芳胺的比、芳胺与醛的比、芳胺的浓度、不同的氨水加入量、不同的反应温度(10～50℃)都可对聚合物纳米微球的粒径进行很好的调控。
本发明的另一方面在于：公开了一种利用上文所述的方法获得的杂原子掺杂的聚合物纳米微球，其氮含量为20％～80％，硫含量为0.1％～10％，且含量可调。纳米微球直径30nm～3μm，且粒径均匀、杂原子分布均匀、粒径尺寸可调、分散性好。
本发明公开了一种含氮硫炭纳米微球的制备方法，即利用上文所述的杂原子掺杂的聚合物纳米微球经惰性气体气氛下焙烧后制得。具体方法为：在上述制备聚合物纳米微球的方法基础上，还包括步骤(4)：将步骤(3)所得的聚合物纳米微球经离心、干燥后，在惰性气体气氛下焙烧后制得杂原子掺杂的炭纳米微球。
优选的，在步骤(3)反应0.2～6小时后，将产物以6000转/分钟离心分离，然后使用20％乙醇溶液洗涤，此过程反复三次(也可不洗涤直接烘干)，离心、烘干，得到粒径均匀、形貌可控、分散性好的纳米微球。
优选的，步骤(4)所述的焙烧条件为300～800℃，优选的条件为400～600℃，进一步优选的条件为500℃。
优选的，步骤(4)所述的焙烧条件为以室温为起始温度，焙烧升温速度相同为2.5℃/分，100℃保持恒温30分钟，中间程序温度保持恒温60分钟，最后焙烧温度保持120分钟，然后自然降温。
更为具体的，在本发明实施例中使用的焙烧条件为：以室温为起始温度，以2.5℃/分升高至100℃，保持恒温30分钟，再以2.5℃/分升至300℃，保持恒温60分钟，再以2.5℃/分升至500℃，保持恒温120分钟，最后自然降温，得到炭纳米微球。
本申请所述的含氮硫炭纳米微球的氮含量为1％～60％，优选20～60％，硫含量为0.1％～8％，且含量可调。纳米微球直径30nm～2μm，且粒径均匀、杂原子分布均匀、尺寸可调、分散性 好。
有益效果：
1.本发明所述方法采用全新的工艺路线，在温和的操作温度(10～50℃)下即可生产；避免了传统工艺中所使用的相对苛刻的70～100℃或水热反应条件；尤其是适用于在常温下(20～35℃)快速进行，更利于推广应用。
2.本发明采用的工艺简单、易操作、产量大、能够根据使用需求，通过控制体系中通式I所示化合物与芳胺的比、芳胺与醛的比、芳胺的浓度、不同的氨水加入量、不同的反应温度(10～50℃)得到大小及形貌可控的聚合物纳米微球/炭纳米微球。
3.本发明所述方法反应快速，步骤(3)在滴加醛后的几分钟之内，即有产物生成，在搅拌条件下，溶液随着时间延长由澄清变浑浊，产物逐渐增多，且直至反应结束后，离心取出所有聚合物纳米微球后的剩余反应液无需弃用，能再回收循环利用。
4.本发明所述方法能够拓展使用高碳数的脂肪二醛，可避免有害物质甲醛的使用。
附图说明
图1：10g三聚氰胺与2,4-二氨基苯磺酸反应纳米微球的SEM图；
图2：不同温度下2,4-二氨基苯磺酸参与反应纳米微球的SEM图；
图3：不同浓度2,4-二氨基苯磺酸参与反应纳米微球的SEM图；
图4：不同三聚氰胺用量下2,4-二氨基苯磺酸参与反应纳米微球的SEM图；
图5：不同氨水用量下2,4-二氨基苯磺酸参与反应纳米微球的SEM图；
图6：不同甲醛用量下2,4-二氨基苯磺酸参与反应纳米微球的SEM图；
图7：邻氨基苯磺酸参与反应纳米微球的SEM图；
图8：间氨基苯磺酸参与反应纳米微球的SEM图；
图9：对氨基苯磺酸参与反应纳米微球的SEM图；
图10：对氨基氯苯参与反应纳米微球的SEM图；
图11：三聚氰胺、间苯二胺、间苯二胺双磺酸参与反应纳米微球的SEM图；
图12：对氨基苯甲醚参与反应纳米微球的SEM图；
图13：对氨基苯甲腈参与反应纳米微球的SEM图；
图14：对氨基苯酚参与反应纳米微球的SEM图；
图15：邻氨基苯甲酸参与反应纳米微球的SEM图；
图16：间氨基苯甲酸参与反应纳米微球的SEM图；
图17：对氨基苯甲酸参与反应纳米微球的SEM图；
图18：苯胺参与反应纳米微球的SEM图；
图19：邻苯二胺参与反应纳米微球的SEM图；
图20；间苯二胺参与反应纳米微球的SEM图；
图21：对苯二胺参与反应纳米微球的SEM图；
图22：2,4-二氨基苯磺酸参与反应纳米微球的SEM图；
图23：4-氨基苯硼酸参与反应纳米微球的SEM图
图24：2,4-二氨基苯磺酸参与反应、使用乙二醛为原料制备的的纳米微球的SEM图；
图25：2,4-二氨基苯磺酸参与反应、使用戊二醛为原料制备的的纳米微球的SEM图；
图26：2,4,6-三氨基嘧啶、2,4-二氨基苯磺酸、甲醛为原料制备的的纳米微球的SEM图；
