CN103466596B - Hollow nanosphere material as well as preparation method and application thereof - Google Patents
Hollow nanosphere material as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of nano material preparation, and discloses a hollow nanosphere material as well as a preparation method and an application thereof. The hollow nanosphere material is obtained by stacking nanospheres, the BET specific surface area of the hollow nanosphere material is 44-1226m<2>g<-1>, the total pore volume of the hollow nanosphere material is 0.15-1.20cm<3>g<-1>; the nanosphere is of a micropore shell-hollow nano structure, the diameter of the hollow cavity is 80-260nm, the thickness of the shell layer is 5-85nm, single-dispersion coefficient is as low as 0.005, and shell layer material is a polymer or carbon. By utilizing a hyper-crosslinking method, the stable inheritance of the hollow cavity of the polymer nanosphere and grid micropores of the shell layer in the normal-pressure drying and high-temperature carbonization processes is achieved; the single-dispersion coefficient of the hollow nanosphere material is as low as 0.005, the specific surface area is as high as 1226m<2>g<-1>, and the total pore volume is as high as 1.20cm<3>g<-1>.
Description
Technical field
The invention belongs to technical field of nanometer material preparation, particularly a kind of Hollow nanosphere material and its preparation method and application.
Background technology
Hollow nanospheres, particularly hollow polymer nanometer ball and Carbon Hollow nanometer ball, it is important nano material, there is unique nanoshells and the spherical nano-hollow chamber of encirclement thereof, be with a wide range of applications in fields such as biological medicine, absorption, separation, catalysis, the energy, nano-reactors.
Hollow polymer nanometer ball adopts the technology such as self-assembly method, template, (micro-) emulsion polymerization to prepare usually, and its sheath polymers can be divided into linear and crosslinked two kinds of structures.Crosslinked object is structure immobilization, and hollow polymer nanometer ball can be made all to be improved in mechanical strength, dimensional stability, solvent resistance and chemical stability etc., and the hollow polymer nanometer ball therefore with crosslinked shell is more common.But the degree of crosslinking of hollow polymer nanometer ball shell is usually lower, although many hollow polymer nanometer balls can keep excellent hollow nanospheres structure in the solution, after the drying by obvious for appearance fold, subside and even break.Meanwhile, for the hollow polymer nanometer ball with crosslinked shell, due to capillary tension powerful in drying process, their crosslinked shell is swelling and three-dimensional network gel hole that is that formed is difficult to be maintained after the drying in good solvent.What is more important, the crosslinked shell of most hollow polymer nanometer ball becomes charcoal poor, therefore directly their charings cannot be formed conductive Carbon Hollow nanometer ball.
Summary of the invention
In order to overcome the shortcoming of above-mentioned prior art with not enough, primary and foremost purpose of the present invention is to provide a kind of Hollow nanosphere material.
Another object of the present invention is the preparation method providing a kind of above-mentioned Hollow nanosphere material.This preparation method constructs by superhigh cross-linking chemical structure, realize each hierarchical pore structure of hollow polymer nanometer ball (comprising the three-dimensional network gel duct of spherical hollow cavity, shell inside) the stable succession in preparation process, thus obtain Hollow nanosphere material.
Still a further object of the present invention is to provide above-mentioned Hollow nanosphere material preparing the application in pharmaceutical carrier, electrode materials and sorbing material.
Object of the present invention is realized by following proposal:
A kind of Hollow nanosphere material, form by nanometer ball is stacking, BET specific surface area is 44 ~ 1226m
2g
-1, total pore volume is 0.15 ~ 1.20cm
3g
-1; Nanometer ball has micropore shell-cavity nanostructure, and cavity diameter is 80 ~ 260nm, and shell thickness is 5 ~ 85nm, and single dispersing coefficient is low to moderate 0.005, and Shell Materials is polymkeric substance or charcoal.
When nano ball shell layer material is polymkeric substance, nanometer ball cavity diameter is 90 ~ 260nm, and shell thickness is 5 ~ 85nm, and BET specific surface area is 44 ~ 441m
2g
-1, total pore volume is 0.15 ~ 1.20cm
3g
-1.
When nano ball shell layer material is charcoal, nanometer ball cavity diameter is 80 ~ 240nm, and shell thickness is 5 ~ 85nm, and BET specific surface area is 522 ~ 1226m
2g
-1, total pore volume is 0.44 ~ 0.85cm
3g
-1.
Preferably, described polymkeric substance refers to polystyrene-divinylbenzene (PSDVB).
The preparation method of above-mentioned Hollow nanosphere material, comprises following concrete steps:
(1) by Sodium dodecylbenzene sulfonate and sodium bicarbonate soluble in water; nitrogen protection; add the alcohol dispersion liquid of improved silica nanometer ball and vigorous stirring; add styrene monomer and Vinylstyrene; heat up and add initiator after stirring; centrifugal, washing, obtains pre-crosslinking polymer nanometer ball.
(2), after the pre-crosslinking polymer nanometer ball that obtains in step (1) is swelling in tetracol phenixin, add the backflow of catalyzer aluminum trichloride (anhydrous) after intensification and carry out Friedel-Crafts and surpass crosslinking reaction.
(3) add acetone/hydrochloric acid mixed solution and stop Friedel-Crafts reaction, filter and obtain solid product, through washing, filter and after drying, obtain super cross-linked polymer nanometer ball.
(4) the super cross-linked polymer nanometer ball obtained in step (3) is immersed in hydrofluoric acid, removes silicon-dioxide, obtain hollow polymer nanometer ball material.
Or the cross-linked polymer nanometer ball obtained in step (3) is placed in charring furnace, under inert gas atmosphere after charing, is immersed in 1 ~ 24h in hydrofluoric acid, remove silicon-dioxide, obtain Carbon Hollow nanometer ball material.
Or being placed in charring furnace by obtaining hollow polymer nanometer ball material in step (4), carbonizing under inert gas atmosphere, obtaining Carbon Hollow nanometer ball material.
Described in step (1), improved silica nanometer ball is prepared by following methods: adopt
legal system is for monodisperse silica nanometer ball, and recycle silicon alkane coupling agent carries out surface modification to it.
Preferably, following operation is specifically comprised:
Ethanol/teos solution and ethanol/ammonia/water solution short mix, stirring reaction 3h at 30 DEG C, obtains monodisperse silica nanometer ball; Drip silane coupling agent ethanolic soln again, reaction 36h, obtains improved silica nanometer ball.
In described ethanol/teos solution, ethanol and tetraethoxy volume ratio are 202.5:22.5.
In described ethanol/ammonia/water solution, ethanol, ammoniacal liquor and water volume ratio are 112.5:8.4:104.1.
In described silane coupling agent ethanolic soln, silane coupling agent volumetric concentration is 2%.
Preferably, described silane coupling agent refers at least one in KH-570 and 3-aminopropyl trimethoxysilane.
The volume ratio of ethanol/teos solution used, ethanol/ammonia/water solution and silane coupling agent ethanolic soln is 225:225:100.
In the alcohol dispersion liquid of improved silica nanometer ball described in step (1), improved silica nanometer ball content is 0.05 ~ 1g/ml.
