CN110203935A - Tube wall is in the right-handed helix nano-tube material and preparation method for radiating hole arrangement - Google Patents
Tube wall is in the right-handed helix nano-tube material and preparation method for radiating hole arrangement Download PDFInfo
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Abstract
The invention discloses a kind of tube walls in the right-handed helix nano-tube material and preparation method of the arrangement of radiation hole, belongs to technical field of nano material.The nano-tube material by one or more length is 100nm~20 μm, diameter is that nano-tube between 3nm~100nm rearranges in space, every nano-tube is the hollow cavity of other end closing setting open at one end, more than one duct is distributed on the side wall of hollow cavity, each duct is the radial duct from center to fringe radiation, and average pore size is 2nm~50nm.The specific surface area of the chirality nano-tube reaches 600~1400m2/ g can be used as the nano-carrier of drug, albumen and gene for interior therapeutic, meanwhile, the chiral nanotubes for having the structure, which can also be assembled further, the fields such as also can be used for chiral catalysis and splits.
Description
Technical field
The present invention relates to mesoporous silicon oxides, belong to technical field of nano material, more particularly to a kind of tube wall in radiation
The right-handed helix nano-tube material and preparation method of hole arrangement.
Background technique
Since Mobile company successfully prepares MCM-41 series mesoporous silicon oxide, mesoporous material is unique uniform because of it
Cellular structure, large specific surface area and Kong Rong, controllable aperture and the surface texture for being easy to modify are widely used in carrier, inhale
Attached, separation and catalysis, semiconductor material and opto-electronic device and the fields such as sensor and regulator array.However, traditional nothing
Sequence mesoporous silica spheres face a series of difficulties such as adsorbance is few, catalytic activity is low, therefore preparing has ordered mesoporous pore canals knot
The earth silicon material of structure possesses important researching value and potential application prospect.Currently, pattern, structure and aperture controllably at
For one of the challenge for preparing silica nano material, the dioxy of the structure of ordered mesoporous pore canals containing radial radial is especially prepared
Silicon nitride material becomes a research hotspot of Many researchers.
For example, Moon etc. using bicontinuous microemulsions system as template, is successfully prepared Jie of orderly radioactivity pore distribution
Hole silica spheres (MoonD, LeeJ, Langmuir, 2012,28,12341-12347).Peng etc. utilizes CTAB-1,3,5- tri-
Methylbenzene-alcohol-water composition microemulsion system does template, and the silica of core-shell structure is prepared as silicon source in TEOS
There is the worm meso-porous of local Hexagonal array, radial ordered mesoporous pore canals, but its aperture be distributed on shell in ball, core center
Smaller (3~7.3nm).The SiO of this core-shell structure2Ball specific surface area (745~912m with higher2/ g) and pore volume
(0.98~1.34cm3/ g), as a result prove that this earth silicon material there are second level cellular structure is expected to urge applied to biology
The fields (PengJ, LiuJ, LiuJ, J.Mater.Chem.A, 2014,2,8118-8125) such as change, absorption.
Chinese invention patent application (application publication number CN102849750A, data of publication of application 2013-01-02) discloses one
Radial hole channel mesoporous silicon oxide of kind and preparation method thereof.It is characterized in that product SiO2Material is spherical morphology, surface light
Sliding, partial size is 700~1000nm, and duct is the radial duct from center to fringe radiation, and there are multistage apertures, and aperture is big
It is small inhomogenous, specific surface area with higher and Kong Rong.Specific preparation method be at room temperature, using water-ethanol-ether as
Cosolvent, cetyl trimethylammonium bromide (CTAB) or hexadecyltrimethylammonium chloride (CTAC) are template, and ammonium hydroxide is
Catalyst promotes silicon source (TEOS) hydrolytie polycondensation and obtains.It is even to must be added to a certain proportion of silane in synthetic system of the invention
Join agent (N- β-(aminoethyl)-γ-aminopropyltrimethoxysilane), the material composition of reaction system is required stringent.
