CN113912040A - Method for regulating and controlling single-component asymmetric particle structure through emulsion size - Google Patents
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- C—CHEMISTRY; METALLURGY
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- 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
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- 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
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/318—Preparation characterised by the starting materials
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- 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
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/336—Preparation characterised by gaseous activating agents
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- 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/026—Wholly aromatic polyamines
Abstract
The invention discloses a method for regulating and controlling a single-component asymmetric particle structure through emulsion size, which relates to the field of asymmetric particles. Then pyrolyzed under the nitrogen atmosphere to be carbonized and NH3And activating to obtain the nitrogen-doped asymmetric carbon nano particles with the retained structures. The single-component asymmetric polymer particles and the nitrogen-containing carbon particles prepared by the invention only need to simply adjust the emulsion liquidThe size of oil drops in the system is only required, the preparation process is simple, the appearance is various, and the macro preparation can be realized.
Description
Technical Field
The invention relates to the field of asymmetric particles, in particular to a method for regulating and controlling a single-component asymmetric particle structure through emulsion size.
Background
Compared with symmetric particles, the anisotropy of the morphology and the composition of the asymmetric particles makes the particles have potential application values in many fields. The emulsion method is one of the methods for preparing asymmetric particles. The two-phase environment of the emulsion interface provides an ideal place for the preparation of asymmetric materials, and the emulsion droplets can also be used as a morphology template for the preparation of particles, so that two feasible routes for preparing asymmetric particles are realized by utilizing the two-phase environment of the emulsion in water and oil and the emulsion droplet template.
For the method using the water-oil two-phase environment of the emulsion, researchers have adopted a "seeded emulsion polymerization method" to prepare asymmetric particles based on the different distribution of polymer monomers in the water-oil two-phase environment and the principle of polymer phase separation. In this method, two vinyl monomers with opposite hydrophilicity and hydrophobicity are usually adopted to polymerize in water and oil phases and connect at the interface, and asymmetric particles with different shapes are finally formed due to the phase separation of the polymers, such as snowman-shaped, dumbbell-shaped, bowl-shaped, pistachio-shaped and the like.
For example, Wangzuotao, in 2017, used "seeded emulsion polymerization", in an oil-in-water system of Sodium Dodecyl Sulfate (SDS)/1-Chlorodecane (CD)/water, mixed with an aqueous solution of non-crosslinked polystyrene particles, magnetically stirred for 16h, added with oleophilic styrene (St) and Divinylbenzene (DVB) seed monomers, initiator Azobisisobutyronitrile (AIBN) and hydrophilic Acrylic Acid (AA)) After anchoring the monomer, continuously reacting for 6h at 40 ℃, and then polymerizing for 4h at 70 ℃ in a water-oil interface to form PSDVB with a Janus structure
PAA particles (symbol)
Representing the hydrophobic concave and hydrophilic convex orientations of Janus particles); different asymmetric morphologies, such as bread-loaf, crescent, hemispherical, pistachio, and the like, can be obtained by adjusting the concentrations of the hydrophilic anchoring monomer and the hydrophobic seed monomer. ("agricultural strand to synthetic chemistry and topologic and inverse Janus properties", Science Advances 2017,3,6, E1603203). However, the preparation process of the method is complicated and time-consuming, and the concentration of the oleophilic and hydrophilic monomer needs to be continuously adjusted; the prepared multicomponent Janus particle has a single appearance.
For the method of the emulsion droplet template, the asymmetric particles are prepared by directly taking the droplets of the inner phase in the emulsion as the morphology template. For example, in 2016, a building male theme group adopts an emulsion-induced interfacial anisotropy assembly strategy, forms an F127/TMB/polydopamine composite micelle by using a water-oil interface in which Trimethylbenzene (TMB) is dispersed in a water phase as a template, grows in particles under the synergistic assembly effect to obtain bowl-shaped mesoporous polydopamine particles, and then is subjected to hydrothermal treatment at 100 ℃ for 24 hours and high-temperature carbonization in a nitrogen atmosphere to obtain the derived bowl-shaped mesoporous carbon particles. (the "Formation of analysis of asymmetry Bowl-Like meso Particles via Emulsion-Induced Interface-isothermal Assembly", J.Am.chem.Soc.2016,138,35, 11306-. The method adopts a complex composite micelle emulsion system, the preparation needs 24 hours of hydrothermal at high temperature, the shape of the asymmetric particles is difficult to be regulated and controlled by a one-pot method, and the large-scale application of the asymmetric material is not facilitated. And the prepared multi-component bowl-shaped particles have single appearance.