Described initiator refers at least one in Potassium Persulphate, Diisopropyl azodicarboxylate and benzoyl peroxide.
Logical nitrogen deoxygenation before described water uses.
Silicon-dioxide used: vinylbenzene: Vinylstyrene: sodium bicarbonate: dodecylbenzene naphthenic acid sodium: initiator: the proportioning of water is (0.5 ~ 5) g:(0.1 ~ 15) ml:(0.05 ~ 5) ml:(0.1 ~ 0.5) g:(0.01 ~ 0.1) g:(0.1 ~ 0.5) g:(50 ~ 500) ml.
Described intensification refers to that Heating temperature is 50 ~ 100 DEG C.
In step (2), the amount of anhydrous tetracol phenixin used is that every 0.1 ~ 5g pre-crosslinking polymer nanometer ball uses 5 ~ 500ml.
The amount of aluminum trichloride (anhydrous) used is that every 1 ~ 50g pre-crosslinking polymer nanometer ball uses 0.1 ~ 5g aluminum trichloride (anhydrous).
Described Friedel-Crafts surpasses the condition of crosslinking reaction for reacting 0.25 ~ 72h at 30 ~ 75 DEG C.
Preferably, Friedel-Crafts reaction is carried out in anhydrous conditions,
In step (3), the amount of acetone/hydrochloric acid mixed solution used is that 0.1 ~ 5g pre-crosslinking polymer nanometer ball uses 20 ~ 500ml.
Preferably, described inert gas atmosphere is the nitrogen atmosphere of 100 ~ 800ml/min flow velocity.
Preferably, the condition of described charing is with the temperature rise rate of 1 ~ 10 DEG C/min to 700 ~ 1100 DEG C, charing 1 ~ 5h.
The amount of hydrofluoric acid used is that every 0.1 ~ 5g surpasses cross-linked polymer nanometer ball use 10ml.
The time of described immersion is 1 ~ 24h.
Above-mentioned Hollow nanosphere material is preparing the application in pharmaceutical carrier, electrode materials and sorbing material.
Mechanism of the present invention is:
The present invention adopts
legal system for monodisperse silica nanometer ball, and carries out surface modification with Silane coupling reagent KH-570 to it, and recycling letex polymerization is at its surface grafting precrosslink polystyrene; Utilize tetracol phenixin to carry out Friedel-Crafts as linking agent and solvent, aluminum trichloride (anhydrous) as catalyzer and surpass crosslinking reaction.There is carbonyl (-CO-) cross-bridge (by-CCl to obtained above
2-cross-bridge obtains through hydrolysis) super cross-linked polymer nanometer ball, directly remove silicon-dioxide and can obtain hollow polymer nanometer ball; Remove silicon-dioxide (or first removing silicon-dioxide high temperature carbonization again) again through high temperature carbonization and then obtain Carbon Hollow nanometer ball.
The present invention, relative to prior art, has following advantage and beneficial effect:
(1) the present invention utilizes carbonyl to surpass cross-linking chemistries, constructs the superhigh cross-linking polymeric shell layer having rigidity, realizes hollow cavity and the stable succession of shell network micropore in constant pressure and dry and high temperature carbonization process of polymer nanocomposite ball;
(2) surpass cross-linking chemistries based on carbonyl not to be only polymer nanocomposite ball and to introduce a large amount of oxygen levels, thus prepare Carbon Hollow nanometer ball; Also be conducive to multifunction and the high performance of hollow polymer and carbon nanospheres, the Hollow nanosphere material of gained has monodispersity (single dispersing coefficient is low to moderate 0.005), and high-specific surface area is (up to 1226m
2g
-1), (total pore volume is up to 1.20cm for high absorption property
3g
-1).
Accompanying drawing explanation
Fig. 1 is the transmission electron microscope picture of the Hollow nanosphere material that embodiment 1 prepares, and wherein, A is hollow polymer nanometer ball material, and B is Carbon Hollow nanometer ball material.
Fig. 2 is the nitrogen adsorption-desorption isotherm figure of the hollow polymer nanometer ball material that embodiment 1 prepares.
Fig. 3 is the nitrogen adsorption-desorption isotherm figure of the Carbon Hollow nanometer ball material that embodiment 1 prepares.
Fig. 4 is the nitrogen adsorption-desorption isotherm figure of the Carbon Hollow nanometer ball material that embodiment 2 prepares.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
Embodiment 1
(1) adopt
legal system is for monodisperse silica nanometer ball, concrete operations are as follows: the mixing solutions preparing ethanol/tetraethoxy (202.5mL/22.4mL) and ethanol/ammonia/water (112.5mL/8.4mL/104.1mL) in Erlenmeyer flask respectively, and short mix is even, setting stir speed (S.S.) is 250rpm, under 30 DEG C of conditions, react 3h, obtain monodisperse silica nanometer ball.Subsequently 2ml Silane coupling reagent KH-570 is dissolved in 100ml ethanol, adds in above-mentioned reaction system with dropping funnel, be added dropwise to complete rear continuation reaction 36h, obtain improved silica nanometer ball.
(2) 0.03g Sodium dodecylbenzene sulfonate and 0.24g sodium bicarbonate are dissolved in the 100mL deionized water of deoxygenation in advance, are stirred well to system even, in system, pass into nitrogen deoxygenation 15min.Add the improved silica alcohol dispersion liquid (being scattered in 10mL ethanol by the improved silica nanometer ball that 1.2g step (1) prepares) of ultrasonic disperse subsequently and vigorous stirring.After system is homogeneous, in system, add vinylbenzene 5mL and Vinylstyrene 1.5mL, stir after 10min and be warming up to 75 DEG C, add 0.12g Potassium Persulphate, centrifugal and remove tensio-active agent by toluene wash after reaction 24h, obtain pre-crosslinking polymer nanometer ball.
(3) get the pre-crosslinking polymer nanometer ball obtained in 1g above-mentioned (2) and be scattered in swelling 12h in 60ml tetracol phenixin, be warmed up to 75 DEG C subsequently, add 2.8g Aluminum chloride anhydrous, back flow reaction 24h.After question response terminates, add the mixed solution 60ml termination reaction of acetone/hydrochloric acid (3:1), cooled and filtered, the solid product mixed solvent obtained washs three times, and with deionized water wash to neutral, dry in 60 DEG C of vacuum chambers, obtain super cross-linked polymer nanometer ball.
(4) getting the super cross-linked polymer nanometer ball that 0.3g above-mentioned (3) obtains is scattered in 10mL hydrofluoric acid, stirs 24h, subsequently centrifugation, with deionized water wash, dries in 60 DEG C of vacuum drying ovens, obtain hollow polymer nanometer ball material.
(5) above-mentioned (3) are obtained super cross-linked polymer nanometer ball and be placed in charring furnace, under inert gas atmosphere, 900 DEG C are warming up to the temperature rise rate of 5 DEG C/min, then constant temperature charing 3h, after adopting hydrofluoric acid dips 24h, concentration is 0.1g/ml, centrifugation subsequently, with deionized water wash, dry in 60 DEG C of vacuum drying ovens, namely obtain Carbon Hollow nanometer ball material.
Transmission electron microscopy is carried out to the above-mentioned hollow polymer nanometer ball material for preparing and Carbon Hollow nanometer ball material, the results are shown in Figure 1.