图27：2,6-二氨基吡啶、2,4-二氨基苯磺酸、甲醛为原料制备的的纳米微球的SEM图；
图28：1,5-二氨基萘、2,4-二氨基苯磺酸、甲醛为原料制备的的纳米微球的SEM图；
图29：3.78g间苯二胺、2,4-二氨基苯磺酸参与反应纳米微球的SEM图；
图30：不同间苯二胺用量下2,4-二氨基苯磺酸参与反应纳米微球的SEM图；
图31：不同温度下间苯二胺、2,4-二氨基苯磺酸参与反应纳米微球的SEM图；
图32：不同间苯二胺用量条件下三聚氰胺、2,4-二氨基苯磺酸反应纳米微球的SEM图；
图33：实施例39获得的纳米微球STEM图；
图34：实施例39获得的纳米微球元素面扫描图；其中，abcd分别对应元素C、N、S、O；
图35：实施例39获得的纳米微球X射线能谱分析图。
具体实施方式
下述非限定性实施例可以使本领域的普通技术人员更全面地理解本发明，但不以任何方式限制本发明。
下述实施例中所述试验方法，如无特殊说明，均为常规方法；所述试剂和材料，如无特殊说明，均可从商业途径获得。
实施例1
将10g(0.08mol)三聚氰胺，3.01g(0.016mol)2,4-二氨基苯磺酸溶解于2000mL水中，滴加5mL氨水，25℃温度，500rpm转速搅速下搅拌至溶液呈均一透明状。加入50mL甲醛水溶液，在经过约3分钟后，液体出现明显浑浊。保持25℃，500rpm搅拌2小时，经离心、洗涤、干燥，进行电镜观察，如图1所示，纳米微球均匀，平均粒径在512nm。
实施例2
将0.19g(0.0015mol)三聚氰胺，0.058g(0.0003mol)2,4-二氨基苯磺酸溶解于50mL水中，滴加0.1mL氨水，5℃、15℃、25℃、35℃、45℃温度下，500rpm转速搅速下搅拌至溶液呈均一透明状。加入1.2mL甲醛水溶液，在经过约45秒后，液体由澄清变浑浊。保持温度，500rpm搅拌2小时。反应完成后，经离心、洗涤、干燥，进行电镜观察，得到含氮硫聚合物纳米微球。如图2所示，a～e温度条件依次为5℃、15℃、25℃、35℃、45℃，纳米微球均匀，平均粒径在148nm、257nm、513nm、627nm、845nm。
实施例3
将0.19g(0.0015mol)三聚氰胺，0.0145g(0.000075mol)、0.029g(0.00015mol)、0.058g(0.0003mol)、0.116g(0.0006mol)、0.174g(0.0009mol)2,4-二氨基苯磺酸溶解于50mL水中，滴加0.1mL氨水，25℃温度，500rpm转速搅速下搅拌至溶液呈均一透明状。加入1.2mL甲醛水溶液，在经过约45秒后，液体由澄清变浑浊。保持25℃，500rpm搅拌2小时。反应完成后，经离心、洗涤、干燥，进行电镜观察，得到含氮硫聚合物纳米微球。如图3所 示，a～e 2,4-二氨基苯磺酸用量依次为0.0145g(0.000075mol)、0.029g(0.00015mol)、0.058g(0.0003mol)、0.116g(0.0006mol)、0.174g(0.0009mol)，纳米微球均匀，平均粒径在793nm、624nm、496nm、307nm、169nm。
实施例4
将0.1g(0.0008mol)、0.125g(0.001mol)、0.25g(0.002mol)、0.33g(0.0026mol)、0.5g(0.004mol)三聚氰胺，0.058g(0.0003mol)2,4-二氨基苯磺酸溶解于50mL水中，滴加0.1mL氨水，25℃温度，500rpm转速搅速下搅拌至溶液呈均一透明状。加入1.2mL甲醛水溶液，在经过约45秒后，液体由澄清变浑浊。保持25℃，500rpm搅拌2小时。反应完成后，经离心、洗涤、干燥，进行电镜观察，得到含氮硫聚合物纳米微球。如图4所示，a～e三聚氰胺用量依次为0.1g(0.0008mol)、0.125g(0.001mol)、0.25g(0.002mol)、0.33g(0.0026mol)、0.5g(0.004mol)，纳米微球均匀，平均粒径在753nm、607nm、531nm、130nm、70nm。
实施例5
将0.19g(0.0015mol)三聚氰胺，0.058g(0.0003mol)2,4-二氨基苯磺酸溶解于50mL水中，滴加0.01mL、0.05mL、0.1mL、0.2mL、0.3mL氨水，25℃温度，500rpm转速搅速下搅拌至溶液呈均一透明状。加入1.2mL甲醛水溶液，在经过约45秒后，液体由澄清变浑浊。保持25℃，500rpm搅拌2小时。反应完成后，经离心、洗涤、干燥，进行电镜观察，得到含氮硫聚合物纳米微球。如图5所示，a～e氨水用量依次为0.01mL、0.05mL、0.1mL、0.2mL、0.3mL，纳米微球均匀，平均粒径在163nm、203nm、537nm、607nm、715nm。