Chinese invention patent application (application publication number CN104129791A, data of publication of application 2014-11-05) discloses one
Kind is containing radial mesopore orbit structure spherical silicon dioxide material and preparation method thereof.It is characterized in that, the invention utilizes CTAB,
The oil-in-water microemulsion system that PVP- ethyl alcohol-hexamethylene-water is formed does template, and silicon source TEOS is in micro emulsion drop ball surface water
Solution, polycondensation, self assembly contain the spherical mesoporous SiO of radial mesopore orbit structure2Nano material.The mesoporous silicon oxide is single
Dispersing ball, particle size range are 350~650nm, and specific surface area is 975~1114m2/ g, aperture are 3.9~4.1nm, mesoporous hole
Road is radiated the edge of ball from the center of ball.
However, mesoporous SiO obtained above2Spherical shape is presented in nano material.
At the same time, the chiral universal phenomenon as nature, is widely present in the more substance of nature, studies table
It is bright, the chirality of vital movement and biomolecule have it is close contact, but in organic chemistry research field, chiral small molecule is urged
Agent is faced with expensive, and is difficult to the problem of recycling.
University Of Suzhou Yang Yonggang professor seminar reported using the derivative of amino acid control silica pattern,
The structure in hole and the chiral control that organic inorganic hybridization silicon dioxide structure is realized under molecular scale.Such as using amino acid derived
The self-assembly of object is template, and silica nanosphere, internal Silica Nanotube, the table with spring like duct has been made
Face is the nano SiO 2 particle that layered mesoporous inside is cylindrical duct and external pipe be helical structure internal gutter is hand
Property arrangement Silica Nanotube etc..
However, the report of the right-handed helix nano-tube of radiation hole arrangement is not presented about tube wall at present.
Summary of the invention
In order to solve the above technical problems, the present invention provides a kind of tube walls in the right-handed helix nano-tube of radiation hole arrangement
Material, it by one or more length is 100nm~20 μm, diameter is that nano-tube between 3nm~100nm is arranged in space
Column composition, the every nano-tube is the hollow cavity of other end closing setting open at one end, on the side wall of hollow cavity
More than one duct is distributed with, each duct is the radial duct from center to fringe radiation, average pore size
For 2nm~50nm.
Specifically, nano-tube is disorderly arranged in three dimensions, but right-handed helix structure is integrally presented in it.
Preferably, the length of nano-tube is 500nm~600nm.
Preferably, the length of nano-tube is 600nm~700nm.
Preferably, the length of nano-tube is 700nm~800nm.
Preferably, the length of nano-tube is 800nm~900nm.
Preferably, the length of nano-tube is 900nm~1000nm.
Preferably, the length of nano-tube is 900nm~1000nm.
Preferably, the length of nano-tube is 1000nm~10000nm.
Preferably, the length of nano-tube is 10000nm~12000nm.
Preferably, the length of nano-tube is 12000nm~2000nm.
Preferably, the diameter of nano-tube is 5nm~90nm.
Preferably, the diameter of nano-tube is 10nm~70nm.
Preferably, the diameter of nano-tube is 30nm~60nm.
Preferably, the diameter of nano-tube is 40nm~50nm.
Preferably, the average pore size in radial duct is 2nm~40nm.
Preferably, the average pore size in radial duct is 5nm~30nm.
Optimal, the average pore size in radial duct is 15nm.