Obtain hollow polymer nanometer ball material and Carbon Hollow nanometer ball dispersion of materials property coefficient is 0.005 with the ZetaPALS instrument test that Brookhaven company of the U.S. produces, illustrate that hollow polymer nanometer ball material and Carbon Hollow nanometer ball material have good monodispersity.
The ASAP2020 adsorption instrument nitrogen adsorption methods test of producing with Micromeritics company of the U.S..Test result is shown in Fig. 2 and Fig. 3, wherein, and the nitrogen adsorption-desorption isotherm figure of Fig. 2 to be the nitrogen adsorption-desorption isotherm figure, Fig. 3 of hollow polymer nanometer ball be Carbon Hollow nanometer ball.The BET specific surface area of hollow polymer nanometer ball is 441m
2g
-1, wherein micropore and external holes surface-area are respectively 246m
2g
-1and 195m
2g
-1; Total pore volume is 0.44cm
3g
-1, wherein Micropore volume and external holes (i.e. mesopore and macropore) pore volume are respectively 0.11cm
3g
-1and 0.33cm
3g
-1.The BET specific surface area of Carbon Hollow nanometer ball is 989m
2g
-1, wherein micropore and external holes surface-area are respectively 386m
2g
-1and 503m
2g
-1; Total pore volume is 0.85cm
3g
-1, wherein Micropore volume and external holes pore volume are respectively 0.17cm
3g
-1and 0.68cm
3g
-1.
Embodiment 2
(1) preparation of hollow polymer nanometer ball is with embodiment 1 step (1) ~ (4).
(2) the above-mentioned hollow polymer nanometer ball material prepared is placed in charring furnace, under inert gas atmosphere, is warming up to 900 DEG C with the temperature rise rate of 5 DEG C/min, then constant temperature charing 3h, namely obtains Carbon Hollow nanometer ball material.
The ASAP2020 adsorption instrument nitrogen adsorption methods test of producing with Micromeritics company of the U.S..Test result is shown in Fig. 4, and the BET specific surface area of the Carbon Hollow nanometer ball prepared is 1034m
2g
-, wherein micropore and external holes surface-area are respectively 848m
2g
-and 186m
2g
-; Total pore volume is cm
3g
-1, wherein Micropore volume and external holes pore volume are respectively 0.40cm
3g
-1and 0.43cm
3g
-1.
With above-mentioned Carbon Hollow nanometer ball for electrode materials, select 6M KOH to be electrolytic solution, be assembled into electrochemical capacitor, recording its quality than electric capacity with electrochemical cyclic voltammetry is 197F/g.
Embodiment 3
(1) preparation of monodisperse silica nanometer ball is with embodiment 1.
(2) 0.03g Sodium dodecylbenzene sulfonate and 0.24g sodium bicarbonate are dissolved in the 100mL deionized water of deoxygenation in advance, are stirred well to system even, in system, pass into nitrogen deoxygenation 15min.Add the improved silica alcohol dispersion liquid (1.2g silica nanosphere is scattered in 10mL ethanol) of ultrasonic disperse subsequently and vigorous stirring.After system is homogeneous, in system, add vinylbenzene 10mL and Vinylstyrene 3mL, stir after 10min and be warming up to 75 DEG C, and add 0.12g initiator potassium persulfate, centrifugal and with adding toluene wash removing tensio-active agent after reaction 24h.
(3) get the pre-crosslinking polymer nanometer ball obtained in 1g above-mentioned (2) and be scattered in swelling 12h in 60ml tetracol phenixin, be warmed up to 75 DEG C subsequently, add 2.8g Aluminum chloride anhydrous, back flow reaction 24h.After question response terminates, add the mixed solution 60ml termination reaction of acetone/hydrochloric acid, cooled and filtered, the solid product mixed solvent obtained washs three times, and with deionized water wash to neutral, dries in 60 DEG C of vacuum chambers.
(4) getting the super cross-linked polymer nanometer ball that 0.3g above-mentioned (3) obtains is scattered in 10mL hydrofluoric acid, stirs 24h, subsequently centrifugation, with deionized water wash, dries in 60 DEG C of vacuum drying ovens, obtain hollow polymer nanometer ball material.
With the ZetaPALS instrument test that Brookhaven company of the U.S. produces, the polydispersity coefficient of hollow polymer nanometer ball is 0.005.
The ASAP2020 adsorption instrument nitrogen adsorption methods test of producing with Micromeritics company of the U.S., the BET specific surface area of the hollow polymer nanometer ball of preparation is 394m
2g
-1, wherein micropore and external holes surface-area are respectively 310m
2g
-1and 83m
2g
-1, total pore volume is 0.32cm
3g
-1.
The IGA Instrument measuring hollow polymer nanometer ball produced with Hiden company of Britain is at normal temperatures to organic steam adsorption-desorption performance, and it is respectively 292mgg to the adsorptive capacity of toluene and methanol steam
-2and 427mgg
-2.
Embodiment 4
(1) preparation of hollow polymer nanometer ball is with embodiment 1 step (1) ~ (4).
(2) hollow polymer nanometer ball is placed in charring furnace, under inert gas atmosphere, is warming up to 1100 DEG C with the temperature rise rate of 5 DEG C/min, then constant temperature charing 3h, namely obtains Carbon Hollow nanometer ball.
The ASAP2020 adsorption instrument nitrogen adsorption methods test of producing with Micromeritics company of the U.S., the BET specific surface area of the Carbon Hollow nanometer ball of preparation is 1139m
2g
-1, wherein micropore and external holes surface-area are respectively 747m
2g
-1and 392m
2g
-1; Total pore volume is 0.70cm
3g
-1, wherein Micropore volume and external holes pore volume are respectively 0.34cm
3g
-1and 0.36cm
3g
-1.
Embodiment 5
(1) preparation of hollow polymer nanometer ball is with embodiment 1 step (1) ~ (4).
(2) hollow polymer nanometer ball is placed in charring furnace, under inert gas atmosphere, is warming up to 1000 DEG C with the temperature rise rate of 5 DEG C/min, then constant temperature charing 3h, namely obtains Carbon Hollow nanometer ball.
The ASAP2020 adsorption instrument nitrogen adsorption methods test of producing with Micromeritics company of the U.S., the BET specific surface area of the Carbon Hollow nanometer ball of preparation is 1180m
2g
-1, wherein micropore and external holes surface-area are respectively 934m
2g
-1and 246m
2g
-1; Total pore volume is 0.70cm
3g
-1, wherein Micropore volume and external holes pore volume are respectively 0.44cm
3g
-1and 0.36cm
3g
-1.
Embodiment 6
(1) preparation of hollow polymer nanometer ball is with embodiment 1 step (1) ~ (4).
(2) hollow polymer nanometer ball is placed in charring furnace, under inert gas atmosphere, is warming up to 800 DEG C with the temperature rise rate of 5 DEG C/min, then constant temperature charing 3h, namely obtains Carbon Hollow nanometer ball.
