CN112592451A - Polymer composite material with rough surface, nano carbon material, preparation method and application - Google Patents

Polymer composite material with rough surface, nano carbon material, preparation method and application Download PDF

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CN112592451A
CN112592451A CN202011480247.XA CN202011480247A CN112592451A CN 112592451 A CN112592451 A CN 112592451A CN 202011480247 A CN202011480247 A CN 202011480247A CN 112592451 A CN112592451 A CN 112592451A
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water
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CN112592451B (en
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陆安慧
徐爽
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Dalian University of Technology
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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
    • 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
    • C08G14/04—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 with phenols
    • C08G14/06—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 with phenols and monomers containing hydrogen attached to nitrogen
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • B01J20/205—Carbon nanostructures, e.g. nanotubes, nanohorns, nanocones, nanoballs
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/18—Carbon
    • 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
    • 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
    • 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
    • C08G14/04—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 with phenols
    • C08G14/06—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 with phenols and monomers containing hydrogen attached to nitrogen
    • C08G14/10—Melamines

Abstract

The invention relates to a polymer composite material with a rough surface, a nano carbon material, a preparation method and application. Phenolic compounds, carbonyl compounds, amino compounds and colloid template solutions are mixed, and sequential polymerization is carried out by utilizing the dynamic difference of a polycondensation reaction, a Schiff base reaction and a Mannich reaction at a micelle interface to generate nano islands or nano particles on the surface or the edge of a nano material, so that the rough structure of the surface of the nano material is constructed. The method does not need additional etching and deposition processes, and has simple and controllable process. The adsorbent prepared by the invention can realize the rapid diffusion of gas, and the diffusion rate is 5-10 times of that of the commercial adsorbent; the catalyst carrier prepared by the method can realize anchoring of metal active particles and inhibition of migration and agglomeration of active components under high temperature conditions, and effectively improves the stability of the catalyst.

Description

Polymer composite material with rough surface, nano carbon material, preparation method and application
Technical Field
The invention belongs to the field of nano materials, and particularly relates to a polymer composite material with a rough surface, a nano carbon material, a preparation method and an application.
Background
The adsorption separation technology is an important technology for industrially separating and purifying the mixed gas, has the characteristics of high adsorption rate and high selectivity, and has the advantages of low energy consumption, low corrosion and high purity when used for separating the mixed gas. The adsorbent is the core of the adsorption separation technology, and the indexes for evaluating the adsorbent mainly comprise adsorption capacity, selectivity, adsorption rate and the like. The adsorption rate influences the energy consumption in the separation process, the faster the adsorption rate is, the less the energy consumption in the chemical production process is, and the research and development of the adsorbent with the rapid adsorption rate are important requirements of the industry.
The two-dimensional lamellar porous material has a short z-axis diffusion path, and theoretically can shorten the transmission path of gas molecules in the normal direction. In Chinese patent CN104437373, biomass is used as a carbon source, and a porous carbon nanosheet material is prepared by alkali activation. Chinese patent CN108975331 takes coal pitch and petroleum pitch as carbon sources, prepares heteroatom-doped porous carbon nano-sheets by a molten salt method, and solves the problem of low utilization rate of a pore structure caused by stacking of two-dimensional nano-sheets by constructing the porous structure. The Chinese patent CN106115660 obtains the porous carbon nano-sheet with smooth surface and uniform size by molecular self-assembly from bottom to top. When the nano-sheet is used as an adsorbent for gas separation, due to the strong surface-surface stacking effect among the nano-sheet layers, the smooth sheets are easy to generate compact accumulation, the pore utilization rate is reduced, the gas transmission pressure drop is increased, and the gas adsorption rate is greatly reduced.
In addition, when the supported catalyst used in industry is applied to a high-temperature reaction process, the problems of migration and agglomeration of metal active particles at high temperature often exist, so that the activity of the catalyst is reduced and even the catalyst is completely inactivated. The design of the structure of the carrier to anchor the metal active particles or limit the migration of the active particles is an effective strategy for inhibiting the agglomeration of active components and improving the stability of the supported catalyst. Chinese patent CN106115660 designs alumina with defects on the surface, which can be used for stabilizing noble metal nanoparticles. By designing the surface morphology of the carrier, a rough structure is manufactured on the surface, and the migration of the active nanoparticles can be limited. Chemical etching, laser and plasma etching techniques, micromachining and the like are commonly used to fabricate rough structures on surfaces.
Disclosure of Invention
The technical problems to be solved by the invention are as follows: the preparation of polymer composite materials with rough surfaces and nano carbon materials in the prior art needs the processes of etching, deposition and the like, and the process is complex.
In view of the defects of the prior art, one of the purposes of the invention is to provide a polymer composite material with a rough surface, the other purpose of the invention is to provide a preparation method of the polymer composite material with the rough surface, the third purpose of the invention is to provide a nanocarbon material with the rough surface, the fourth purpose of the invention is to provide a preparation method of the nanocarbon material with the rough surface, and the fifth purpose of the invention is to provide application of the nanocarbon material with the rough surface in the aspect of an adsorbent or a catalyst carrier.
The technical scheme of the invention is as follows:
a rough-surface composite material, which is spherical, rod-shaped, sheet-shaped or polyhedral in morphology and is obtained by a preparation method comprising the following steps:
(1) dispersing the nano material in water, and adding a surfactant according to needs or heating, cooling and standing to obtain a colloid template solution, wherein the colloid template solution comprises the following components in parts by weight: nano materials: water is 0.004-0.025: 20;
(2) adding a phenolic compound, a carbonyl compound, the colloidal template solution prepared in the step (1) and a water or alcohol-water mixture according to a ratio, wherein the carbonyl compound is an aldehyde compound or a ketone compound, the molar ratio of the phenolic compound to the carbonyl compound is 0.1-2: 1, the weight ratio of the phenolic compound to the water or alcohol-water mixture is 1: 900-2500, and the weight ratio of the phenolic compound to the colloidal template solution is 1: 20-200;
(3) adding an amino compound into the mixture obtained in the step (2), and carrying out pre-reaction to obtain a product A, wherein the molar ratio of the amino compound to the phenolic compound obtained in the step (2) is 0.04-0.4: 1;
(4) continuously reacting the product A obtained in the step (3), wherein the reaction temperature is 0-120 ℃, and obtaining a product B;
(5) and (4) filtering, washing and drying the product B obtained in the step (4) to obtain the composite material with a rough surface.
In the step (1), when the surfactant exists, the weight ratio of the surfactant: and the ratio of water to water is 0.005-0.02: 20.
The molar ratio of the phenolic compound to the carbonyl compound in the step (2) is 1-2: 1.
In the step (2), the volume ratio of the alcohol solvent to the water in the alcohol-water mixture is 0.01-3: 1.
The molar ratio of the amino compound in the step (3) to the phenolic compound in the step (2) is 0.04-0.2: 1.
The phenolic compound is one or more than two of phenol, resorcinol, phloroglucinol, 2, 3-xylenol and bisphenol A, and is preferably phloroglucinol.
The carbonyl compound is one or more than two of formaldehyde, glyoxal, 4-pyridylaldehyde, 2-pyridylaldehyde, benzaldehyde, terephthalaldehyde, isophthalaldehyde and acetophenone, and is preferably benzaldehyde or terephthalaldehyde.
The amino compound is one or two of aniline, p-phenylenediamine, benzidine, ethylenediamine, 1, 6-hexanediamine, cyclohexanediamine, p-aminobenzoic acid, melamine, alanine and lysine, and preferably aniline.
The alcohol solvent is one or more than two of methanol, ethanol and glycol, and preferably ethanol.
The nano material is graphene oxide, hydrotalcite, boron nitride, stearic acid, phase-change wax, laponite, nano cobalt hydroxide, polymer nanospheres, ZnO nanorods, ZIF-8 nanoparticles and Fe2O3One of a carbide, nitride or carbonitride of nanocubes and transition metals.
The surfactant is one or more than two of F127, P123, cetyl trimethyl ammonium bromide and polyvinylpyrrolidone.