Further, the specific surface area of the nano-tube material is 600~1400m2/g。
Preferably, the specific surface area of the nano-tube material is 700~1200m2/g。
Optimal, the specific surface area of the nano-tube material is 800m2/g。
Optimal, the specific surface area of the nano-tube material is 1000m2/g。
In order to preferably realize technical purpose of the invention, the invention also discloses above-mentioned tube walls in the right side of radiation hole arrangement
The preparation method of hand spiral nano-tube material, it includes using cationic colloidal for template, using esters of silicon acis as silicon source, preparation
Obtain the chiral nano-tube that tube wall duct is arranged radially.Further, the cationic colloidal includes having following knot
The compound of structure formula:
Wherein, m=2~18, n=2~20；R is CH3, (CH3)2CH-, (CH3)2CH2H- or Ph-CH2-。
Preferably, the m=10, n=16 and R are CH3, then cationic colloidal has following particular chemical formula,
Specifically, the cationic colloidal for having above-mentioned chemical structural formula is to use l-Alanine for reaction raw materials, successively pass through
Going through BOC protection, amidation, de- BOC protection, amidation, upper pyridine and hexafluorophosphate replaces bromide to be made.
Specifically, synthetic route is as follows:
Further, the preparation method includes following detailed process:
1) cationic colloidal is added in deionized water, preparation obtains cationic aqueous solution；
Preferably, the concentration of the cationic aqueous solution is 10~50mg/mL.
Preferably, rate-determining steps 1) in mixing speed be 100~1500rpm, stir 1s~100min.
2) it is added aqueous slkali and alkylol into the cationic aqueous solution that step 1) obtains, adjustment solution ph is 7.5~
14,1s~100min is stirred, mixed solution is obtained；
Preferably, rate-determining steps 2) in mixing speed be 100~1500rpm, stir 1s~100min.
3) esters of silicon acis is added into mixed solution made from step 2), reaction generates white colloidal, then washed and calcining
Tube wall is obtained in the right-handed helix nano-tube material of radiation hole arrangement.
Preferably, it is washed respectively at least once in step 2) using ethyl alcohol and hydrochloric acid.
Further, the volume ratio of aqueous slkali described in step 2) and alkylol is 9:1~8:2.
Further, aqueous slkali described in step 2) includes tetramethylammonium hydroxide, ammonium hydroxide, sodium hydroxide or potassium hydroxide
One or more of configuration acquired solution.
Preferably, the mass percentage concentration of the concentrated ammonia liquor is 20~25%.
Preferably, the sodium hydroxide molar concentration is 1~5M/L.
Preferably, the sodium hydroxide molar concentration is 1~5M/L.
Preferably, the mass percentage concentration of the tetramethylammonium hydroxide is 1~25%.
Further, alkylol described in step 2) includes in ethyl alcohol, normal propyl alcohol, isopropanol, n-butanol or isobutanol
It is at least one.
Preferably, the alkylol is isopropanol.
Preferably, control reaction temperature is 0~20 DEG C in step 3), and the reaction time is 1~10h.
Further, esters of silicon acis described in step 3) includes tetraethyl orthosilicate, positive quanmethyl silicate, bis- (three second of 1,2-
At least one of oxygroup silicon) ethylene, bis- (triethoxysilicane) benzene of 1,2- or bis- (triethoxy silicon substrate) benzene of 1,4-.
Preferably, the esters of silicon acis accounts for the 0.5~5% of reaction system volume.
Further, calcination condition described in step 3) is to control 500~600 DEG C of temperature, calcines 4~8h.
Preferably, 550 DEG C of temperature are controlled, 5h is calcined, the hole for obtaining target material is more uniform.
Beneficial effects of the present invention are as follows:
It is template the present invention provides a kind of cationic colloidal, tube wall is successfully prepared in the right hand spiral shell of radiation hole arrangement
Nano-tube material is revolved, preparation method is simple, and the specific surface area of nano-tube material obtained reaches 600~1400m2/ g,
The aperture that hole is radiated on surface reaches 2nm~50nm, which can be used as the nano-carrier of drug, albumen and gene for body
Interior treatment, meanwhile, the chiral nanotubes for having the structure, which can also be assembled further, the fields such as also can be used for chiral catalysis and splits.