The ASAP2020 adsorption instrument nitrogen adsorption methods test of producing with Micromeritics company of the U.S., the BET specific surface area of the Carbon Hollow nanometer ball of preparation is 672m
2g
-1, wherein micropore and external holes surface-area are respectively 552m
2g
-1and 120m
2g
-1; Total pore volume is 0.63cm
3g
-1, wherein Micropore volume and external holes pore volume are respectively 0.26cm
3g
-1and 0.37cm
3g
-1.
Embodiment 7
(1) preparation of hollow polymer nanometer ball is with embodiment 1 step (1) ~ (4).
(2) hollow polymer nanometer ball is placed in charring furnace, under inert gas atmosphere, is warming up to 700 DEG C with the temperature rise rate of 5 DEG C/min, then constant temperature charing 3h, namely obtains Carbon Hollow nanometer ball.
The ASAP2020 adsorption instrument nitrogen adsorption methods test of producing with Micromeritics company of the U.S., the BET specific surface area of the Carbon Hollow nanometer ball of preparation is 522m
2g
-1, wherein micropore and external holes surface-area are respectively 416m
2g
-1and 106m
2g
-1; Total pore volume is 0.46cm
3g
-1, wherein Micropore volume and external holes pore volume are respectively 0.19cm
3g
-1and 0.27cm
3g
-1.
Embodiment 8
(1) preparation of hollow polymer nanometer ball is with embodiment 1 step (1) ~ (4).
(2) hollow polymer nanometer ball is placed in charring furnace, under inert gas atmosphere, is warming up to 900 DEG C with the temperature rise rate of 1 DEG C/min, then constant temperature charing 3h, namely obtains Carbon Hollow nanometer ball.
The ASAP2020 adsorption instrument nitrogen adsorption methods test of producing with Micromeritics company of the U.S., the BET specific surface area of the Carbon Hollow nanometer ball of preparation is 1226m
2g
-1.
Embodiment 9
(1) preparation of hollow polymer nanometer ball is with embodiment 1 step (1) ~ (4).
(2) hollow polymer nanometer ball is placed in charring furnace, under inert gas atmosphere, is warming up to 900 DEG C with the temperature rise rate of 2 DEG C/min, then constant temperature charing 3h, namely obtains Carbon Hollow nanometer ball.
The ASAP2020 adsorption instrument nitrogen adsorption methods test of producing with Micromeritics company of the U.S., the BET specific surface area of the Carbon Hollow nanometer ball of preparation is 989m
2g
-1.
Embodiment 10
(1) preparation of hollow polymer nanometer ball is with embodiment 1 step (1) ~ (4).
(2) hollow polymer nanometer ball is placed in charring furnace, under inert gas atmosphere, is warming up to 900 DEG C with the temperature rise rate of 10 DEG C/min, then constant temperature charing 3h, namely obtains Carbon Hollow nanometer ball.
The ASAP2020 adsorption instrument nitrogen adsorption methods test of producing with Micromeritics company of the U.S., the BET specific surface area of the Carbon Hollow nanometer ball of preparation is 1005m
2g
-1.
Embodiment 11
(1) preparation of hollow polymer nanometer ball is with embodiment 1 step (1) ~ (4).
(2) hollow polymer nanometer ball is placed in charring furnace, under inert gas atmosphere, is warming up to 900 DEG C with the temperature rise rate of 5 DEG C/min, then constant temperature charing 1h, namely obtains Carbon Hollow nanometer ball.
The ASAP2020 adsorption instrument nitrogen adsorption methods test of producing with Micromeritics company of the U.S., the BET specific surface area of the Carbon Hollow nanometer ball of preparation is 731m
2g
-1.
Embodiment 12
(1) preparation of hollow polymer nanometer ball is with embodiment 1 step (1) ~ (4).
(2) hollow polymer nanometer ball is placed in charring furnace, under inert gas atmosphere, is warming up to 900 DEG C with the temperature rise rate of 5 DEG C/min, then constant temperature charing 2h, namely obtains Carbon Hollow nanometer ball.
The ASAP2020 adsorption instrument nitrogen adsorption methods test of producing with Micromeritics company of the U.S., the BET specific surface area of the Carbon Hollow nanometer ball of preparation is 919m
2g
-1.
Embodiment 13
(1) preparation of hollow polymer nanometer ball is with embodiment 1 step (1) ~ (4).
(2) hollow polymer nanometer ball is placed in charring furnace, under inert gas atmosphere, is warming up to 900 DEG C with the temperature rise rate of 5 DEG C/min, then constant temperature charing 5h, namely obtains Carbon Hollow nanometer ball.
The ASAP2020 adsorption instrument nitrogen adsorption methods test of producing with Micromeritics company of the U.S., the BET specific surface area of the Carbon Hollow nanometer ball of preparation is 1052m
2g
-1.
Embodiment 14
(1) preparation of pre-crosslinking polymer nanometer ball is with embodiment 1 step (1) ~ (2).Get 1g pre-crosslinking polymer nanometer ball and be scattered in swelling 24h in 60ml tetracol phenixin, be warmed up to 75 DEG C subsequently, add 2.8g Aluminum chloride anhydrous, back flow reaction 0.25h.After question response terminates, add the mixed solution 60ml termination reaction of acetone/hydrochloric acid, cooled and filtered, the solid product mixed solvent obtained washs three times, and with deionized water wash to neutral, dries in 60 DEG C of vacuum chambers.
(2) getting the super cross-linked polymer nanometer ball that 0.3g above-mentioned (1) obtains is scattered in 10mL hydrofluoric acid, stirs 24h, subsequently centrifugation, with deionized water wash, dries in 60 DEG C of vacuum drying ovens, obtain hollow polymer nanometer ball.
With the ZetaPALS instrument test that Brookhaven company of the U.S. produces, the polydispersity coefficient of hollow polymer nanometer ball is 0.005.
The ASAP2020 adsorption instrument nitrogen adsorption methods test of producing with Micromeritics company of the U.S., the BET specific surface area of the hollow polymer nanometer ball of preparation is 49m
2g
-1, total pore volume is 0.16cm
3g
-1.
Embodiment 15
(1) preparation of pre-crosslinking polymer nanometer ball is with embodiment 1 step (1) ~ (2).Get 1g pre-crosslinking polymer nanometer ball and be scattered in swelling 24h in 60ml tetracol phenixin, be warmed up to 75 DEG C subsequently, add 2.8g Aluminum chloride anhydrous, back flow reaction 0.5h.After question response terminates, add the mixed solution 60ml termination reaction of acetone/hydrochloric acid, cooled and filtered, the solid product mixed solvent obtained washs three times, and with deionized water wash to neutral, dries in 60 DEG C of vacuum chambers.
(2) getting the super cross-linked polymer nanometer ball that 0.3g above-mentioned (1) obtains is scattered in 10mL hydrofluoric acid, stirs 24h, subsequently centrifugation, with deionized water wash, dries in 60 DEG C of vacuum drying ovens, obtain hollow polymer nanometer ball.
With the ZetaPALS instrument test that Brookhaven company of the U.S. produces, the polydispersity coefficient of hollow polymer nanometer ball is 0.005.
The ASAP2020 adsorption instrument nitrogen adsorption methods test of producing with Micromeritics company of the U.S., the BET specific surface area of the hollow polymer nanometer ball of preparation is 95m
2g
-1, wherein micropore and external holes surface-area are respectively 23m
2g
-1and 72m
2g
-1; Total pore volume is 0.15cm
3g
-1.