The reaction temperature in the step (4) is 60-80 ℃.
The invention also provides a preparation method of the composite material with the rough surface, which comprises the following steps:
(1) dispersing the nano material in water, and adding a surfactant according to needs or heating, cooling and standing to obtain a colloid template solution, wherein the colloid template solution comprises the following components in parts by weight: nano materials: water is 0.004-0.025: 20;
(2) adding a phenolic compound, a carbonyl compound, the colloidal template solution prepared in the step (1) and a water or alcohol-water mixture according to a ratio, wherein the carbonyl compound is an aldehyde compound or a ketone compound, the molar ratio of the phenolic compound to the carbonyl compound is 0.1-2: 1, the weight ratio of the phenolic compound to the water or alcohol-water mixture is 1: 900-2500, and the weight ratio of the phenolic compound to the colloidal template solution is 1: 20-200;
(3) adding an amino compound into the mixture obtained in the step (2), and carrying out pre-reaction to obtain a product A, wherein the molar ratio of the amino compound to the phenolic compound obtained in the step (2) is 0.04-0.4: 1;
(4) continuously reacting the product A obtained in the step (3), wherein the reaction temperature is 0-120 ℃, and obtaining a product B;
(5) and (4) filtering, washing and drying the product B obtained in the step (4) to obtain the composite material with a rough surface.
The invention also provides a nano carbon material with a rough surface.
The nano carbon material with the rough surface is obtained by carbonizing the composite material with the rough surface under the inert atmosphere condition, and the shape of the nano carbon material with the rough surface is spherical, rod-shaped, sheet-shaped or polyhedral.
The carbonization treatment process comprises the steps of firstly heating to 300-400 ℃, preserving heat for 60-120min, and then heating to 500-1200 ℃ for carbonization treatment; preferably, the carbonization temperature rise rate is 1-5 ℃ per minute-1The carbonization treatment time is preferably 60 to 240 min.
The invention also provides a preparation method of the nano carbon material with the rough surface, which comprises the following steps:
(1) dispersing the nano material in water, and adding a surfactant according to needs or heating, cooling and standing to obtain a colloid template solution, wherein the colloid template solution comprises the following components in parts by weight: nano materials: water is 0.004-0.025: 20;
(2) adding a phenolic compound, a carbonyl compound, the colloidal template solution prepared in the step (1) and a water or alcohol-water mixture according to a ratio, wherein the carbonyl compound is an aldehyde compound or a ketone compound, the molar ratio of the phenolic compound to the carbonyl compound is 0.1-2: 1, the weight ratio of the phenolic compound to the water or alcohol-water mixture is 1: 900-2500, and the weight ratio of the phenolic compound to the colloidal template solution is 1: 20-200;
(3) adding an amino compound into the mixture obtained in the step (2), and carrying out pre-reaction to obtain a product A, wherein the molar ratio of the amino compound to the phenolic compound obtained in the step (2) is 0.04-0.4: 1;
(4) continuously reacting the product A obtained in the step (3), wherein the reaction temperature is 0-120 ℃, and obtaining a product B;
(5) and (4) filtering, washing and drying the product B obtained in the step (4) to obtain the composite material with a rough surface.
(6) And (5) carbonizing the composite material with the rough surface obtained in the step (5) under the inert atmosphere condition to obtain the nano carbon material with the rough surface.
The invention also provides the application of the nano carbon material with the rough surface in the aspects of adsorbents or catalyst carriers.
The invention has the beneficial effects that: the invention adopts solution synthesis, sequentially polymerizes at a micelle interface according to the kinetic difference of polycondensation reaction, Schiff base reaction and Mannich reaction, generates nano islands or nano particles on the surface or the edge of the nano material, thereby constructing the rough structure of the surface of the nano material, and can change the quantity and the height of the nano islands or the nano particles through the design of a formula and a process, thereby realizing the regulation and control of the rough structure of the surface of the nano material. The method does not need additional etching and deposition processes, and has simple and controllable process. The adsorbent prepared by the invention can realize the rapid diffusion of gas, and the diffusion rate is 5-10 times of that of the commercial adsorbent; the catalyst carrier prepared by the method can realize anchoring of metal active particles and inhibition of migration and agglomeration of active components under high temperature conditions, and effectively improves the stability of the catalyst.
Drawings
FIG. 1 is a scanning electron micrograph of a polymer sheet having a rough surface prepared in example 1;
FIG. 2 is a scanning electron microscope image of the nano-carbon sheet with rough surface prepared in example 1;
FIG. 3 is a scanning electron microscope image of the carbon nanospheres prepared in example 6 with rough surfaces;
FIG. 4 is a transmission electron micrograph of the catalyst 1 prepared in example 3 before reaction;
FIG. 5 is a transmission electron micrograph of the catalyst 1 prepared in example 3 after reaction;
FIG. 6 is a transmission electron micrograph of catalyst 2 prepared in comparative example 3 before reaction;
fig. 7 is a transmission electron microscope image of catalyst 2 prepared in comparative example 3 after reaction.
Detailed Description
It is an object of the present invention to provide a polymer composite having a rough surface.
In a preferred embodiment of the present invention, specifically, a rough-surface composite material, which has a spherical, rod-like, sheet-like or polyhedral morphology, is obtained by a preparation method comprising the steps of:
(1) dispersing the nano material in water, adding a surfactant according to needs and/or heating to 70-90 ℃, cooling to 25-40 ℃ and standing to obtain a colloidal template solution, wherein the colloidal template solution comprises the following components in parts by weight: nano materials: water is 0.004-0.025: 20;
in particular, the hydrophilic nano material can be dissolved in water, and if the hydrophilic nano material is a hydrophobic nano material, a surfactant is added and/or heating is needed to increase the dispersibility of the hydrophilic nano material in water; the hydrophilic nano material dispersion liquid can be directly mixed with water, and if the hydrophilic nano material dispersion liquid is hydrophobic nano material dispersion liquid, a surfactant is required to be added to improve the dispersibility.
(2) Adding a phenolic compound, a carbonyl compound, the colloidal template solution prepared in the step (1) and an alcohol-water compound into a reaction kettle in proportion, and stirring for 30-60min, wherein the molar ratio of the phenolic compound to the carbonyl compound is 0.1-2: 1, the carbonyl compound is an aldehyde compound or a ketone compound, the weight ratio of the phenolic compound to the alcohol-water mixture is 1: 900-2500, and the weight ratio of the phenolic compound to the colloidal template solution is 1: 20-200;
(3) adding an amino compound into the reaction kettle, stirring or standing for 15-30min for pre-reaction to obtain a product A, wherein the molar ratio of the amino compound to the phenolic compound in the step (2) is 0.04-0.4: 1;
(4) starting a reflux device, and continuously reacting the product A obtained in the step (3), wherein the reaction temperature is 0-120 ℃, and the reaction time is 4-36h, so as to obtain a product B;
(5) and (4) carrying out centrifugal filtration, washing and drying on the product B obtained in the step (4) under the condition of 8000r/min to obtain the composite material with a rough surface.
In the step (1), when the surfactant exists, the weight ratio of the surfactant: and the ratio of water to water is 0.005-0.02: 20.
The molar ratio of the phenolic compound to the carbonyl compound in the step (2) is 1-2: 1.
In the step (2), the volume ratio of the alcohol solvent to the water in the alcohol-water mixture is 0.01-3: 1.
The molar ratio of the amino compound in the step (3) to the phenolic compound in the step (2) is 0.04-0.2: 1.
The phenolic compound is one or more than two of phenol, resorcinol, phloroglucinol, 2, 3-xylenol and bisphenol A, and is preferably phloroglucinol.
The carbonyl compound is one or more than two of formaldehyde, glyoxal, 4-pyridylaldehyde, 2-pyridylaldehyde, benzaldehyde, terephthalaldehyde, isophthalaldehyde and acetophenone, and is preferably benzaldehyde or terephthalaldehyde.
The amino compound is one or two of aniline, p-phenylenediamine, benzidine, ethylenediamine, 1, 6-hexanediamine, cyclohexanediamine, p-aminobenzoic acid, melamine, alanine and lysine, and preferably aniline.