实施例6
将0.19g(0.0015mol)三聚氰胺，0.058g(0.0003mol)2,4-二氨基苯磺酸溶解于50mL水中，滴加0.1mL氨水，25℃温度，500rpm转速搅速下搅拌至溶液呈均一透明状。加入0.337mL、0.5mL、0.675mL、1mL、1.35mL甲醛水溶液，在经过约45秒后，液体由澄清变浑浊。保持25℃，500rpm搅拌2小时。反应完成后，经离心、洗涤、干燥，进行电镜观察，得到含氮硫聚合物纳米微球。如图6所示，a～e甲醛用量依次为0.337mL、0.5mL、0.675mL、1mL、1.35mL，纳米微球均匀，平均粒径在245nm、470nm、600nm、624nm、624nm。
实施例7
将0.19g(0.0015mol)三聚氰胺，0.0519g(0.0003mol)邻氨基苯磺酸溶解于50mL水中，滴加0.1mL氨水，25℃温度，500rpm转速搅速下搅拌至溶液呈均一透明状。加入1.2mL甲醛水溶液，在经过约7分钟后，液体出现明显浑浊。保持25℃，500rpm搅拌2小时。反应后，经离心、洗涤、干燥，得到含氮硫聚合物纳米微球，进行电镜观察，如图7所示，纳米微球平均粒径在912nm。
实施例8
将0.19g(0.0015mol)三聚氰胺，0.0519g(0.0003mol)间氨基苯磺酸溶解于50mL水中，滴加0.1mL氨水，25℃温度，500rpm转速搅速下搅拌至溶液呈均一透明状。加入1.2mL甲醛水溶液，在经过约5分钟后，液体出现明显浑浊。保持25℃，500rpm搅拌2小时。反 应后，经离心、洗涤、干燥，得到含氮硫聚合物纳米微球，进行电镜观察，如图8所示，纳米微球均匀，平均粒径在800nm。
实施例9
将0.19g(0.0015mol)三聚氰胺，0.0519g(0.0003mol)对氨基苯磺酸溶解于50mL水中，滴加0.1mL氨水，25℃温度，500rpm转速搅速下搅拌至溶液呈均一透明状。加入1.2mL甲醛水溶液，在经过约6分钟后，液体出现明显浑浊。保持25℃，500rpm搅拌2小时。反应后，经离心、洗涤、干燥，得到含氮硫聚合物纳米微球，进行电镜观察，如图9所示，纳米微球均匀，平均粒径在867nm。
实施例10
将0.19g(0.0015mol)三聚氰胺，0.0381g(0.0003mol)对氨基氯苯溶解于50mL水中，滴加0.1mL氨水，25℃温度，500rpm转速搅速下搅拌至溶液呈均一透明状。加入1.2mL甲醛水溶液，在经过约10分钟后，液体出现明显浑浊。保持25℃，500rpm搅拌4小时。反应后，经离心、洗涤、干燥，得到含氮硫聚合物纳米微球，进行电镜观察，如图10所示，纳米微球平均粒径在1376nm。
实施例11
取等摩尔比例混合的三聚氰胺与间苯二胺共0.001mol；和0.0003mol间苯二胺双磺酸溶解于50mL水中，滴加0.1mL氨水，25℃温度，500rpm转速搅速下搅拌至溶液呈均匀状。加入1.5mL甲醛水溶液，在经过约2分钟后，液体出现明显浑浊。保持25℃，500rpm搅拌4小时。反应后，经离心、洗涤、干燥，进行电镜观察，如图11所示。
实施例12
将0.19g(0.0015mol)三聚氰胺，0.0371g(0.0003mol)对氨基苯甲醚溶解于50mL水中，滴加0.1mL氨水，25℃温度，500rpm转速搅速下搅拌至溶液呈均匀分散状。加入1.2mL甲醛水溶液，在经过约7分钟后，液体出现明显浑浊。保持25℃，500rpm搅拌6小时。反应后，经离心、洗涤、干燥，得到含氮硫聚合物纳米微球，进行电镜观察，如图12所示。
实施例13
将0.19g(0.0015mol)三聚氰胺，0.0354g(0.0003mol)对氨基苯甲腈溶解于50mL水中，滴加0.1mL氨水，25℃温度，500rpm转速搅速下搅拌至溶液呈均一透明状。加入1.2mL甲醛水溶液，在经过约7分钟后，液体出现明显浑浊。保持25℃，500rpm搅拌4小时。反应后，经离心、洗涤、干燥，得到含氮硫聚合物纳米微球，进行电镜观察，如图13所示，产品颗粒均匀，平均粒径在1071nm。
实施例14