Embodiment 16
(1) preparation of pre-crosslinking polymer nanometer ball is with embodiment 1 step (1) ~ (2).Get 1g pre-crosslinking polymer nanometer ball and be scattered in swelling 24h in 60ml tetracol phenixin, be warmed up to 75 DEG C subsequently, add 2.8g Aluminum chloride anhydrous, back flow reaction 1h.After question response terminates, add the mixed solution 60ml termination reaction of acetone/hydrochloric acid, cooled and filtered, the solid product mixed solvent obtained washs three times, and with deionized water wash to neutral, dries in 60 DEG C of vacuum chambers.
(2) getting the super cross-linked polymer nanometer ball that 0.3g above-mentioned (1) obtains is scattered in 10mL hydrofluoric acid, stirs 24h, subsequently centrifugation, with deionized water wash, dries in 60 DEG C of vacuum drying ovens, obtain hollow polymer nanometer ball.
With the ZetaPALS instrument test that Brookhaven company of the U.S. produces, the polydispersity coefficient of hollow polymer nanometer ball is 0.005.
The ASAP2020 adsorption instrument nitrogen adsorption methods test of producing with Micromeritics company of the U.S., the BET specific surface area of the hollow polymer nanometer ball of preparation is 190m
2g
-1, wherein micropore and external holes surface-area are respectively 85m
2g
-1and 105m
2g
-1; Total pore volume is 0.19cm
3g
-1, wherein Micropore volume and external holes pore volume are respectively 0.04cm
3g
-1and 0.15cm
3g
-1.
Embodiment 17
(1) preparation of pre-crosslinking polymer nanometer ball is with embodiment 1 step (1) ~ (2).Get 1g pre-crosslinking polymer nanometer ball and be scattered in swelling 24h in 60ml tetracol phenixin, be warmed up to 75 DEG C subsequently, add 2.8g Aluminum chloride anhydrous, back flow reaction 2h.After question response terminates, add the mixed solution 60ml termination reaction of acetone/hydrochloric acid, cooled and filtered, the solid product mixed solvent obtained washs three times, and with deionized water wash to neutral, dries in 60 DEG C of vacuum chambers.
(2) getting the super cross-linked polymer nanometer ball that 0.3g above-mentioned (1) obtains is scattered in 10mL hydrofluoric acid, stirs 24h, subsequently centrifugation, with deionized water wash, dries in 60 DEG C of vacuum drying ovens, obtain hollow polymer nanometer ball.
With the ZetaPALS instrument test that Brookhaven company of the U.S. produces, the polydispersity coefficient of hollow polymer nanometer ball is 0.005.
The ASAP2020 adsorption instrument nitrogen adsorption methods test of producing with Micromeritics company of the U.S., the BET specific surface area of the hollow polymer nanometer ball of preparation is 148m
2g
-1, wherein micropore and external holes surface-area are respectively 54m
2g
-1and 94m
2g
-1; Total pore volume is 0.17cm
3g
-1, wherein Micropore volume and external holes pore volume are respectively 0.02cm
3g
-1and 0.15cm
3g
-1.
Embodiment 18
(1) preparation of pre-crosslinking polymer nanometer ball is with embodiment 1 step (1) ~ (2).Get 1g pre-crosslinking polymer nanometer ball and be scattered in swelling 24h in 60ml tetracol phenixin, be warmed up to 75 DEG C subsequently, add 2.8g Aluminum chloride anhydrous, back flow reaction 4h.After question response terminates, add the mixed solution 60ml termination reaction of acetone/hydrochloric acid, cooled and filtered, the solid product mixed solvent obtained washs three times, and with deionized water wash to neutral, dries in 60 DEG C of vacuum chambers.
(2) getting the super cross-linked polymer nanometer ball that 0.3g above-mentioned (1) obtains is scattered in 10mL hydrofluoric acid, stirs 24h, subsequently centrifugation, with deionized water wash, dries in 60 DEG C of vacuum drying ovens, obtain hollow polymer nanometer ball.
With the ZetaPALS instrument test that Brookhaven company of the U.S. produces, the polydispersity coefficient of hollow polymer nanometer ball is 0.005.
The ASAP2020 adsorption instrument nitrogen adsorption methods test of producing with Micromeritics company of the U.S., the BET specific surface area of the hollow polymer nanometer ball of preparation is 209m
2g
-1, wherein micropore and external holes surface-area are respectively 89m
2g
-1and 120m
2g
-1; Total pore volume is 0.20cm
3g
-1, wherein Micropore volume and external holes pore volume are respectively 0.04cm
3g
-1and 0.16cm
3g
-1.
Embodiment 19
(1) preparation of pre-crosslinking polymer nanometer ball is with embodiment 1 step (1) ~ (2).Get 1g pre-crosslinking polymer nanometer ball and be scattered in swelling 24h in 60ml tetracol phenixin, be warmed up to 75 DEG C subsequently, add 2.8g Aluminum chloride anhydrous, back flow reaction 8h.After question response terminates, add the mixed solution 60ml termination reaction of acetone/hydrochloric acid, cooled and filtered, the solid product mixed solvent obtained washs three times, and with deionized water wash to neutral, dries in 60 DEG C of vacuum chambers.
(2) getting the super cross-linked polymer nanometer ball that 0.3g above-mentioned (1) obtains is scattered in 10mL hydrofluoric acid, stirs 24h, subsequently centrifugation, with deionized water wash, dries in 60 DEG C of vacuum drying ovens, obtain hollow polymer nanometer ball.
With the ZetaPALS instrument test that Brookhaven company of the U.S. produces, the polydispersity coefficient of hollow polymer nanometer ball is 0.005.
The ASAP2020 adsorption instrument nitrogen adsorption methods test of producing with Micromeritics company of the U.S., the BET specific surface area of the hollow polymer nanometer ball of preparation is 343m
2g
-1, wherein micropore and external holes surface-area are respectively 167m
2g
-1and 195m
2g
-1; Total pore volume is 0.27cm
3g
-1, wherein Micropore volume and external holes pore volume are respectively 0.08cm
3g
-1and 0.19cm
3g
-1.
Embodiment 20
(1) preparation of pre-crosslinking polymer nanometer ball is with embodiment 1 step (1) ~ (2).Get 1g pre-crosslinking polymer nanometer ball and be scattered in swelling 24h in 60ml tetracol phenixin, be warmed up to 75 DEG C subsequently, add 2.8g Aluminum chloride anhydrous, back flow reaction 16h.After question response terminates, add the mixed solution termination reaction of acetone/hydrochloric acid, cooled and filtered, the solid product mixed solvent obtained washs three times, and with deionized water wash to neutral, dries in 60 DEG C of vacuum chambers.
(2) getting the super cross-linked polymer nanometer ball that 0.3g above-mentioned (1) obtains is scattered in 10mL hydrofluoric acid, stirs 24h, subsequently centrifugation, with deionized water wash, dries in 60 DEG C of vacuum drying ovens, obtain hollow polymer nanometer ball.