The alcohol solvent is one or more than two of methanol, ethanol and glycol, and preferably ethanol.
The nano material is graphene oxide, hydrotalcite, boron nitride, stearic acid, phase-change wax, laponite, nano cobalt hydroxide, polymer nanospheres, ZnO nanorods, ZIF-8 nanoparticles and Fe2O3One of a carbide, nitride or carbonitride of nanocubes and transition metals.
The surfactant is one or more than two of F127, P123, cetyl trimethyl ammonium bromide and polyvinylpyrrolidone.
In the step (4), the reaction temperature is 60-80 ℃, and the reaction time is 4-10 h.
In the embodiment of the invention, graphene oxide, nano cobalt hydroxide, polymer nanospheres, ZnO nanorods, ZIF-8 nanoparticles and Fe2O3Nanocubes and Ti3C2TxAll adopt dispersion liquid.
The preparation method of the graphene oxide dispersion liquid comprises the following steps:
(1) weighing 7.5g of potassium permanganate and 1.5g of graphite powder, and grinding for 2 hours in a ball mill at the rotating speed of 300 r/min;
(2) slowly adding the ground mixture into a three-neck flask filled with 115mL of sulfuric acid and 40mL of phosphoric acid under the ice bath condition, and reacting for 2h at the temperature of 34-36 ℃;
(3) weighing 230mL of deionized water, pouring the deionized water into a dropping funnel, slowly dropwise adding the deionized water into the three-neck flask, controlling the temperature below 50 ℃, and completing dropwise adding within 2 hours;
(4) after the water is added, reacting for 2 hours at the temperature of 34-36 ℃;
(5) the stirring was stopped, the reaction mixture was poured into a 1L beaker, and 700mLH was added2O, stirred well with a glass rod, and 12.5mL (30%) H was added slowly2O2Reacting for 10-15 min;
(6) centrifuging and filtering, sequentially washing the lower layer material with 5% hydrochloric acid solution for 4 times and deionized water for 8 times, and dialyzing until no sulfate radical and phosphate radical are detected;
(7) performing ultrasonic oscillation for 4 hours to obtain a Graphene Oxide (GO) dispersion liquid;
(8) and calibrating the concentration of the graphene oxide dispersion liquid to be 10g/L by adopting a drying and weighing method.
The preparation method of the hydrotalcite dispersion liquid comprises the following steps:
(1) weighing 0.297g of zinc nitrate hexahydrate in a 100mL conical flask, adding 50mL of water, and stirring at room temperature to obtain a zinc nitrate aqueous solution;
(2) weighing 0.187g of aluminum nitrate nonahydrate in a 100mL conical flask, adding 50mL of water, stirring at room temperature to obtain an aluminum nitrate aqueous solution, pouring the aluminum nitrate solution into a zinc nitrate aqueous solution, and uniformly mixing;
(3) weighing 0.12g of urea in a 50mL conical flask, and adding 20mL of water to obtain a urea solution;
(4) slowly adding the urea solution into a mixed solution obtained by aluminum nitrate and zinc nitrate, and uniformly stirring;
(5) transferring the mixed solution into a 150mL hydrothermal kettle to react for 48h at 110 ℃;
(6) after the reaction is finished, cooling to room temperature, centrifuging the reaction solution at the rotating speed of 8000r/min, and washing with deionized water and ethanol to obtain a white product. Dispersing in 50mL of deionized water to obtain hydrotalcite powder;
(7) and calibrating the concentration of the hydrotalcite dispersion liquid to be 5g/L by adopting a drying and weighing method.
The preparation method of the nano cobalt hydroxide dispersion liquid comprises the following steps:
(1) weighing 1.164g of cobalt nitrate hexahydrate and 0.1g of polyvinylpyrrolidone into a conical flask, adding 30mL of deionized water, and stirring for dissolving to obtain a pink solution;
(2) measuring 8mL of hydrazine hydrate (85%) and dropwise adding the hydrazine hydrate into the solution, and stirring for 30 min;
(3) transferring the solution into a 100mL hydrothermal kettle, and reacting at 160 ℃ for 18 h;
(4) and cooling to room temperature after the reaction is finished, centrifuging the reaction solution at the rotating speed of 6000r/min, and washing with deionized water and ethanol to obtain a pink product. Dispersing in 50mL of deionized water to obtain a nano cobalt hydroxide dispersion liquid;
(5) the concentration of the nano cobalt hydroxide dispersion is calibrated to be 10g/L by adopting a drying and weighing method.
The preparation method of the polymer nanosphere dispersion liquid comprises the following steps:
(1) weighing 0.44g of resorcinol and 0.2g of surfactant F127 into a round-bottom flask, adding 400mL of deionized water, and stirring at 28 ℃ for 30 min;
(2) weighing 584uL of 30 wt% formaldehyde solution, adding into the solution, and stirring for 15min to obtain white solution;
(3) weighing 90mg of ethylamine, adding into the mixed solution, and stirring for 30 min;
(4) measuring 1mL of 1.5M ammonia water solution, adding into the mixed solution, and stirring for 15 min;
(5) adjusting the temperature to 80 ℃, stirring for 18h, stopping stirring, standing and cooling to room temperature;
(6) centrifuging, washing with deionized water until the pH value is neutral, and adding 100mL of deionized water to obtain a polymer nanosphere dispersion liquid;
(7) the concentration of the polymer nanosphere dispersion liquid is calibrated to be 3g/L by adopting a drying and weighing method.
The preparation method of the ZnO nanorod dispersion liquid comprises the following steps:
(1) weighing 0.3g of zinc chloride and 0.065g of hexamethylenetetramine, respectively dissolving in 100mL of deionized water and 30mL of deionized water, and stirring at room temperature until the zinc chloride and the hexamethylenetetramine are dissolved;
(2) measuring 50mL of zinc chloride solution and 10mL of hexamethylenetetramine solution, mixing the zinc chloride solution and the hexamethylenetetramine solution in a beaker, uniformly stirring, transferring the mixture to a 100mL hydrothermal kettle, reacting for 4 hours at 90 ℃, and cooling to room temperature;
(3) centrifuging, washing with deionized water until the pH value is neutral, and adding 300mL of deionized water to obtain a ZnO nanorod dispersion liquid;
(4) the concentration of the ZnO nanorod dispersion liquid is calibrated to be 1g/L by adopting a drying and weighing method.
The preparation method of the ZIF-8 nanoparticle dispersion liquid comprises the following steps:
(1) weighing 0.735g of zinc nitrate hexahydrate in a 250mL beaker, adding 150mL of methanol, and stirring for dissolving to obtain a zinc nitrate solution;
(2) weighing 1.523g of 2-methylimidazole in a 100mL beaker, adding 80mL of methanol, and stirring for dissolving to obtain a 2-methylimidazole solution;
(3) adding the 2-methylimidazole solution into a zinc nitrate solution, and stirring for 1h at 25 ℃;
(4) stopping stirring after the reaction is finished, centrifuging the reaction solution, washing the reaction solution with methanol until the pH value is close to neutral to obtain a ZIF-8 product, and adding 200mL of deionized water to obtain a ZIF-8 nano particle dispersion solution;
(5) and calibrating the concentration of the ZIF-8 nano particle dispersion liquid by adopting a drying and weighing method to be 5 g/L.
Said Fe2O3The preparation method of the nano cubic dispersion liquid comprises the following steps:
(1) weighing 0.404g of ferric nitrate nonahydrate and 0.6g of polyvinylpyrrolidone, adding 36mL of N, N-dimethylformamide solution, and stirring for 30 min;
(2) stopping stirring, transferring the solution into a 70mL hydrothermal kettle, and reacting at 180 ℃ for 30h
(3) After the reaction is finished, cooling to room temperature;
(4) centrifuging the product, washing with deionized water and ethanol solution 4-5 times, adding 300mL of water to obtain Fe2O3A nano-cubic dispersion liquid;
(5) calibrating Fe by adopting drying and weighing method2O3The concentration of the nano cubic dispersion liquid is 2 g/L.