Most of the asymmetric particles prepared by the two methods are multi-component particles, the preparation of single-component particles with asymmetric morphology is very difficult, and the single-component asymmetric particles only have bowl-shaped morphology at present. The shape of the asymmetric particles is single, and the asymmetric particles are usually in the shapes of a dumbbell, a snowman and a bowl, and one formula has one shape, so that the diversity of the asymmetric shapes cannot be flexibly regulated and controlled.
Accordingly, those skilled in the art have been devoted to developing a method for constructing a variety of asymmetric single-component polymer particles and carbon derivative particles thereof with a flexible and controllable particle morphology.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, the technical problem to be solved by the present invention is how to develop a method for constructing a plurality of asymmetric single-component polymer particles and carbon derivative particles thereof with flexible and controllable particle morphology.
To achieve the above objects, the present invention provides a method for controlling a structure of a one-component asymmetric particle by emulsion size, the method comprising the steps of:
step 4, carbonizing the PmPD single-component asymmetric polymer nano particles through a calcination procedure, and adding N2Pyrolyzing at 800 deg.C under atmosphere, carbonizing, and adding NH at 800 deg.C3The gas flow is activated to obtain the nitrogen-doped asymmetric carbon particles.
Further, the dosage ratio of the EtOH and the TMB in the step 1 is 0-20: 1-6.4.
Further, the size range of the PmPD asymmetric polymer nanoparticles in the step 3 is 240-650 nm.
Further, the shape of the PmPD asymmetric polymer nano particles in the step 3 is mushroom-shaped, hub-shaped or rubber-shaped.
Further, the amount of P123 used in step 1 was 43 mg.
Further, the amount of TMB used in step 1 was 250. mu.L.
Further, the mPD dosage in the step 2 is 250 mg.
Further, the dosage of the APS in the step 2 is 200 mg.
Further, the heating rate of the pyrolysis carbonization in the step 4 is 2 ℃ min-1The heating time is 2 h.
Further, NH in step 43The flow rate of the gas flow is 60ml min-1And the activation time is 30 min.
The invention has the following technical effects:
(1) the invention adopts simple one-pot emulsion template method to prepare single-component asymmetric polymer particles (APNs) and nitrogen-containing carbon particles (ACNs), only needs to simply adjust the size of oil drops in an emulsion system, has simple preparation process and various shapes, and can realize macroscopic preparation. The prepared single-component asymmetric particles have special shapes (including mushroom shapes, hub shapes and rubber shapes).
(2) The invention proves that the 'oil drop size' in the emulsion can determine the morphology of the prepared asymmetric polymer and the carbon derivative particles thereof.
(3) The invention combines the advantages of single-component asymmetric nano particles, an emulsion template method and a nitrogen-doped carbon material, so that the prepared ACNs become ideal electrode materials of small-volume portable energy storage devices, and the prepared ACNs have wide application prospects in the fields of oxidation-reduction catalysis and energy storage and conversion. ACNs have higher bulk density and Specific Surface Area (SSAs) than spherical nitrogen-doped carbon particles (SCNs) of the same diameter, and are ideal electrode materials for small-volume portable energy storage devices.
The conception, the specific structure and the technical effects of the present invention will be further described with reference to the accompanying drawings to fully understand the objects, the features and the effects of the present invention.