With the ZetaPALS instrument test that Brookhaven company of the U.S. produces, the polydispersity coefficient of hollow polymer nanometer ball is 0.005.
The ASAP2020 adsorption instrument nitrogen adsorption methods test of producing with Micromeritics company of the U.S., the BET specific surface area of the hollow polymer nanometer ball of preparation is 392m
2g
-1, wherein micropore and external holes surface-area are respectively 188m
2g
-1and 204m
2g
-1; Total pore volume is 0.44cm
3g
-1, wherein Micropore volume and external holes pore volume are respectively 0.09cm
3g
-1and 0.35cm
3g
-1.
Embodiment 21
(1) preparation of pre-crosslinking polymer nanometer ball is with embodiment 1 step (1) ~ (2).Get 1g pre-crosslinking polymer nanometer ball and be scattered in swelling 24h in 60ml tetracol phenixin, be warmed up to 75 DEG C subsequently, add 2.8g Aluminum chloride anhydrous, back flow reaction 48h.After question response terminates, add the mixed solution 60ml termination reaction of acetone/hydrochloric acid, cooled and filtered, the solid product mixed solvent obtained washs three times, and with deionized water wash to neutral, dries in 60 DEG C of vacuum chambers.
(2) getting the super cross-linked polymer nanometer ball that 0.3g above-mentioned (1) obtains is scattered in 10mL hydrofluoric acid, stirs 24h, subsequently centrifugation, with deionized water wash, dries in 60 DEG C of vacuum drying ovens, obtain hollow polymer nanometer ball.
With the ZetaPALS instrument test that Brookhaven company of the U.S. produces, the polydispersity coefficient of hollow polymer nanometer ball is 0.005.
The ASAP2020 adsorption instrument nitrogen adsorption methods test of producing with Micromeritics company of the U.S., the BET specific surface area of the hollow polymer nanometer ball of preparation is 386m
2g
-1, wherein micropore and external holes surface-area are respectively 205m
2g
-1and 181m
2g
-1; Total pore volume is 0.33cm
3g
-1, wherein Micropore volume and external holes pore volume are respectively 0.09cm
3g
-1and 0.24cm
3g
-1.
Embodiment 22
(1) preparation of monodisperse silica nanometer ball is with embodiment 1.
(2) 0.03g Sodium dodecylbenzene sulfonate and 0.24g sodium bicarbonate are dissolved in the 100mL deionized water of deoxygenation in advance, are stirred well to system even, in system, pass into nitrogen deoxygenation 15min.Add the improved silica alcohol dispersion liquid (1.2g silica nanosphere is scattered in 10mL ethanol) of ultrasonic disperse subsequently and vigorous stirring.After system is homogeneous, in system, add vinylbenzene 0.5mL and Vinylstyrene 0.15mL, stir after 10min and be warming up to 75 DEG C, and add 0.12g initiator potassium persulfate, centrifugal and remove tensio-active agent by toluene wash after reaction 24h.
(3) get the pre-crosslinking polymer nanometer ball obtained in 1g above-mentioned (2) and be scattered in swelling 12h in 60ml tetracol phenixin, be warmed up to 75 DEG C subsequently, add 2.8g Aluminum chloride anhydrous, back flow reaction 24h.After question response terminates, add the mixed solution 60ml termination reaction of acetone/hydrochloric acid, cooled and filtered, the solid product mixed solvent obtained washs three times, and with deionized water wash to neutral, dries in 60 DEG C of vacuum chambers.
(4) getting the super cross-linked polymer nanometer ball that 0.3g above-mentioned (3) obtains is scattered in 10mL hydrofluoric acid, stirs 24h, subsequently centrifugation, with deionized water wash, dries in 60 DEG C of vacuum drying ovens, obtain hollow polymer nanometer ball.
With the ZetaPALS instrument test that Brookhaven company of the U.S. produces, the polydispersity coefficient of hollow polymer nanometer ball is 0.046.
The ASAP2020 adsorption instrument nitrogen adsorption methods test of producing with Micromeritics company of the U.S., the BET specific surface area of the hollow polymer nanometer ball of preparation is 441m
2g
-1, wherein micropore and external holes surface-area are respectively 194m
2g
-1and 247m
2g
-1; Total pore volume is 1.40cm
3g
-1.
The IGA Instrument measuring hollow polymer nanometer ball produced with Hiden company of Britain is at normal temperatures to organic steam adsorption-desorption performance, and it is respectively 369mgg to the adsorptive capacity of toluene and methanol steam
-2and 729mgg
-2.
Embodiment 23
(1) preparation of monodisperse silica nanometer ball is with embodiment 1.
(2) 0.03g Sodium dodecylbenzene sulfonate and 0.24g sodium bicarbonate are dissolved in the 100mL deionized water of deoxygenation in advance, are stirred well to system even, in system, pass into nitrogen deoxygenation 15min.Add the improved silica alcohol dispersion liquid (1.2g silica nanosphere is scattered in 10mL ethanol) of ultrasonic disperse subsequently and vigorous stirring.After system is homogeneous, in system, add vinylbenzene 2mL and Vinylstyrene 0.6mL, stir after 10min and be warming up to 75 DEG C, and add 0.12g initiator potassium persulfate, centrifugal and remove tensio-active agent by toluene wash after reaction 24h.
(3) get the pre-crosslinking polymer nanometer ball obtained in 1g above-mentioned (2) and be scattered in swelling 12h in 60ml tetracol phenixin, be warmed up to 75 DEG C subsequently, add 2.8g Aluminum chloride anhydrous, back flow reaction 24h.After question response terminates, add the mixed solution 60ml termination reaction of acetone/hydrochloric acid, cooled and filtered, the solid product mixed solvent obtained washs three times, and with deionized water wash to neutral, dries in 60 DEG C of vacuum chambers.
(4) getting the super cross-linked polymer nanometer ball that 0.3g above-mentioned (3) obtains is scattered in 10mL hydrofluoric acid, stirs 24h, subsequently centrifugation, with deionized water wash, dries in 60 DEG C of vacuum drying ovens, obtain hollow polymer nanometer ball.
With the ZetaPALS instrument test that Brookhaven company of the U.S. produces, the polydispersity coefficient of hollow polymer nanometer ball is 0.046.
The ASAP2020 adsorption instrument nitrogen adsorption methods test of producing with Micromeritics company of the U.S., the BET specific surface area of the hollow polymer nanometer ball of preparation is 347m
2g
-1, wherein micropore and external holes surface-area are respectively 254m
2g
-1and 93m
2g
-1; Total pore volume is 0.41cm
3g
-1, wherein Micropore volume and external holes pore volume are respectively 0.07cm
3g
-1and 0.34cm
3g
-1.
The IGA Instrument measuring hollow polymer nanometer ball produced with Hiden company of Britain is at normal temperatures to organic steam adsorption-desorption performance, and it is respectively 271mgg to the adsorptive capacity of toluene and methanol steam
-2and 302mgg
-2.
Embodiment 24
(1) preparation of pre-crosslinking polymer nanometer ball is with embodiment 23 step (1) ~ (2).Get 0.5g pre-crosslinking polymer nanometer ball and be scattered in swelling 8h in 60ml tetracol phenixin, be warmed up to 75 DEG C subsequently, add 2g Aluminum chloride anhydrous, back flow reaction 48h.After question response terminates, add the mixed solution termination reaction of acetone/hydrochloric acid, cooled and filtered, the solid product mixed solvent obtained washs three times, and with deionized water wash to neutral, dries in 60 DEG C of vacuum chambers.