The Ti3C2TxThe dispersion was prepared according to the method described in Angewandte Chemie International Edition, 2017,56,1825, and specifically prepared as follows:
(1) weighing 1g of Ti3AlC2Putting the powder into 15mL of 50 wt% hydrofluoric acid solution, stirring for 24h at room temperature, centrifuging, washing for 4-5 times by using deionized water, and drying for 48h at room temperature;
(2) weighing 15mL of dimethyl sulfoxide, adding the dimethyl sulfoxide into the dried powder, stirring for 24h at room temperature, centrifuging, washing for 4-5 times by using deionized water, and adding 500mL of water;
(3) under the protection of argon, the dispersion is subjected to ultrasonic treatment for 4 to 8 hours and is centrifuged for 5 to 6 times to obtain Ti3C2TxA dispersion liquid;
(4) ti calibration by drying and weighing method3C2TxThe concentration of the dispersion was 4 g/L.
Another object of the present invention is to provide a method for preparing the above composite material with a rough surface, comprising the following steps:
(1) dispersing the nano material in water, and adding a surfactant according to needs or heating, cooling and standing to obtain a colloid template solution, wherein the colloid template solution comprises the following components in parts by weight: nano materials: water is 0.004-0.025: 20;
(2) adding a phenolic compound, a carbonyl compound, the colloidal template solution prepared in the step (1) and an alcohol-water compound into a reaction kettle in proportion, and stirring for 30-60min, wherein the molar ratio of the phenolic compound to the carbonyl compound is 0.1-2: 1, the carbonyl compound is an aldehyde compound or a ketone compound, the weight ratio of the phenolic compound to the alcohol-water mixture is 1: 900-2500, and the weight ratio of the phenolic compound to the colloidal template solution is 1: 20-200;
(3) adding an amino compound into the reaction kettle, stirring or standing for 15-30min for pre-reaction to obtain a product A, wherein the molar ratio of the amino compound to the phenolic compound in the step (2) is 0.04-0.4: 1
(4) Starting a reflux device, and continuously reacting the product A obtained in the step (3), wherein the reaction temperature is 0-120 ℃, and the reaction time is 4-36h, so as to obtain a product B;
(5) and (4) carrying out centrifugal filtration, washing and drying on the product B obtained in the step (4) under the condition of 8000r/min to obtain the composite material with a rough surface.
The invention also aims to provide a nano carbon material with a rough surface.
The nano carbon material with the rough surface is obtained by carbonizing the composite material with the rough surface under the inert atmosphere condition, and the shape of the nano carbon material with the rough surface is spherical, rod-shaped, sheet-shaped or polyhedral.
The carbonization treatment process comprises the steps of firstly heating to 300-400 ℃, preserving heat for 60-120min, and then heating to 500-1200 ℃ for carbonization treatment; preferably, the carbonization temperature rise rate is 1-5 ℃ per minute-1The carbonization treatment time is preferably 60 to 240 min.
The fourth purpose of the invention is to provide a preparation method of the nano carbon material with the rough surface, which comprises the following steps:
(1) dispersing the nano material in water, and adding a surfactant according to needs or heating, cooling and standing to obtain a colloid template solution, wherein the colloid template solution comprises the following components in parts by weight: nano materials: water is 0.004-0.025: 20;
(2) adding a phenolic compound, a carbonyl compound, the colloidal template solution prepared in the step (1) and an alcohol-water compound into a reaction kettle in proportion, and stirring for 30-60min, wherein the molar ratio of the phenolic compound to the carbonyl compound is 0.1-2: 1, the carbonyl compound is an aldehyde compound or a ketone compound, the weight ratio of the phenolic compound to the alcohol-water mixture is 1: 900-2500, and the weight ratio of the phenolic compound to the colloidal template solution is 1: 20-200;
(3) adding an amino compound into the reaction kettle, stirring or standing for 15-30min for pre-reaction to obtain a product A, wherein the molar ratio of the amino compound to the phenolic compound in the step (2) is 0.04-0.4: 1
(4) Starting a reflux device, and continuously reacting the product A obtained in the step (3), wherein the reaction temperature is 0-120 ℃, and the reaction time is 4-36h, so as to obtain a product B;
(5) and (4) carrying out centrifugal filtration, washing and drying on the product B obtained in the step (4) under the condition of 8000r/min to obtain the composite material with a rough surface.
(6) And (5) carbonizing the composite material with the rough surface obtained in the step (5) under the argon atmosphere condition to obtain the nano carbon material with the rough surface.
The fifth purpose of the invention is to provide the application of the nano carbon material with rough surface in the aspect of adsorbent or catalyst carrier.
The rough surface polymer composite material, the nanocarbon material, the preparation method and the application of the invention will be specifically described through specific examples and experimental examples.
The inventive examples and comparative examples used starting materials and equipment sources as shown in table 1.
TABLE 1 examples of the invention and comparative examples use sources of raw materials and equipment
Figure BDA0002837267910000111
Figure BDA0002837267910000121
Figure BDA0002837267910000131
Figure BDA0002837267910000141
Figure BDA0002837267910000151
The morphological characteristic data of the polymer material with rough surface and the nanocarbon material in the following examples are measured by a scanning electron microscope.
Example 1
(1) Preparation of polymer sheet having rough surface
A. Weighing 20mg of surfactant F127, 12mg of hydrophobic stearic acid and 20g of water, adding into a reactor, heating to 80 ℃, stirring for 4 hours, cooling to 40 ℃, and standing for 24 hours to obtain a two-dimensional nanosheet colloid template solution;
B. preparing 300g of ethanol/water mixture according to the volume ratio of ethanol to water of 2:1, adding the mixture into a reaction kettle, then weighing 101mg of terephthalaldehyde, 126mg of phloroglucinol and 10g of the colloidal template solution, sequentially adding the weighed materials into the reaction kettle, and stirring for 30 min;
C. weighing 0.1mL of 0.4mol/L phenylenediamine solution, adding into a reaction kettle, and stirring for 15 min;
D. starting a reflux device, and reacting for 4 hours at the temperature of 80 ℃;
E. and (3) centrifugally filtering, washing and drying the reaction product at 8000r/min to obtain the polymer sheet with a rough surface.
(2) Preparation of nano carbon sheet with rough surface
And (3) putting the polymer sheet with the rough surface prepared in the step (1) into a carbonization furnace for carbonization treatment, protecting with argon, heating from room temperature to 400 ℃ at a speed of 2 ℃/min, keeping the temperature for 120min, heating to 800 ℃ at a speed of 5 ℃/min, and keeping the temperature for 120min to obtain the nano carbon sheet with the rough surface.
Scanning electron micrographs of the polymer sheet with rough surface prepared in example 1 are shown in FIG. 1, and it can be seen from FIG. 1 that the length of the polymer sheet with rough surface: 5-7um, width: 0.9-1.3um, thickness: 50nm, the length of the surface nano island particles is 250-400nm, and the height of the surface nano island particles is 50 nm.
Fig. 2 is a scanning electron microscope image of the nano carbon sheet with a rough surface prepared in example 1, and it can be seen from fig. 2 that the length of the nano carbon sheet with a rough surface is: 4-6.5um, width: 0.8-1.0um, thickness: 6-15nm, the length of the surface nano island particles is 100-150nm, and the height of the surface nano island particles is 6-15 nm.
Example 2
(1) Preparation of polymer sheet having rough surface
A. Weighing 15mg of surfactant P123, 10mg of hydrophobic boron nitride and 30g of water, adding the materials into a reactor, heating to 70 ℃, stirring for 6 hours, cooling to 30 ℃, and standing for 24 hours to obtain a two-dimensional nanosheet colloid template solution;
B. weighing 300g of water, adding the water into a reaction kettle, weighing 92mg of m-phthalaldehyde, 151mg of phloroglucinol and 15g of the colloidal template solution, sequentially adding the weighed materials into the reaction kettle, and stirring for 60 min;
C. measuring 0.3mol/L of benzidine 0.5mL solution, adding the solution into a reaction kettle, and standing for 30 min;
D. starting a reflux device, and reacting for 6 hours at 100 ℃;
E. and (3) centrifugally filtering, washing and drying the reaction product at 8000r/min to obtain the polymer sheet with a rough surface.