将0.19g(0.0015mol)三聚氰胺，0.0328g(0.0003mol)对氨基苯酚溶解于50mL水中，滴加0.1mL氨水，25℃温度，500rpm转速搅速下搅拌至溶液呈均一透明状。加入1.2mL甲醛水溶液，在经过约2分钟后，液体出现明显浑浊。保持25℃，500rpm搅拌4小时。反应后，经离心、洗涤、干燥，得到含氮硫聚合物纳米微球，进行电镜观察，如图14所示，产品颗粒均匀，平均粒径在466nm。
实施例15
将0.19g(0.0015mol)三聚氰胺，0.0411g(0.0003mol)邻氨基苯甲酸溶解于50mL水中，滴加0.1mL氨水，25℃温度，500rpm转速搅速下搅拌至溶液呈均匀分散状。加入1.2mL甲醛水溶液，在经过约6分钟后，液体出现明显浑浊。保持25℃，500rpm搅拌2小时。反应后，经离心、洗涤、干燥，得到含氮硫聚合物纳米微球，进行电镜观察，如图15所示，产品颗粒均匀，平均粒径在1015nm。
实施例16
将0.19g(0.0015mol)三聚氰胺，0.0411g(0.0003mol)间氨基苯甲酸溶解于50mL水中，滴加0.1mL氨水，25℃温度，500rpm转速搅速下搅拌至溶液呈均一透明状。加入1.2mL甲醛水溶液，在经过约5分钟后，液体出现明显浑浊。保持25℃，500rpm搅拌2小时。反应后，经离心、洗涤、干燥，得到含氮硫聚合物纳米微球，进行电镜观察，如图16所示，产品颗粒均匀，平均粒径在1003nm。
实施例17
将0.19g(0.0015mol)三聚氰胺，0.0411g(0.0003mol)对氨基苯甲酸溶解于50mL水中，滴加0.1mL氨水，25℃温度，500rpm转速搅速下搅拌至溶液呈均一透明状。加入1.2mL甲醛水溶液，在经过约6分钟后，液体出现明显浑浊。保持25℃，500rpm搅拌2小时。反应后，经离心、洗涤、干燥，得到含氮硫聚合物纳米微球，进行电镜观察，如图17所示，纳米微球平均粒径在862nm。
实施例18
将0.19g(0.0015mol)三聚氰胺，0.0281g(0.0003mol)苯胺溶解于50mL水中，滴加0.1mL氨水，25℃温度，500rpm转速搅速下搅拌至溶液呈均一透明状。加入1.2mL甲醛水溶液，在经过约20分钟后，液体出现明显浑浊。保持25℃，500rpm搅拌6小时。反应后，经离心、洗涤、干燥，得到含氮硫聚合物纳米微球，进行电镜观察，如图18所示，纳米微球平均粒径在1377nm。
实施例19
将0.19g(0.0015mol)三聚氰胺，0.0324g(0.0003mol)邻苯二胺溶解于50mL水中，滴加0.1mL氨水，25℃温度，500rpm转速搅速下搅拌至溶液呈均一透明状。加入1.2mL甲醛水溶液，在经过约9分钟后，液体出现明显浑浊。保持25℃，500rpm搅拌4小时。反应后，经离心、洗涤、干燥，得到含氮硫聚合物纳米微球，进行电镜观察，如图19所示，纳米微球平均粒径在1546nm。
实施例20
将0.19g(0.0015mol)三聚氰胺，0.0324g(0.0003mol)间苯二胺溶解于50mL水中，滴加0.1mL氨水，25℃温度，500rpm转速搅速下搅拌至溶液呈均一透明状。加入1.2mL甲醛水溶液，在经过约7分钟后，液体出现明显浑浊。保持25℃，500rpm搅拌4小时。反应后，经离心、洗涤、干燥，得到含氮硫聚合物纳米微球，进行电镜观察，如图20所示，纳米微球平均粒径在2078nm。
实施例21
将0.19g(0.0015mol)三聚氰胺，0.0324g(0.0003mol)对苯二胺溶解于50mL水中，滴加0.1mL氨水，25℃温度，500rpm转速搅速下搅拌至溶液呈均一透明状。加入1.2mL甲醛水溶液，在经过约10分钟后，液体出现明显浑浊。保持25℃，500rpm搅拌4小时。反应后，经离心、洗涤、干燥，进行电镜观察，如图21所示，纳米微球平均粒径在1355nm。
实施例22
将0.294g(0.0015mol)1,2,6-三苯胺，0.058g(0.0003mol)2,4-二氨基苯磺酸溶解于50mL水中，滴加0.1mL氨水，25℃温度，500rpm转速搅速下搅拌至溶液呈均一透明状。加入1.2mL甲醛水溶液，在经过约10分钟后，液体出现明显浑浊。保持25℃，500rpm搅拌4小时。反应后，经离心、洗涤、干燥，得到含氮硫聚合物纳米微球，进行电镜观察，如图22所示。
实施例23
将0.19g(0.0015mol)三聚氰胺，0.0411g(0.0003mol)4-氨基苯硼酸溶解于50mL水中，滴加0.1mL氨水，25℃温度，500rpm转速搅速下搅拌至溶液呈均一透明状。加入1.2mL甲醛水溶液，在经过约4.25分钟后，液体出现明显浑浊。保持25℃，500rpm搅拌4小时。反应后，经离心、洗涤、干燥，得到含氮硫聚合物纳米微球，进行电镜观察，如图23所示，纳米微球均匀，平均粒径在543nm。