Drawings
FIG. 1 is a schematic diagram of the principles of the present invention;
FIG. 2 is a diagram of the topographic characterization of Asymmetric Polymer Nanoparticles (APNs) in accordance with a preferred embodiment of the present invention, wherein a is a schematic diagram of three types of particles APN-1, APN-2, and APN-3, b is a TEM image of APN-1, c is a TEM image of APN-2, and d is a TEM image of APN-3;
FIG. 3 is a schematic view of the morphology of nitrogen-doped Asymmetric Carbon Nanoparticles (ACNs) according to a preferred embodiment of the present invention, wherein a is a schematic view of three types of particles ACN-1, ACN-2, and ACN-3, b is a TEM image of ACN-1, c is a TEM image of ACN-2, and d is a TEM image of ACN-3;
FIG. 4 is a graph of the size of oil droplets in an emulsion plotted against the particle morphology, wherein the abscissa is TMB/H, in accordance with a preferred embodiment of the present invention2The volume ratio of O/EtOH, (n%) is (EtOH/(EtOH + H)2O))％。
Detailed Description
The technical contents of the preferred embodiments of the present invention will be more clearly and easily understood by referring to the drawings attached to the specification. The present invention may be embodied in many different forms of embodiments and the scope of the invention is not limited to the embodiments set forth herein.
In the drawings, structurally identical elements are represented by like reference numerals, and structurally or functionally similar elements are represented by like reference numerals throughout the several views. The size and thickness of each component shown in the drawings are arbitrarily illustrated, and the present invention is not limited to the size and thickness of each component. The thickness of the components may be exaggerated where appropriate in the figures to improve clarity.
Example 1
As shown in figure 1, the principle schematic diagram of the "one-pot emulsion template method" is that a commercial Pluronic triblock copolymer P123 (poly (ethylene oxide) -b-poly (propylene oxide) -b-poly (ethylene oxide)) is used as a porous template, a non-ionic surfactant and m-phenylenediamine (mPD) are used as a carbon source, mesitylene (TMB) is used as an oil phase, Ammonium Persulfate (APS) is used as an initiator to control the average size of oil drops in the emulsion (oil drop size: 240-plus 830nm) by simply adjusting the content of ethanol (EtOH) and TMB in an emulsion system, as shown in figure 4, a series of single-component Asymmetric Polymer Nanoparticles (APNs) with abundant forms and sizes in the range of 240-plus 650nm are accurately and controllably constructed, and the APNs of mushroom-shaped, hub-shaped and acorn-shaped mesoporous poly (m-phenylenediamine) (PmNs) are shown in figure 2. And then pyrolyzed at 800 ℃ in a nitrogen atmosphere, carbonized and activated by NH3 to obtain nitrogen-doped Asymmetric Carbon Nanoparticles (ACNs) with a reserved structure, as shown in figure 3. The emulsion is easy to remove as a template, the preparation process can be simplified, and the environmental pollution is reduced. The specific process is as follows:
(1) an emulsion template was prepared by first dissolving commercial Pluronic triblock copolymer P123 in water and stirring vigorously at room temperature until the solution was clear. Then adding TMB to emulsify the solution to obtain emulsion; the oil drop with the average particle size of 240-830nm is obtained by regulating the dosage of EtOH and TMB and adjusting the particle size of the oil drop of the emulsion.
(2) The formed emulsion is used as a template to guide the mPD monomer to auto-polymerize under APS initiation.
(3) And after the reaction is completed, efficiently removing the emulsion template by using water and ethanol, and drying to obtain black polymer particles PmPD.
(4) The prepared asymmetric PmPD particles are carbonized in N through a calcination procedure2Further calcining at 800 ℃ under the atmosphere to obtain the nitrogen-doped asymmetric carbon particles.