(2) Preparation of nano carbon sheet with rough surface
And (3) putting the polymer sheet with the rough surface prepared in the step (1) into a carbonization furnace for carbonization treatment, protecting with argon, heating from room temperature to 300 ℃ at a speed of 3 ℃/min, keeping the temperature for 60min, heating to 900 ℃ at a speed of 5 ℃/min, and keeping the temperature for 180min to obtain the nano carbon sheet with the rough surface.
Length of rough-surface polymer sheet: 5-6um, width: 2-4um, thickness: 70nm, the length of the surface nano island particles is 200-300nm, and the height of the surface nano island particles is 50nm
Length of the carbon nano-sheet with rough surface: 3-4um, width: 2-3um, thickness: 20-25nm, the length of the surface nano island particles is 150-200nm, and the height of the surface nano island particles is 15-20 nm.
Example 3
(1) Preparation of polymer sheet having rough surface
A. Weighing 5mg of surfactant cetyl trimethyl ammonium bromide, 10mg of hydrophobic stearic acid and 20g of water, adding the weighed materials into a reactor, heating to 90 ℃, stirring for 8 hours, cooling to 25 ℃, and standing for 24 hours to obtain a two-dimensional nanosheet colloid template solution;
B. preparing 400g of ethanol/water mixture according to the volume ratio of ethanol to water of 0.5:1, adding the mixture into a reaction kettle, then weighing 145mg of glyoxal, 189mg of 2, 3-xylenol and 10g of the colloidal template solution, sequentially adding the mixture into the reaction kettle, and stirring for 45 min;
C. measuring 0.6mL of 1.0mol/L L-lysine solution, adding into a reaction kettle, and stirring for 30 min;
D. starting a reflux device, and reacting for 6 hours at the temperature of 80 ℃;
E. and (3) centrifugally filtering, washing and drying the reaction product at 8000r/min to obtain the polymer sheet with a rough surface.
(2) Preparation of nano carbon sheet with rough surface
And (2) putting the polymer sheet with the rough surface prepared in the step (1) into a carbonization furnace for carbonization treatment, protecting with argon, heating from room temperature to 400 ℃ at a speed of 3 ℃/min, keeping the temperature for 60min, heating to 1000 ℃ at a speed of 5 ℃/min, and keeping the temperature for 150min to obtain the nano carbon sheet with the rough surface.
Length of rough-surface polymer sheet: 2-4um, width: 1-3um, thickness: 50nm, the length of the surface nano island particles is 100-200nm, and the height of the nano island is 30-50 nm.
Length of the carbon nano-sheet with rough surface: 1-2um, width: 0.2-1.5um, thickness: 10-20nm, the length of the surface nano island particles is 50-100nm, and the height of the nano island is 5-10 nm.
Example 4
(1) Preparation of polymer sheet having rough surface
A. Weighing 6mg of hydrophilic laponite and 25g of water, adding into a reactor, and stirring for 5 hours to obtain a two-dimensional nanosheet colloid template solution;
B. preparing 300g of methanol/water mixture according to the volume ratio of methanol to water of 1:1, adding the mixture into a reaction kettle, then weighing 107mg of 4-pyridylaldehyde, 252mg of phloroglucinol and 10g of the colloidal template solution, sequentially adding the mixture into the reaction kettle, and stirring for 30 min;
C. weighing 0.5mol/L beta-alanine 0.2mL, adding into a reaction kettle, and standing for 15 min;
D. starting a reflux device, and reacting for 6 hours at the temperature of 75 ℃;
E. and (3) centrifugally filtering, washing and drying the reaction product at 8000r/min to obtain the polymer sheet with a rough surface.
(2) Preparation of nano carbon sheet with rough surface
And (2) putting the polymer sheet with the rough surface prepared in the step (1) into a carbonization furnace for carbonization treatment, protecting with argon, heating from room temperature to 350 ℃ at a speed of 3 ℃/min, keeping the temperature for 60min, heating to 600 ℃ at a speed of 3 ℃/min, and keeping the temperature for 240min to obtain the nano carbon sheet with the rough surface.
Length of rough-surface polymer sheet: 4-5um, width: 4-7um, thickness: 65nm, the surface nano-island particle length is 100-300 nm.
Length of the carbon nano-sheet with rough surface: 2-3um, width: 3-5um, thickness: 20-30nm and the length of the surface nano island particle is 80-130 nm.
Example 5
(1) Preparation of polymer sheet having rough surface
A. Weighing 18mg of surfactant F127, 6mg of hydrophobic phase-change wax and 30g of water, adding into a reactor, heating to 80 ℃, stirring for 4 hours, cooling to 25 ℃, and standing for 24 hours to obtain a two-dimensional nanosheet colloid template solution;
B. preparing 400g of ethylene glycol/water mixture according to the volume ratio of ethylene glycol/water of 3:1, adding the mixture into a reaction kettle, then weighing 240mg of acetophenone, 252mg of phenol and 20g of the colloidal template solution, sequentially adding the mixture into the reaction kettle, and stirring for 45 min;
C. weighing 0.35mL of 0.5mol/L ethylenediamine solution, adding into a reaction kettle, and stirring for 15 min;
D. starting a reflux device, and refluxing for 8 hours at 120 ℃;
E. and (3) centrifugally filtering, washing and drying the reaction product at 8000r/min to obtain the polymer sheet with a rough surface.
(2) Preparation of nano carbon sheet with rough surface
And (2) putting the polymer sheet with the rough surface prepared in the step (1) into a carbonization furnace for carbonization treatment, protecting with argon, heating from room temperature to 400 ℃ at a speed of 3 ℃/min, keeping the temperature for 60min, heating to 500 ℃ at a speed of 4 ℃/min, and keeping the temperature for 200min to obtain the nano carbon sheet with the rough surface.
Length of rough-surface polymer sheet: 6-8um, width: 5-7um, thickness: 70nm, the length of the surface nano island particle is 100-300 nm.
Length of the carbon nano-sheet with rough surface: 5-6um, width: 4-6um, thickness: 5-10nm and the length of the surface nano island particle is 80-120 nm.
Example 6
(1) Preparation of rough-surface polymer spheres
A. Weighing 5mL of hydrophilic polymer nanosphere dispersion liquid and 20g of water, adding the dispersion liquid into a reactor, and stirring for 4 hours to obtain a zero-dimensional nanosphere colloidal template solution;
B. preparing 300g of ethanol/water mixture according to the volume ratio of ethanol to water of 0.1:1, adding the mixture into a reaction kettle, then weighing 134mg of terephthalaldehyde, 168mg of resorcinol and 5g of the colloidal template solution, sequentially adding the weighed materials into the reaction kettle, and stirring for 30 min;
C. weighing 0.5mL of 0.3mol/L hexamethylenediamine solution, adding into a reaction kettle, and stirring for 15 min;
D. starting a reflux device, and reacting for 36 hours at the temperature of 0 ℃;
E. and (3) centrifugally filtering, washing and drying the reaction product at 8000r/min to obtain the polymer sheet with a rough surface.
(2) Preparation of nano carbon ball with rough surface
And (2) putting the polymer sheet with the rough surface prepared in the step (1) into a carbonization furnace for carbonization treatment, protecting with argon, heating from room temperature to 1000 ℃ at a speed of 3 ℃/min, keeping the temperature for 120min, heating to 1200 ℃ at a speed of 3 ℃/min, and keeping the temperature for 150min to obtain the nano carbon ball with the rough surface.
Diameter of polymer sphere having rough surface: 370nm and the length of the surface nano island particle is 60-80 nm.
The scanning electron microscope image of the carbon nanosphere with rough surface prepared in example 6 is shown in fig. 3, and it can be seen from fig. 3 that the diameter of the carbon nanosphere with rough surface is as follows: 250nm and the length of the surface nano island particle is 20-40 nm.