实施例24
将0.19g(0.0015mol)三聚氰胺，0.058g(0.0003mol)2,4-二氨基苯磺酸溶解于50mL水中，滴加0.1mL氨水，25℃温度，500rpm转速搅速下搅拌至溶液呈均一透明状。加入1mL乙二醛水溶液，在经过约20小时后，液体出现明显浑浊。保持25℃，500rpm搅拌4小时。反应后，经离心、洗涤、干燥，得到含氮硫聚合物纳米微球，进行电镜观察，如图24所示，纳米微球平均粒径在440nm。
实施例25
将0.19g(0.0015mol)三聚氰胺，0.058g(0.0003mol)2,4-二氨基苯磺酸溶解于50mL水中，滴加0.1mL氨水，25℃温度，500rpm转速搅速下搅拌至溶液呈均一透明状。加入1.4mL戊二醛水溶液，在经过约10分钟后，液体出现明显浑浊。保持25℃，500rpm搅拌4小时。反应后，经离心、洗涤、干燥，得到含氮硫聚合物纳米微球，进行电镜观察，如图25所示，纳米微球平均粒径在400nm。
实施例26
将0.19g(0.0015mol)2,4,6-三氨基嘧啶，0.058g(0.0003mol)2,4-二氨基苯磺酸溶解于50mL水中，滴加0.1mL氨水，25℃温度，500rpm转速搅速下搅拌至溶液呈均一透明状。加入1.2mL甲醛水溶液，在经过约7分钟后，液体出现明显浑浊。保持25℃，500rpm搅拌2小时。反应后，经离心、洗涤、干燥，得到含氮硫聚合物纳米微球，进行电镜观察，如图26所示，纳米微球均匀，平均粒径在243nm。
实施例27
将0.16g(0.0015mol)2,6-二氨基吡啶，0.058g(0.0003mol)2,4-二氨基苯磺酸溶解于50mL水中，滴加0.1mL氨水，25℃温度，500rpm转速搅速下搅拌至溶液呈均一透明状。加入1.2mL甲醛水溶液，在经过约7分钟后，液体出现明显浑浊。保持25℃，500rpm搅拌2小时。反应后，经离心、洗涤、干燥，得到含氮硫聚合物纳米微球，进行电镜观察，如图27所示。
实施例28
将0.24g(0.0015mol)1,5-二氨基萘，0.058g(0.0003mol)2,4-二氨基苯磺酸溶解于50mL水中，滴加0.1mL氨水，25℃温度，500rpm转速搅速下搅拌至溶液呈均一透明状。加入1.2mL甲醛水溶液，在经过约7分钟后，液体出现明显浑浊。保持25℃，500rpm搅拌2小时。反应后，经离心、洗涤、干燥，得到含氮硫聚合物纳米微球，进行电镜观察，如图28所示，纳米微球均匀，平均粒径在106nm。
实施例29
将3.78g(0.035mol)间苯二胺，0.58g(0.003mol)2,4-二氨基苯磺酸溶解于500mL水中，滴加0.5mL氨水，25℃、温度，500rpm转速搅速下搅拌至溶液呈均一透明状。加入12mL甲醛水溶液，在经过约2秒后，液体由澄清变浑浊。保持温度，500rpm搅拌2小时。反应完成后，经离心、洗涤、干燥，进行电镜观察，得到含氮硫聚合物纳米微球。如图29所示，纳米微球均匀，平均粒径在172nm。
实施例30
将0.378g(0.0035mol)、0.351g(0.00325mol)、0.324g(0.003mol)间苯二胺，0.058g(0.0003mol)2,4-二氨基苯磺酸溶解于50mL水中，滴加0.05mL氨水，25℃、温度，500rpm转速搅速下搅拌至溶液呈均一透明状。加入1.2mL甲醛水溶液，在经过约2秒后，液体由澄清变浑浊。保持温度，500rpm搅拌2小时。反应完成后，经离心、洗涤、干燥，进行电镜观察，得到含氮硫聚合物纳米微球。如图30所示，a～c间苯二胺用量依次为0.378g(0.0035mol)、0.351g(0.00325mol)、0.324g(0.003mol)，纳米微球均匀，平均粒径在353nm、259nm、240nm。
实施例31
将0.324g(0.003mol)间苯二胺，0.058g(0.0003mol)2,4-二氨基苯磺酸溶解于50mL水中，滴加0.05mL氨水，5℃、15℃、25℃温度，500rpm转速搅速下搅拌至溶液呈均一透明状。加入1.2mL甲醛水溶液，在经过约2秒后，液体由澄清变浑浊。保持温度，500rpm搅拌2小时。反应完成后，经离心、洗涤、干燥，进行电镜观察，得到含氮硫聚合物纳米微球。如图31所示，a～c温度依次为5℃、15℃、25℃，纳米微球均匀，平均粒径在504nm、456nm、240nm。