(2) getting the super cross-linked polymer nanometer ball that 0.3g above-mentioned (1) obtains is scattered in 10mL hydrofluoric acid, stirs 24h, subsequently centrifugation, with deionized water wash, dries in 60 DEG C of vacuum drying ovens, obtain hollow polymer nanometer ball.
The ASAP2020 adsorption instrument nitrogen adsorption methods test of producing with Micromeritics company of the U.S., the BET specific surface area of the hollow polymer nanometer ball of preparation is 213m
2g
-1.
Embodiment 25
(1) adopt
legal system is for monodisperse silica nanometer ball, concrete operations are as follows: the mixing solutions preparing ethanol/tetraethoxy (150mL/24mL) and ethanol/ammonia/water (60mL/20mL/40mL) in Erlenmeyer flask respectively, and short mix is even, setting stir speed (S.S.) is 250rpm, under 30 DEG C of conditions, react 3h.Subsequently 2ml Silane coupling reagent KH-570 is dissolved in 100ml ethanol, adds in above-mentioned reaction system with dropping funnel, be added dropwise to complete rear continuation reaction 36h.
(2) 0.03g Sodium dodecylbenzene sulfonate and 0.24g sodium bicarbonate are dissolved in the 100mL deionized water of deoxygenation in advance, are stirred well to system even, in system, pass into nitrogen deoxygenation 15min.Add the improved silica alcohol dispersion liquid (1.2g silica nanosphere is scattered in 10mL ethanol) of ultrasonic disperse subsequently and vigorous stirring.After system is homogeneous, in system, add vinylbenzene 5mL and Vinylstyrene 1.5mL, stir after 10min and be warming up to 75 DEG C, and add 0.12g initiator potassium persulfate, centrifugal and remove tensio-active agent by toluene wash after reaction 24h.
(3) get the pre-crosslinking polymer nanometer ball obtained in 1g above-mentioned (2) and be scattered in swelling 12h in 60ml tetracol phenixin, be warmed up to 75 DEG C subsequently, add 2.8g Aluminum chloride anhydrous, back flow reaction 24h.After question response terminates, add the mixed solution termination reaction of acetone/hydrochloric acid, cooled and filtered, the solid product mixed solvent obtained washs three times, and with deionized water wash to neutral, dries in 60 DEG C of vacuum chambers.
(4) getting the cross-linked polymer nanometer ball that 0.3g above-mentioned (3) obtains is scattered in 10mL hydrofluoric acid, stirs 24h, subsequently centrifugation, with deionized water wash, dries in 60 DEG C of vacuum drying ovens, obtain hollow polymer nanometer ball.
With the ZetaPALS instrument test that Brookhaven company of the U.S. produces, the polydispersity coefficient of hollow polymer nanometer ball is 0.005.
The ASAP2020 adsorption instrument nitrogen adsorption methods test of producing with Micromeritics company of the U.S., the BET specific surface area of the hollow polymer nanometer ball of preparation is 386m
2g
-1, wherein micropore and external holes surface-area are respectively 205m
2g
-1and 181m
2g
-1; Total pore volume is 0.33cm
3g
-1, wherein Micropore volume and external holes pore volume are respectively 0.09cm
3g
-1and 0.24cm
3g
-1.
Embodiment 26
(1) preparation of monodisperse silica nanometer ball is with embodiment 1.
(2) 0.03g Sodium dodecylbenzene sulfonate and 0.24g sodium bicarbonate are dissolved in the 100mL deionized water of deoxygenation in advance, are stirred well to system even, in system, pass into nitrogen deoxygenation 15min.Add the improved silica alcohol dispersion liquid (1.2g silica nanosphere is scattered in 10mL ethanol) of ultrasonic disperse subsequently and vigorous stirring.After system is homogeneous, in system, add vinylbenzene 3mL and Vinylstyrene 2mL, stir after 10min and be warming up to 75 DEG C, and add 0.12g initiator potassium persulfate, centrifugal and with adding toluene wash removing tensio-active agent after reaction 12h.
(3) get the pre-crosslinking polymer nanometer ball obtained in 1g above-mentioned (2) and be scattered in swelling 8h in 60ml tetracol phenixin, be warmed up to 30 DEG C subsequently, add 2.8g Aluminum chloride anhydrous, back flow reaction 24h.After question response terminates, add the mixed solution termination reaction of acetone/hydrochloric acid, cooled and filtered, the solid product mixed solvent obtained washs three times, and with deionized water wash to neutral, dries in 60 DEG C of vacuum chambers.
(4) getting the super cross-linked polymer nanometer ball that 0.3g above-mentioned (3) obtains is scattered in 10mL hydrofluoric acid, stirs 24h, subsequently centrifugation, with deionized water wash, dries in 60 DEG C of vacuum drying ovens, obtain hollow polymer nanometer ball.
With the ZetaPALS instrument test that Brookhaven company of the U.S. produces, the polydispersity coefficient of hollow polymer nanometer ball is 0.005.
The ASAP2020 adsorption instrument nitrogen adsorption methods test of producing with Micromeritics company of the U.S., the BET specific surface area of the hollow polymer nanometer ball of preparation is 44m
2g
-1.
Embodiment 27
(1) preparation of pre-crosslinking polymer nanometer ball is with embodiment 26 step (1) ~ (2).Get 0.5g pre-crosslinking polymer nanometer ball and be scattered in swelling 8h in 60ml tetracol phenixin, be warmed up to 75 DEG C subsequently, add 2g Aluminum chloride anhydrous, back flow reaction 24h.After question response terminates, add the mixed solution termination reaction of acetone/hydrochloric acid, cooled and filtered, the solid product mixed solvent obtained washs three times, and with deionized water wash to neutral, dries in 60 DEG C of vacuum chambers.
(2) getting the super cross-linked polymer nanometer ball that 0.3g above-mentioned (1) obtains is scattered in 10mL hydrofluoric acid, stirs 24h, subsequently centrifugation, with deionized water wash, dries in 60 DEG C of vacuum drying ovens, obtain hollow polymer nanometer ball.
The ASAP2020 adsorption instrument nitrogen adsorption methods test of producing with Micromeritics company of the U.S., the BET specific surface area of the hollow polymer nanometer ball of preparation is 321m
2g
-1, total pore volume is 0.30cm
3g
-1.
Embodiment 28
(1) preparation of pre-crosslinking polymer nanometer ball is with embodiment 26 step (1) ~ (2).Get 0.5g pre-crosslinking polymer nanometer ball and be scattered in swelling 8h in 60ml tetracol phenixin, be warmed up to 75 DEG C subsequently, add 2g Aluminum chloride anhydrous, back flow reaction 0.5h.After question response terminates, add the mixed solution termination reaction of acetone/hydrochloric acid, cooled and filtered, the solid product mixed solvent obtained washs three times, and with deionized water wash to neutral, dries in 60 DEG C of vacuum chambers.