Example 7
(1) Preparation of rough-surfaced Polymer rods
A. Weighing 20mg of surfactant cetyl trimethyl ammonium bromide, 7mL of hydrophobic ZnO nanorod dispersion liquid and 30g of water, adding the mixture into a reactor, and stirring for 6 hours to obtain a one-dimensional nanorod colloidal template solution;
B. preparing 400g of methanol/water mixture according to the volume ratio of methanol to water of 0.3:1, adding the mixture into a reaction kettle, then weighing 2.28g of glyoxal, 260mg of phloroglucinol and 30g of the colloidal template solution, sequentially adding the mixture into the reaction kettle, and stirring for 30 min;
C. weighing 0.7mL of 1mol/L aniline solution, adding into a reaction kettle, and stirring for 15 min;
D. starting a reflux device, and reacting for 20 hours at the temperature of 60 ℃;
E. and (3) centrifugally filtering, washing and drying the reaction product at 8000r/min to obtain the polymer rod with a rough surface.
(2) Preparation of carbon nano-rod with rough surface
And (2) putting the polymer sheet with the rough surface prepared in the step (1) into a carbonization furnace for carbonization treatment, protecting with argon, heating from room temperature to 400 ℃ at a speed of 3 ℃/min, keeping the temperature for 60min, heating to 700 ℃ at a speed of 5 ℃/min, and keeping the temperature for 180min to obtain the nano carbon rod with the rough surface.
Length of rough-surfaced polymer rod: 5-6um, width: 0.7-1um, surface nano island particle length 50-70nm
Length of carbon nano-rod with rough surface: 4-5um, width: 0.5-0.8nm and the length of the surface nano island particle is 40-50 nm.
Example 8
(1) Preparation of polymer sheet having rough surface
A. Weighing 2.5mL of hydrophilic graphene oxide dispersion liquid, weighing 30mg of surfactant F127 and 50g of water, adding the surfactant F127 and the water into a reactor, and stirring for 5 hours to obtain a two-dimensional nanosheet colloid template solution;
B. preparing 300g of ethanol/water mixture according to the volume ratio of ethanol to water of 0.01:1, adding the mixture into a reaction kettle, then weighing 101mg of benzaldehyde, 126mg of 2, 3-xylenol and 20g of the colloidal template solution, sequentially adding the weighed materials into the reaction kettle, and stirring for 30 min;
C. measuring 0.6mL of 0.25mol/L para aminobenzoic acid solution, adding into a reaction kettle, and stirring for 15 min;
D. starting a reflux device, and reacting for 30 hours at the temperature of 30 ℃;
E. and (3) centrifugally filtering, washing and drying the reaction product at 8000r/min to obtain the polymer sheet with a rough surface.
(2) Preparation of nano carbon sheet with rough surface
And (2) putting the polymer sheet with the rough surface prepared in the step (1) into a carbonization furnace for carbonization treatment, protecting with argon, heating from room temperature to 400 ℃ at a speed of 3 ℃/min, keeping the temperature for 60min, heating to 800 ℃ at a speed of 5 ℃/min, and keeping the temperature for 180min to obtain the nano carbon sheet with the rough surface.
Length of rough-surface polymer sheet: 10-20um, width: 10-15um, thickness: 50nm, the length of the surface nano island particles is 200-400nm, and the height of the surface nano island particles is 50 nm.
Length of the carbon nano-sheet with rough surface: 10-15um, width: 8-10um, thickness: 10-12nm, the length of the surface nano island particles is 150-200nm, and the height of the surface nano island particles is 10-12 nm.
Example 9
(1) Preparation of polymer sheet having rough surface
A. Weighing 2mL of hydrophilic hydrotalcite dispersion liquid and 20g of water, adding the hydrotalcite dispersion liquid and the water into a reactor, and stirring for 5 hours to obtain a two-dimensional nanosheet colloid template solution;
B. preparing 400g of ethanol/water mixture according to the volume ratio of ethanol to water of 2:1, adding the mixture into a reaction kettle, then weighing 2.85g of glyoxal, 262mg of phloroglucinol and 10g of the colloidal template solution, sequentially adding the mixture into the reaction kettle, and stirring for 30 min;
C. measuring 0.5mol/L cyclohexanediamine 0.15mL solution, adding into a reaction kettle, and stirring for 15 min;
D. starting a reflux device, and reacting for 6 hours at 70 ℃;
E. and (3) centrifugally filtering, washing and drying the reaction product at 8000r/min to obtain the polymer sheet with a rough surface.
(2) Preparation of nano carbon sheet with rough surface
And (2) putting the polymer sheet with the rough surface prepared in the step (1) into a carbonization furnace for carbonization treatment, protecting with argon, heating from room temperature to 400 ℃ at a speed of 3 ℃/min, keeping the temperature for 60min, heating to 900 ℃ at a speed of 5 ℃/min, and keeping the temperature for 80min to obtain the nano carbon sheet with the rough surface.
Edge length of rough-surfaced polymer sheet: 80-100nm in size and polygonal. Thickness: 20-30nm, the length of the surface nano island particles is 10-15nm, and the height of the nano island particles is 5-10nm
The length of the carbon nano-sheet with rough surface is 80-100nm, and the carbon nano-sheet is polygonal. Thickness: 10-15nm, the length of the surface nano island particles is 8-10nm, and the height of the nano island particles is 5-6 nm.
Example 10
(1) Preparation of roughened Polymer cubes
A. 10mg of surfactant poly was weighedVinylpyrrolidone, 12.5ml of hydrophobic Fe2O3Adding the nano cubic dispersion liquid and 20g of water into a reactor, stirring for 6 hours, and stirring and mixing to obtain a three-dimensional cubic colloidal template solution;
B. preparing 200g of ethanol/water mixture according to the volume ratio of ethanol to water of 2.5:1, adding the mixture into a reaction kettle, weighing 82mg of terephthalaldehyde, 122mg of phloroglucinol and 10g of the colloid template solution, sequentially adding the weighed materials into the reaction kettle, and stirring for 30 min;
C. measuring 0.6mL of 0.35mol/L aniline solution, adding into a reaction kettle, and stirring for 15 min;
D. starting a reflux device, and reacting for 15h at the temperature of 60 ℃;
E. and (3) centrifugally filtering, washing and drying the reaction product at 8000r/min to obtain the polymer sheet with a rough surface.
(2) Preparation of nano carbon cube with rough surface
And (2) putting the polymer nanocubes with rough surfaces prepared in the step (1) into a carbonization furnace for carbonization treatment, protecting with argon, heating from room temperature to 400 ℃ at a speed of 1 ℃/min, keeping the temperature for 60min, heating to 1000 ℃ at a speed of 1 ℃/min, and keeping the temperature for 180min to obtain the carbon nanorods with rough surfaces.
Edge length of rough-surfaced polymer cube: 20-40nm, surface nano island particle length 10-15nm
The side length of the nano carbon cube with rough surface is as follows: 10-20nm and the length of the surface nano island particle is 5-7 nm.
Example 11
1) Preparation of polymer sheet having rough surface
A. Weighing 1.5mL of hydrophilic nano cobalt hydroxide dispersion liquid and 20g of water, adding the dispersion liquid into a reactor, and stirring for 5 hours to obtain a two-dimensional nanosheet colloid template solution;
B. preparing 200g of ethanol/water mixture according to the volume ratio of ethanol to water of 0.8:1, adding the mixture into a reaction kettle, then weighing 100mg of 2-pyridylaldehyde, 218mg of bisphenol A and 10g of the colloidal template solution, sequentially adding the weighed materials into the reaction kettle, and stirring for 30 min;
C. measuring 30mg of melamine, adding the melamine into a reaction kettle, and stirring for 15 min;
D. starting a reflux device, and reacting for 24 hours at 40 ℃;
E. and (3) centrifugally filtering, washing and drying the reaction product at 8000r/min to obtain the polymer sheet with a rough surface.
(2) Preparation of nano carbon sheet with rough surface
And (2) placing the polymer sheet with the rough surface prepared in the step (1) into a carbonization furnace for carbonization treatment, protecting with argon, heating from room temperature to 400 ℃ at the speed of 2 ℃/min, keeping the temperature for 60min, heating to 1100 ℃ at the speed of 2 ℃/min, and keeping the temperature for 180min to obtain the nano carbon sheet with the rough surface.