实施例32
将0.126g(0.001mol)三聚氰胺与0.252g(0.002mol)、0.189g(0.0015mol)、0.126g(0.001mol)间苯二胺，0.116g(0.0006mol)2,4-二氨基苯磺酸溶解于50mL水中，滴加0.1mL氨水，25℃温度，500rpm转速搅速下搅拌至溶液呈均一透明状。加入2mL甲醛水溶液，在经过约2秒后，液体由澄清变浑浊。保持温度，500rpm搅拌2小时。反应完成后，经离心、洗涤、干燥，进行电镜观察，得到含氮硫聚合物纳米微球。如图32所示，a～c间苯二胺用量依次为0.252 g(0.002mol)、0.189g(0.0015mol)、0.126g(0.001mol)，纳米微球均匀，平均粒径在62nm、56nm、47nm。
实施例33
将0.19g(0.0015mol)三聚氰胺，0.0411g(0.0003mol)2-氨基苯硼酸溶解于50mL水中，滴加0.1mL氨水，25℃温度，500rpm转速搅速下搅拌至溶液呈均一透明状。加入1.2mL甲醛水溶液，在经过约4.25分钟后，液体出现明显浑浊。保持25℃，500rpm搅拌6小时。反应后，经离心、洗涤、干燥，得到含氮硫聚合物纳米微球。
实施例34
将0.19g(0.0015mol)三聚氰胺，0.0411g(0.0003mol)3-氨基苯硼酸溶解于50mL水中，滴加0.1mL氨水，25℃温度，500rpm转速搅速下搅拌至溶液呈均一透明状。加入1.2mL甲醛水溶液，在经过约4.25分钟后，液体出现明显浑浊。保持25℃，500rpm搅拌6小时。反应后，经离心、洗涤、干燥，得到含氮硫聚合物纳米微球。
实施例35
将0.19g(0.0015mol)三聚氰胺，0.058g(0.0003mol)对氨基酚磷酸单酯溶解于50mL水中，滴加0.1mL氨水，25℃温度，500rpm转速搅速下搅拌至溶液呈均一透明状。加入1.2mL甲醛水溶液，在经过约7分钟后，液体出现明显浑浊。保持25℃，500rpm搅拌6小时。反应后，经离心、洗涤、干燥，得到含氮硫聚合物纳米微球。
实施例36
将0.19g(0.0015mol)三聚氰胺，0.058g(0.0003mol)2,4-二氨基苯磺酸溶解于50mL水中，滴加0.1mL氨水，25℃温度，500rpm转速搅速下搅拌至溶液呈均一透明状。加入1.1mL丙二醛水溶液，在经过约10分钟后，液体出现明显浑浊。保持25℃，500rpm搅拌4小时。反应后，经离心、洗涤、干燥，得到含氮硫聚合物纳米微球。
实施例37
将0.19g(0.0015mol)三聚氰胺，0.058g(0.0003mol)2,4-二氨基苯磺酸溶解于50mL水中，滴加0.1mL氨水，25℃温度，500rpm转速搅速下搅拌至溶液呈均一透明状。加入1.25mL丁二醛水溶液，在经过约10分钟后，液体出现明显浑浊。保持25℃，500rpm搅拌4小时。反应后，经离心、洗涤、干燥，得到含氮硫聚合物纳米微球。
实施例38
将0.19g(0.0015mol)三聚氰胺，0.058g(0.0003mol)2,4-二氨基苯磺酸溶解于50mL水中，滴加0.1mL氨水，25℃温度，500rpm转速搅速下搅拌至溶液呈均一透明状。加入1.5mL己二醛水溶液，在经过约10分钟后，液体出现明显浑浊。保持25℃，500rpm搅拌4小时。反应后，经离心、洗涤、干燥，得到含氮硫聚合物纳米微球。
实施例39
以三聚氰胺，2,4-二氨基苯磺酸，甲醛反应为例：
干燥后得到含氮硫聚合物纳米微球，焙烧采用DTL 1200型管式炉程序升温，室温为起始温度，以2.5℃/分升高至100℃，保持恒温30分钟，再以2.5℃/分升至300℃，保持恒温60 分钟，再以2.5℃/分升至500℃，保持恒温120分钟，最后自然降温，得到碳化的纳米微球。
其它产品焙烧升温速度相同为2.5℃/分，100℃保持恒温30分钟，中间程序温度保持恒温60分钟，最后焙烧温度保持120分钟，然后自然降温。
实施例40
对实施例39制备的聚合物纳米微球进行扫描电镜、元素面扫及X射线能谱分析；结果如图33(STEM图)、图34(元素面扫描图)、图35(X射线能谱分析图)。
对于任何熟悉本领域的技术人员而言，在不脱离本发明技术方案范围情况下，都可利用上述揭示的技术内容对本发明技术方案作出许多可能的变动和修饰，或修改为等同变化的等效实施例。因此，凡是未脱离本发明技术方案的内容，依据本发明的技术实质对以上实施例所做的任何简单修改、等同变化及修饰，均应仍属于本发明技术方案保护的范围内。