(2) getting the super cross-linked polymer nanometer ball that 0.3g above-mentioned (1) obtains is scattered in 10mL hydrofluoric acid, stirs 24h, subsequently centrifugation, with deionized water wash, dries in 60 DEG C of vacuum drying ovens, obtain hollow polymer nanometer ball.
The ASAP2020 adsorption instrument nitrogen adsorption methods test of producing with Micromeritics company of the U.S., the BET specific surface area of the hollow polymer nanometer ball of preparation is 82m
2g
-1.
Embodiment 29
(1) preparation of pre-crosslinking polymer nanometer ball is with embodiment 26 step (1) ~ (2).Get 0.5g pre-crosslinking polymer nanometer ball and be scattered in swelling 8h in 60ml tetracol phenixin, be warmed up to 75 DEG C subsequently, add 2g Aluminum chloride anhydrous, back flow reaction 48h.After question response terminates, add the mixed solution termination reaction of acetone/hydrochloric acid, cooled and filtered, the solid product mixed solvent obtained washs three times, and with deionized water wash to neutral, dries in 60 DEG C of vacuum chambers.
(2) getting the super cross-linked polymer nanometer ball that 0.3g above-mentioned (1) obtains is scattered in 10mL hydrofluoric acid, stirs 24h, subsequently centrifugation, with deionized water wash, dries in 60 DEG C of vacuum drying ovens, obtain hollow polymer nanometer ball.
The ASAP2020 adsorption instrument nitrogen adsorption methods test of producing with Micromeritics company of the U.S., the BET specific surface area of the hollow polymer nanometer ball of preparation is 116m
2g
-1.Total pore volume is 0.20cm
3g
-1.
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not restricted to the described embodiments; change, the modification done under other any does not deviate from spirit of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (9)
1. a Hollow nanosphere material, is characterized in that: form by nanometer ball is stacking, and BET specific surface area is 44 ~ 1226 m
2g
-1, total pore volume is 0.15 ~ 1.20 cm
3g
-1; Nanometer ball has micropore shell-cavity nanostructure, and cavity diameter is 80 ~ 260 nm, and shell thickness is 5 ~ 85 nm, and single dispersing coefficient is low to moderate 0.005, and Shell Materials is polymkeric substance or charcoal;
Described Hollow nanosphere material is prepared by the method comprising following concrete steps:
(1) by Sodium dodecylbenzene sulfonate and sodium bicarbonate soluble in water, nitrogen protection, add the alcohol dispersion liquid of improved silica nanometer ball and vigorous stirring, add styrene monomer and Vinylstyrene, heat up and add initiator after stirring, centrifugal, washing, obtains pre-crosslinking polymer nanometer ball;
(2), after the pre-crosslinking polymer nanometer ball that obtains in step (1) is swelling in tetracol phenixin, add the backflow of catalyzer aluminum trichloride (anhydrous) after intensification and carry out Friedel-Crafts and surpass crosslinking reaction;
(3) add acetone/hydrochloric acid mixed solution and stop Friedel-Crafts reaction, filter and obtain solid product, through washing, filter and after drying, obtain super cross-linked polymer nanometer ball;
(4) the super cross-linked polymer nanometer ball obtained in step (3) is immersed in hydrofluoric acid, removes silicon-dioxide, obtain hollow polymer nanometer ball material;
Or the cross-linked polymer nanometer ball obtained in step (3) is placed in charring furnace, under inert gas atmosphere after charing, is immersed in 1 ~ 24 h in hydrofluoric acid, remove silicon-dioxide, obtain Carbon Hollow nanometer ball material;
Or being placed in charring furnace by obtaining hollow polymer nanometer ball material in step (4), carbonizing under inert gas atmosphere, obtaining Carbon Hollow nanometer ball material;
Silicon-dioxide used in step (1): vinylbenzene: Vinylstyrene: sodium bicarbonate: dodecylbenzene naphthenic acid sodium: initiator: the proportioning of water is (0.5 ~ 5) g: (0.1 ~ 15) ml: (0.05 ~ 5) ml: (0.1 ~ 0.5) g: (0.01 ~ 0.1) g: (0.1 ~ 0.5) g: (50 ~ 500) ml;
In step (2), the amount of anhydrous tetracol phenixin used is that every 0.1 ~ 5 g pre-crosslinking polymer nanometer ball uses 5 ~ 500 ml;
Friedel-Crafts described in step (2) surpasses the condition of crosslinking reaction for reacting 0.25 ~ 72 h at 30 ~ 75 DEG C.
2. Hollow nanosphere material according to claim 1, is characterized in that: when nano ball shell layer material is polymkeric substance, and described nanometer ball cavity diameter is 90 ~ 260 nm, and shell thickness is 5 ~ 85 nm, and BET specific surface area is 44 ~ 441 m
2g
-1, total pore volume is 0.15 ~ 1.20 cm
3g
-1.
3. Hollow nanosphere material according to claim 1, is characterized in that: when nano ball shell layer material is charcoal, and described nanometer ball cavity diameter is 80 ~ 240 nm, and shell thickness is 5 ~ 85 nm, and BET specific surface area is 522 ~ 1226 m
2g
-1, total pore volume is 0.44 ~ 0.85 cm
3g
-1.
4. Hollow nanosphere material according to claim 1, is characterized in that: described polymkeric substance refers to polystyrene-divinylbenzene.
5. Hollow nanosphere material according to claim 1, is characterized in that: described in step (1), improved silica nanometer ball is prepared by following methods: adopt
legal system is for monodisperse silica nanometer ball, and recycle silicon alkane coupling agent carries out surface modification to it.
6. Hollow nanosphere material according to claim 1, is characterized in that: in the alcohol dispersion liquid of improved silica nanometer ball described in step (1), improved silica nanometer ball content is 0.05 ~ 1 g/ml; Described initiator refers at least one in Potassium Persulphate, Diisopropyl azodicarboxylate and benzoyl peroxide; Described intensification refers to that Heating temperature is 50 ~ 100 DEG C.
7. Hollow nanosphere material according to claim 1, is characterized in that: in step (2), the amount of aluminum trichloride (anhydrous) used is that every 1 ~ 50 g pre-crosslinking polymer nanometer ball uses 0.1 ~ 5 g aluminum trichloride (anhydrous).
8. Hollow nanosphere material according to claim 1, is characterized in that: in step (3), the amount of acetone/hydrochloric acid mixed solution used is that 0.1 ~ 5 g pre-crosslinking polymer nanometer ball uses 20 ~ 500 ml; The condition of described charing is with the temperature rise rate of 1 ~ 10 DEG C/min to 700 ~ 1100 DEG C, charing 1 ~ 5 h; The amount of hydrofluoric acid used is that every 0.1 ~ 5 g surpasses cross-linked polymer nanometer ball and uses 10 ml; The time of described immersion is 1 ~ 24 h.
9. the Hollow nanosphere material according to any one of Claims 1 to 4 is preparing the application in pharmaceutical carrier, electrode materials and sorbing material.
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| CN107999028A (en) * | 2018-01-09 | 2018-05-08 | 陕西师范大学 | The application of lar nanometric cavities structure porous hydrophobic material and preparation method and adsorbing separation 5 hydroxymethyl furfural |
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