Edge length of rough-surfaced polymer sheet: 2um, polygonal, thickness: 50nm, the length of the surface nano island particles is 50nm, and the height of the nano island particles is 30nm
The side length of the carbon nano-sheet with rough surface is as follows: 1.5um, polygon, thickness: 30nm, the length of the surface nano island particles is 40nm, and the height of the nano island particles is 20 nm.
Example 12
1) Preparation of rough-surfaced polymeric polyhedra
A. Weighing 8mL of ZIF-8 hydrophobic nanoparticle dispersion liquid and 40g of water, adding the mixture into a reactor, and stirring for 5 hours to obtain a colloidal template solution;
B. preparing 400g of ethanol/water mixture according to the volume ratio of ethanol to water of 0.4:1, adding the mixture into a reaction kettle, then weighing 100mg of formaldehyde, 200mg of phloroglucinol and 10g of the colloidal template solution, sequentially adding the mixture into the reaction kettle, and stirring for 30 min;
C. weighing 0.25mol/L p-phenylenediamine solution 0.4mL, adding into a reaction kettle, and stirring for 15 min;
D. starting a reflux device, and reacting for 6 hours at 70 ℃;
E. and (3) centrifugally filtering, washing and drying the reaction product at 8000r/min to obtain the polymer sheet with a rough surface.
(2) Preparation of nano carbon polyhedron with rough surface
And (2) putting the polymer sheet with the rough surface prepared in the step (1) into a carbonization furnace for carbonization treatment, protecting with argon, heating from room temperature to 400 ℃ at a speed of 3 ℃/min, keeping the temperature for 60min, heating to 1100 ℃ at a speed of 3 ℃/min, and keeping the temperature for 180min to obtain the nano carbon sheet with the rough surface.
Edge length of polymer polyhedron with rough surface: 0.8-1um, and the length of the surface nano island particle is 30 nm.
The side length of the nano carbon polyhedron with rough surface is as follows: 0.5-0.7um, and the length of the surface nano island particle is 20 nm.
Example 13
1) Preparation of polymer sheet having rough surface
A. 2mL of hydrophilic Ti was measured3C2TxAdding the dispersion and 20g of water into a reactor, and stirring for 6 hours to obtain a colloidal template solution;
B. preparing 400g of methanol/water mixture according to the volume ratio of methanol to water of 0.5:1, adding the mixture into a reaction kettle, then weighing 120mg of benzaldehyde, 188mg of phenol and 10g of the colloidal template solution, sequentially adding the mixture into the reaction kettle, and stirring for 30 min;
C. weighing 0.8mL of 0.25mol/L p-phenylenediamine solution, adding the solution into a reaction kettle, and stirring for 15 min;
D. starting a reflux device, and reacting for 10 hours at the temperature of 50 ℃;
E. and (3) centrifugally filtering, washing and drying the reaction product at 8000r/min to obtain the polymer sheet with a rough surface.
(2) Preparation of nano carbon sheet with rough surface
And (2) putting the polymer sheet with the rough surface prepared in the step (1) into a carbonization furnace for carbonization treatment, protecting with argon, heating from room temperature to 400 ℃ at a speed of 3 ℃/min, keeping the temperature for 90min, heating to 800 ℃ at a speed of 4 ℃/min, and keeping the temperature for 60min to obtain the nano carbon sheet with the rough surface.
Edge length of rough-surfaced polymer sheet: 1-2um, and the length of the surface nano island particle is 40-70 nm.
The side length of the carbon nano-sheet with rough surface is as follows: 1-2um, and the length of the surface nano island particle is 30-60 nm.
Comparative example 1
The adsorbent is commercial YK30-60 coconut shell carbon.
Comparative example 2
The adsorbent is CMS-260 carbon molecular sieve sold in the market.
Comparative example 3
10g of asphalt is weighed and added into 200mL of nitric acid solution with the concentration of 10mol/L, and the mixture is refluxed for 12 hours at 80 ℃. Dispersing the oxidized asphalt substance in urea solution, stirring at 25 deg.C for 1h, and drying at 70 deg.C overnight to obtain nitrogen-containing asphalt substance. And (3) putting the nitrogen-containing asphalt substance into a tubular furnace to pyrolyze for 3h at 600 ℃ under the argon atmosphere to obtain the asphalt-based carbon material. Mixing the asphalt-based carbon material with KOH (weight ratio of 1:4), and activating for 2h at 750 ℃ to obtain the asphalt-based smooth carbon nanosheet.
Experimental example 1
The gas diffusion rate and IAST separation selectivity coefficient were determined using the samples of examples 1 and 2 and comparative examples 1 to 3 as adsorbents.
The gas diffusion rate experimental method is as follows: the adsorbent pairs of examples 1, comparative examples 1 and 3 were tested for CH using an intelligent gravimetric analyzer IGA-100 at 25 ℃ and 13mbar4The diffusion rate of (c); adsorbent pair C of example 2 and comparative example 2 was tested using an intelligent gravimetric analyzer IGA-100 at 25 ℃ and 500mbar3H6The results of the experiment are shown in Table 2.
The IAST separation selectivity test method is as follows: static adsorption testing of a single gas was performed using a Micromeritics ASAP 2020 physical adsorption apparatus from Micromeritics corporation for inventive examples 1, 2 and comparative examples 1-3, as follows: weighing 100mg of adsorbent sample, filling the adsorbent sample into a sample tube, degassing for 6h at 200 ℃ under a vacuum condition, then placing the sample tube in a constant-temperature water bath, filling test gas into the sample tube, measuring the adsorption amounts of the adsorbent under different pressures at the adsorption temperature of 25 ℃, fitting by using a Langmuir-Freundlich equation, calculating the adsorption amounts (q) of the gas under different partial pressures (P) according to the Langmuir equation according to the fitting result, and then calculating the IAST separation selectivity coefficient S by an IAST methodi,jThe calculation formula is as follows:
Figure BDA0002837267910000251
wherein q isiAnd q isjDenotes the amount of adsorption of i, j components on the adsorbent, yi、yjThe mole fractions of components i, j, respectively, in the gas phase.
Results of the IAST separation Selectivity coefficient experiments are shown in Table 2:
TABLE 2 gas diffusion coefficient and IAST separation selection coefficient
Numbering Gas diffusion rate, m2/s IAST separation selectivity coefficient
Example 1 8.8*10-11(CH4) 10(CH4/N2)
Example 2 3.5*10-11(C3H6) 18(C3H6/C3H8)
Comparative example 1 1.5*10-11(CH4) 1(CH4/N2)
Comparative example 2 0.3*10-11(C3H6) 1(C3H6/C3H8)
Comparative example 3 1.0*10-11(CH4) 4(CH4/N2)
As can be seen from Table 2, the adsorbent prepared by the nanocarbon material prepared by the method can realize rapid diffusion of gas, the diffusion rate is 5-10 times that of the commercial adsorbent, and the IAST separation selectivity coefficient is also obviously superior to that of the commercial adsorbent and the smooth carbon nanomaterial.
Experimental example 2
The sample of example 3 of the present invention was used as a carrier for the catalyst loaded with Cu metal to prepare catalyst 1, and the sample of comparative example 3 was used as a carrier for the catalyst loaded with Cu metal to prepare catalyst 2, which were used for ethanol conversion dehydrogenation to prepare acetaldehyde, respectively, at a reaction temperature of 300 ℃, with transmission electron microscopes before and after the reaction of catalyst 1 as shown in fig. 4 and 5, and transmission electron microscopes before and after the reaction of catalyst 2 as shown in fig. 6 and 7.
As can be seen from FIGS. 4 and 5, the Cu particle size in catalyst 1 was 5-8nm and remained substantially unchanged before and after the reaction; as can be seen from FIGS. 6 and 7, the Cu particle size in the catalyst 2 before the reaction is 5-12nm, and after the reaction, the Cu particle has a significant agglomeration structure and the particle size is 20-40 nm.