Claims (15)

  1. 一种杂原子掺杂的聚合物纳米微球的制备方法，包括以下步骤：
    (1)在10～50℃条件下；将芳胺、通式I所示化合物溶解于水，其中通式I所示化合物为：
    Figure PCTCN2019094807-appb-100001
    R 1选自H,NH 2；
    R 2选自H,COOH,SO 3H,B(OH) 2,OPO(OH) 2,Cl,OCH 3,CN,OH,SH,NO 2；
    R 3选自H,SO 3H；
    (2)向上述体系中加入氨水，搅拌均匀；
    (3)向上述体系中加入醛，搅拌反应，得到聚合物纳米微球；
    其中，步骤(1)所述芳胺选自下述的一种或几种：三聚氰胺，或1,3-苯二胺、1,4-苯二胺、1,3-苯二甲胺、1,4-苯二甲胺、三(4-氨基苯基)胺、2,4,6-三氨基嘧啶、2,6-二氨基吡啶、1,5-二氨基萘、1,4-二氨基萘、2,3-二氨基萘、1,8-二氨基萘。
  2. 根据权利要求1所述的制备方法，其特征在于：所述步骤(1)中通式I所示化合物包括：2,4-二氨基苯磺酸、邻氨基苯磺酸、间氨基苯磺酸、对氨基苯磺酸、间苯二胺双磺酸、3,5-二氨基苯甲酸、对氨基氯苯、对氨基苯甲醚、对氨基苯甲腈、对氨基苯酚、邻氨基苯甲酸、间氨基苯甲酸、对氨基苯甲酸、苯胺、邻苯二胺、间苯二胺、对苯二胺、对氨基苯硫酚、对硝基苯胺、邻(间、对)氨基苯硼酸、对氨基酚磷酸单酯。
  3. 根据权利要求1或2所述的制备方法，其特征在于：所述步骤(1)中芳胺形成溶液的浓度为0.015～1.0mol/L。
  4. 根据权利要求1～3中任一项所述的制备方法，其特征在于：通式I所示化合物溶液浓度为0.015～0.2mol/L。
  5. 根据权利要求1～4中任一项所述的制备方法，其特征在于：所述步骤(3)中使用的醛选自甲醛、乙二醛、丙二醛、丁二醛、戊二醛或己二醛。
  6. 根据权利要求1～5中任一项所述的制备方法，其特征在于：所述步骤(3)中的醛采用滴加的方式添加，其使用量为醛基量相对于芳胺5～12倍当量。
  7. 根据权利要求1～6中任一项所述的制备方法，其特征在于：步骤(1)～(3)所使用的温度条件为20～35℃。
  8. 根据权利要求1～7中任一项所述的制备方法，其特征在于：步骤(2)所述的加入氨水溶液采用滴加的方式，搅拌时间为1～10分钟。
  9. 根据权利要求1～8中任一项所述的制备方法，其特征在于：步骤(3)中，加入醛后搅拌反应0.2～6小时。
  10. 根据权利要求1～9中任一项所述的制备方法，其特征在于：还包括步骤(4)将所得 的聚合物纳米微球经离心、干燥后，在惰性气体气氛下焙烧后制得杂原子掺杂的炭纳米微球。
  11. 根据权利要求10所述的制备方法，其特征在于：步骤(3)反应0.2～6小时后，将产物以6000转/分钟离心分离，然后使用20％乙醇溶液洗涤3次，离心、烘干，或者不洗涤直接烘干，得到聚合物纳米微球。
  12. 根据权利要求10所述的制备方法，其特征在于：步骤(4)中，所述的焙烧条件为300～800℃。
  13. 根据权利要求1～9中任一项所述的制备方法获得的聚合物纳米微球，其特征在于：所述聚合物纳米微球的氮含量20％～80％，硫含量0.1％～10％；纳米微球直径30nm～3μm，粒径均匀、杂原子分布均匀。
  14. 根据权利要求10～12所述的制备方法获得的炭纳米微球，其特征在于：所述炭纳米微球的氮含量1％～60％，硫含量0.1％～8％；纳米微球直径30nm～2μm，粒径均匀、杂原子分布均匀。
  15. 根据权利要求14所述的制备方法获得的炭纳米微球，其特征在于：所述炭纳米微球的氮含量20％～60％.
PCT/CN2019/094807 2018-07-31 2019-07-05 一种杂原子掺杂的聚合物纳米微球/炭纳米微球及其制备方法 WO2020024766A1 (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US17/265,199 US11919772B2 (en) 2018-07-31 2019-07-05 Heteroatom doped polymer nanospheres/carbon nanospheres and preparation method thereof