Example 2
Preparation of APNs: 43mg of P123 were first dissolved in 10ml of water in a 20ml glass vessel. Next, the mixture was stirred vigorously at room temperature for 2h until the solution was clear. Then 250. mu.l of TMB was added to the solution and a stable white emulsion was obtained after sonication for 1min at room temperature using a probe sonicator (120W). The particle size of the oil droplets in the emulsion was characterized by confocal laser microscopy. After emulsification, 85mg of mPD was added to the emulsion and the mixture was stirred for a further 1 h. Next, 200mg APS was added to the emulsion to induce self-polymerization of the mPD monomer. After 12h of reaction, three cycles of washing with water and ethanol and centrifugation yielded black poly-m-phenylenediamine polymer particles (PmPD). The final product was dried at 60 ℃ under vacuum for 1 day to give APN-1 with a TMB/Water/EtOH volume ratio of 1/40/0. APNs (APN-1, APN-2 and APN-3) at other ratios can be obtained by simply adjusting the amount of EtOH or TMB in the emulsion system while keeping the other experimental parameters unchanged, and the detailed emulsion formulation is given in Table 1.
Preparing ACNs: the dried APNs powder was transferred into a corundum crucible and carbonized by the calcination procedure (preheated at 350 ℃ for 2h and in N2At 2 deg.C for min under atmosphere-1Further heating at 800 deg.C for 2h to obtain ACNs. Finally, using NH at 800 ℃3Gas flow (60ml min)-1) And activating the prepared carbon material for 30min to obtain the ACNs.
TABLE 1 preparation formulation of PmPD asymmetric particles
The foregoing detailed description of the preferred embodiments of the invention has been presented. It should be understood that numerous modifications and variations could be devised by those skilled in the art in light of the present teachings without departing from the inventive concepts. Therefore, the technical solutions available to those skilled in the art through logic analysis, reasoning and limited experiments based on the prior art according to the concept of the present invention should be within the scope of protection defined by the claims.
Claims (10)
1. A method for regulating the structure of a one-component asymmetric particle by emulsion size, comprising the steps of:
step 1, preparing an emulsion template, firstly dissolving P123 in H2Stirring at room temperature until the solution is clear, adding TMB to emulsify the solution, adding EtOH to obtain emulsion oil drops, and regulating the particle size of the emulsion oil drops by regulating the using amounts of the EtOH and the TMB to ensure that the average particle size of the emulsion oil drops is 240-830 nm;
step 2, using the emulsion oil drops as emulsion templates to guide the mPD monomer to self-polymerize under the initiation of APS;
step 3, after the reaction is completed, efficiently removing the emulsion template by using water and ethanol, and drying to obtain black PmPD single-component asymmetric polymer nanoparticles;
step 4, carbonizing the PmPD single-component asymmetric polymer nano particles through a calcination procedure, and adding N2Pyrolyzing at 800 deg.C under atmosphere, carbonizing, and adding NH at 800 deg.C3The gas flow is activated to obtain the nitrogen-doped asymmetric carbon particles.
2. The method for regulating the structure of a one-component asymmetric particle by emulsion size of claim 1, wherein the EtOH and TMB are used in a ratio ranging from 0-20:1-6.4 in step 1.
3. The method for regulating the structure of a single-component asymmetric particle by emulsion size as claimed in claim 1, wherein the size range of the PmPD asymmetric polymer nanoparticle in step 3 is 240-650 nm.
4. The method for regulating the structure of single-component asymmetric particles according to claim 1, wherein the PmPD asymmetric polymer nanoparticles of step 3 are mushroom-shaped, hub-shaped, or rubbery-shaped.
5. The method for regulating the structure of a one-component asymmetric particle by emulsion size of claim 1, wherein the amount of P123 used in step 1 is 43 mg.
6. The method for regulating the structure of a one-component asymmetric particle by emulsion size of claim 1, wherein the amount of TMB used in step 1 is 250 μ L.
7. The method for regulating the structure of a one-component asymmetric particle by emulsion size of claim 1, wherein the mPD in step 2 is used in an amount of 250 mg.
8. The method for regulating the structure of single-component asymmetric particles by emulsion size according to claim 1, wherein the amount of APS used in step 2 is 200 mg.
9. The method for size-controlling one-component asymmetric particle structures by emulsion of claim 1, wherein the pyrolysis of step 4 is carbonized at a heating rate of 2 ℃ for min-1The heating time is 2 h.
10. The method for regulating a one-component asymmetric particle structure by emulsion size of claim 1, wherein NH of step 43The flow rate of the gas flow is 60ml min-1And the activation time is 30 min.
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