In conclusion, the invention utilizes the dynamic difference of the polycondensation reaction, the Schiff base reaction and the Mannich reaction at the micelle interface to carry out sequential polymerization, and generates nano islands or nano particles on the surface or the edge of the nano material, thereby constructing the rough structure of the surface of the nano material, and the quantity and the height of the nano islands or the nano particles can be changed through the design of the formula and the process, thereby realizing the regulation and control of the rough structure of the surface of the nano material. The adsorbent prepared by the invention can realize the rapid diffusion of gas, and the diffusion rate is 5-10 times of that of the commercial adsorbent; the catalyst carrier prepared by the method can realize anchoring of metal active particles and inhibition of migration and agglomeration of active components under high temperature conditions, and effectively improves the stability of the catalyst.
The foregoing is considered as illustrative and not restrictive in character, and that various modifications, equivalents, and improvements made within the spirit and principles of the invention are intended to be included within the scope of the invention.

Claims (17)

1. The rough-surface composite material is characterized by being spherical, rod-shaped, flaky or polyhedral in morphology and obtained by a preparation method comprising the following steps of:
(1) dispersing the nano material in water, adding a surfactant according to needs and/or heating, cooling and standing to obtain a colloid template solution, wherein the colloid template solution comprises the following components in parts by weight: nano materials: water is 0.004-0.025: 20;
(2) adding a phenolic compound, a carbonyl compound, the colloidal template solution prepared in the step (1) and a water or alcohol-water mixture according to a ratio, wherein the carbonyl compound is an aldehyde compound or a ketone compound, the molar ratio of the phenolic compound to the carbonyl compound is 0.1-2: 1, the weight ratio of the phenolic compound to the water or alcohol-water mixture is 1: 900-2500, and the weight ratio of the phenolic compound to the colloidal template solution is 1: 20-200;
(3) adding an amino compound into the mixture obtained in the step (2), and carrying out pre-reaction to obtain a product A, wherein the molar ratio of the amino compound to the phenolic compound obtained in the step (2) is 0.04-0.4: 1;
(4) continuously reacting the product A obtained in the step (3), wherein the reaction temperature is 0-120 ℃, and obtaining a product B;
(5) and (4) filtering, washing and drying the product B obtained in the step (4) to obtain the composite material with a rough surface.
2. The rough-surface composite material according to claim 1, wherein in the step (1), when the surfactant is present, the ratio of the surfactant to the total weight of the surfactant is: and the ratio of water to water is 0.005-0.02: 20.
3. The rough-surface composite material according to claim 1 or 2, wherein the molar ratio of the phenolic compound to the carbonyl compound in the step (2) is 1-2: 1.
4. The rough surface composite of any of claims 1-3, wherein the volume ratio of alcohol solvent to water in the alcohol-water mixture in step (2) is 0.01-3: 1.
5. The rough surface composite of any of claims 1-4, wherein the molar ratio of amino compound in step (3) to phenolic compound in step (2) is 0.04 to 0.2: 1.
6. The rough-surface composite according to any of claims 1 to 5, wherein the phenolic compound is one or more of phenol, resorcinol, phloroglucinol, 2, 3-xylenol, and bisphenol A, preferably phloroglucinol.
7. The surface-roughened composite material according to any one of claims 1 to 6, wherein the carbonyl compound is one or more of formaldehyde, glyoxal, 4-pyridineformaldehyde, 2-pyridineformaldehyde, benzaldehyde, terephthalaldehyde, isophthalaldehyde and acetophenone, preferably benzaldehyde or terephthalaldehyde.
8. The rough-surface composite according to any of claims 1 to 7, characterized in that the amino compound is one or two of aniline, p-phenylenediamine, benzidine, ethylenediamine, 1, 6-hexanediamine, cyclohexanediamine, p-aminobenzoic acid, melamine, alanine and lysine, preferably aniline.
9. The surface-roughened composite material according to any one of claims 1-8, wherein the alcohol solvent is one or more of methanol, ethanol and ethylene glycol, preferably ethanol.
10. The rough surface composite of any of claims 1-9, wherein the nanomaterial is graphene oxide, hydrotalcite, boron nitride, stearic acid, phase change wax, laponite, nano cobalt hydroxide, polymeric nanospheres, ZnO nanorods, ZIF-8 nanoparticles, Fe nanoparticles2O3One of a carbide, nitride or carbonitride of nanocubes and transition metals.
11. The rough surface composite of any of claims 1-10, wherein the surfactant is one or more of F127, P123, cetyltrimethylammonium bromide, and polyvinylpyrrolidone.
12. The rough-surface composite material according to any one of claims 1 to 11, wherein the reaction temperature in step (4) is 60 to 80 ℃.
13. A method of preparing a roughened composite material according to any one of claims 1-12, comprising the steps of:
(1) dispersing the nano material in water, and adding a surfactant according to needs or heating, cooling and standing to obtain a colloid template solution, wherein the colloid template solution comprises the following components in parts by weight: nano materials: water is 0.004-0.025: 20;
(2) adding a phenolic compound, a carbonyl compound, the colloidal template solution prepared in the step (1) and a water or alcohol-water mixture according to a ratio, wherein the carbonyl compound is an aldehyde compound or a ketone compound, the molar ratio of the phenolic compound to the carbonyl compound is 0.1-2: 1, the weight ratio of the phenolic compound to the water or alcohol-water mixture is 1: 900-2500, and the weight ratio of the phenolic compound to the colloidal template solution is 1: 20-200;
(3) adding an amino compound into the mixture obtained in the step (2), and carrying out pre-reaction to obtain a product A, wherein the molar ratio of the amino compound to the phenolic compound obtained in the step (2) is 0.04-0.4: 1;
(4) continuously reacting the product A obtained in the step (3), wherein the reaction temperature is 0-120 ℃, and obtaining a product B;
(5) and (4) filtering, washing and drying the product B obtained in the step (4) to obtain the composite material with a rough surface.
14. A nano carbon material with a rough surface, which is obtained by carbonizing the composite material with a rough surface of any one of claims 1 to 12 under an inert atmosphere, wherein the shape of the nano carbon material with a rough surface is spherical, rod-shaped, sheet-shaped or polyhedral.
15. The nano-carbon material with a rough surface as claimed in claim 14, wherein the carbonization treatment process comprises heating to 300-400 ℃, maintaining the temperature for 60-120min, and then heating to 500-1200 ℃ for carbonization treatment; preferably, the carbonization temperature rise rate is 1-5 ℃ per minute-1The carbonization treatment time is preferably 60 to 240 min.
16. The method for preparing the nano carbon material with the rough surface as claimed in claim 14 or 15, which is characterized by comprising the following steps:
(1) dispersing the nano material in water, and adding a surfactant according to needs or heating, cooling and standing to obtain a colloid template solution, wherein the colloid template solution comprises the following components in parts by weight: nano materials: water is 0.004-0.025: 20;
(2) adding a phenolic compound, a carbonyl compound, the colloidal template solution prepared in the step (1) and a water or alcohol-water mixture according to a ratio, wherein the carbonyl compound is an aldehyde compound or a ketone compound, the molar ratio of the phenolic compound to the carbonyl compound is 0.1-2: 1, the weight ratio of the phenolic compound to the water or alcohol-water mixture is 1: 900-2500, and the weight ratio of the phenolic compound to the colloidal template solution is 1: 20-200;
(3) adding an amino compound into the mixture obtained in the step (2), and carrying out pre-reaction to obtain a product A, wherein the molar ratio of the amino compound to the phenolic compound obtained in the step (2) is 0.04-0.4: 1;
(4) continuously reacting the product A obtained in the step (3), wherein the reaction temperature is 0-120 ℃, and obtaining a product B;
(5) and (4) filtering, washing and drying the product B obtained in the step (4) to obtain the composite material with a rough surface.
(6) And (5) carbonizing the composite material with the rough surface obtained in the step (5) under the inert atmosphere condition to obtain the nano carbon material with the rough surface.
17. Use of the nano-carbon sheet with rough surface according to claim 14 or 15 in adsorbent or catalyst carrier.
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