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
CN201810857851.6A CN108822274B (zh) 2018-07-31 2018-07-31 一种杂原子掺杂的聚合物纳米微球及其制备方法
CN201810857851.6 2018-07-31
CN201810858599.0 2018-07-31
CN201810858599.0A CN108862240B (zh) 2018-07-31 2018-07-31 一种杂原子掺杂炭纳米微球及其制备方法

Publications (1)

Publication Number Publication Date
WO2020024766A1 true WO2020024766A1 (zh) 2020-02-06

Family

ID=69230511

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2019/094807 WO2020024766A1 (zh) 2018-07-31 2019-07-05 一种杂原子掺杂的聚合物纳米微球/炭纳米微球及其制备方法

Country Status (2)

Country Link
US (1) US11919772B2 (zh)
WO (1) WO2020024766A1 (zh)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113582158A (zh) * 2021-09-08 2021-11-02 广东石油化工学院 微米碳球材料及制备方法与用途
CN113666360A (zh) * 2021-08-17 2021-11-19 太原理工大学 一种基于混合酚制备纳米碳球的方法及纳米碳球
CN113929923A (zh) * 2021-11-29 2022-01-14 湖北大学 纳米球形共价有机框架及其粒径可控的制备方法与应用

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113980718B (zh) * 2021-11-19 2022-04-29 陕西科技大学 一种碳球/二维共价有机聚合物纳米颗粒的制备方法
CN114588937B (zh) * 2022-03-16 2023-07-21 浙江大学 一种哒嗪掺杂改性c3n4光催化剂的制备方法及应用
CN117070214A (zh) * 2023-08-25 2023-11-17 山西大学 一种锰、氯、氮掺杂的疏水性碳量子点荧光探针及其制备方法和应用

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100092370A1 (en) * 2008-10-10 2010-04-15 Headwaters Technology Innovation, Llc Preparation of a carbon nanomaterial using a reverse microemulsion
CN104772088A (zh) * 2015-04-02 2015-07-15 北京科技大学 一种无模板共价有机骨架空心微球聚合物的制备方法
CN106654278A (zh) * 2016-11-29 2017-05-10 南方科技大学 一种新型碳球及其制备方法与应用
CN108822274A (zh) * 2018-07-31 2018-11-16 大连理工大学 一种杂原子掺杂的聚合物纳米微球及其制备方法
CN108862240A (zh) * 2018-07-31 2018-11-23 大连理工大学 一种杂原子掺杂炭纳米微球及其制备方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100092370A1 (en) * 2008-10-10 2010-04-15 Headwaters Technology Innovation, Llc Preparation of a carbon nanomaterial using a reverse microemulsion
CN104772088A (zh) * 2015-04-02 2015-07-15 北京科技大学 一种无模板共价有机骨架空心微球聚合物的制备方法
CN106654278A (zh) * 2016-11-29 2017-05-10 南方科技大学 一种新型碳球及其制备方法与应用
CN108822274A (zh) * 2018-07-31 2018-11-16 大连理工大学 一种杂原子掺杂的聚合物纳米微球及其制备方法
CN108862240A (zh) * 2018-07-31 2018-11-23 大连理工大学 一种杂原子掺杂炭纳米微球及其制备方法

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113666360A (zh) * 2021-08-17 2021-11-19 太原理工大学 一种基于混合酚制备纳米碳球的方法及纳米碳球
CN113582158A (zh) * 2021-09-08 2021-11-02 广东石油化工学院 微米碳球材料及制备方法与用途
CN113582158B (zh) * 2021-09-08 2023-11-10 广东石油化工学院 微米碳球材料及制备方法与用途
CN113929923A (zh) * 2021-11-29 2022-01-14 湖北大学 纳米球形共价有机框架及其粒径可控的制备方法与应用
CN113929923B (zh) * 2021-11-29 2023-02-24 湖北大学 纳米球形共价有机框架及其粒径可控的制备方法与应用

Also Published As

Publication number Publication date
US11919772B2 (en) 2024-03-05
US20210253428A1 (en) 2021-08-19

Similar Documents

Publication Publication Date Title
WO2020024766A1 (zh) 一种杂原子掺杂的聚合物纳米微球/炭纳米微球及其制备方法
CN108822274B (zh) 一种杂原子掺杂的聚合物纳米微球及其制备方法
CN108862240B (zh) 一种杂原子掺杂炭纳米微球及其制备方法
Luo et al. Aryl-modified graphene quantum dots with enhanced photoluminescence and improved pH tolerance
CN110283288B (zh) 一种可大量生产的杂原子掺杂的具有空腔结构聚合物纳米微球及其制备方法
CN111943227B (zh) 一种低缺陷和低水含量的普鲁士白类似物的制备方法
CN107312181B (zh) 一种快速制备Cu-BTC的方法
CN105585043B (zh) 一种花状纳米氧化铈材料的制备方法
CN113845902B (zh) 一种具有绿色荧光的碳氧共掺杂氮化硼量子点及其制备方法与应用
CN113189162B (zh) 一种基于钙钛矿@共价有机框架复合材料的电化学发光方法
CN108996557B (zh) 一种空心球结构氧化镍/氧化铜复合纳米材料及其制备方法
CN113415821B (zh) 一种中空ZnxCd1-xS固溶体纳米球的制备方法及其应用
KR20120041215A (ko) 나노크기로 도핑된 산화 아연 입자의 제조 및 처리 방법
CN113501548A (zh) 具有高比表面积的介孔金属氧化物空心材料及其制备方法
CN110817843B (zh) 一种低共熔溶剂、其应用和碳量子点及其制备方法
JP5958139B2 (ja) 炭素−鉄系結晶体複合ナノシートの製造方法
CN110563036A (zh) 一种富含氧空位的氧化铋纳米材料及其制备方法
CN111139065A (zh) 一种生物基发光纳米材料及其制备方法和应用
CN114105107B (zh) 具有不同形貌的高度单分散MoSe2纳米材料的制备方法
CN109721093B (zh) 一种微纳米船形二氧化铈及其制备方法
CN114105906B (zh) 一种有机电荷转移共晶及其制备方法和应用
Fan et al. Phase reversal behavior on two-dimension plane of fluorinated graphene during defluorination
CN105712401A (zh) 钒酸钙微米球材料及其制备方法和应用
CN109573976A (zh) 一种掺氮多孔碳及其制备方法和应用
CN111569879B (zh) 一种利用凹凸棒石制备硅酸盐/碳复合材料的方法及其应用

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19843683

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 19843683

Country of ref document: EP

Kind code of ref document: A1