Detailed description of the invention
Fig. 1 is transmission electron microscope picture of 2 silicon nano material of the embodiment of the present invention before removing template；
Fig. 2 is the transmission electron microscope picture of 2 nano-tube material of the embodiment of the present invention；
Fig. 3 is the transmission electron microscope picture after the nano-tube material amplification factor of Fig. 2；
Fig. 4 is the scanning electron microscope (SEM) photograph of the nano-tube material of Fig. 2；
Fig. 5 is the scanning electron microscope (SEM) photograph of 3 nano-tube material of the embodiment of the present invention；
Fig. 6 is the scanning electron microscope (SEM) photograph of 4 nano-tube material of the embodiment of the present invention；
Fig. 7 is the scanning electron microscope (SEM) photograph of 4 nano-tube material of the embodiment of the present invention；
Fig. 8 is the microscopic appearance structural schematic diagram of 5 nano-tube material of the embodiment of the present invention；
Fig. 9 is the microscopic appearance structural schematic diagram of 5 nano-tube material of the embodiment of the present invention；
Figure 10 is the radial distribution figure that the present invention implements 2 obtained silicon nano material surface ducts；
Figure 11 is that the present invention implements 2 obtained silicon nano materials to the adsorption-desorption test chart of nitrogen.
Specific embodiment
In order to better explain the present invention, below in conjunction with the specific embodiment main contents that the present invention is furture elucidated, but
The contents of the present invention are not limited solely to following embodiment.
Embodiment 1
Present embodiment discloses the preparation of cationic colloidal L-16Ala11PyPF6, the conjunction for using the content of present invention to announce
It is carried out at route, and intermediate product L-16Ala11PyBr is also chiral small molecule template, is transformed into L- by it
16Ala11PyPF6, it is only necessary to place it in completion ion exchange in phosphate.
Embodiment 2
The present embodiment further discloses the preparation process of chiral nano-tube, specific as follows:
Taking L-16Ala11PyPF6 chirality small molecule template made from 12mg/mL above-described embodiment 1 to be dissolved in volume ratio is 8:2
Concentrated ammonia liquor and normal propyl alcohol mixed solution in, control reaction system at 20 DEG C hereinafter, be slowly added to 20 μ L tetraethoxysilanes,
The reaction product that the reaction was continued after addition obtains be the nano-tube material with template, structure as shown in Figure 1, in conjunction with
Fig. 1 is it is found that the nano-tube material its surface and not formed duct before removing template.
Ethyl alcohol and concentrated hydrochloric acid elution is respectively adopted again to remove template, is placed on 550 DEG C of Muffle furnace temperature programming calcining 5h,
The nano-tube material for having structure shown in Fig. 2, Fig. 3 and Fig. 4 is obtained, in conjunction with Fig. 2 it is found that silicon made from the embodiment of the present invention is received
Rice material is nano-tube material, is formed uniformly several ducts on its surface, and the duct is from center to fringe radiation
Radial duct, average pore size are 3~5nm.The specific surface area of further measurement nano-tube material is 950m2/g.Into
One step Fig. 3 and Fig. 4 is combined it is found that right-handed helix structure is presented in nano-tube material made from the embodiment of the present invention.
Embodiment 3
On the basis of above-described embodiment 2, other reaction conditions are remained unchanged, and only control the temperature of reaction system 25
DEG C with complete reaction, obtained silica nanosphere shown in fig. 5, control reaction system temperature be 25 DEG C~90 DEG C it
Between, tube wall cannot be obtained in the right-handed helix nano-tube material of radiation hole arrangement.This illustrates reaction temperature to silicon of the present invention
The structure of nano material is affected.
Embodiment 4
On the basis of above-described embodiment 2, other reaction conditions are remained unchanged, by the volume ratio tune of concentrated ammonia liquor and normal propyl alcohol
Whole is 7:3, and reaction has obtained the mixture of silica nanosphere and nanotube shown in fig. 6.
Similarly, on the basis of above-described embodiment 2, other reaction conditions are remained unchanged, and the quality percentage of concentrated ammonia liquor is dense
Degree is diluted to 2.5% by 25% and completes to test, and has obtained the silica nanometer material shown in Fig. 7 for having undefined structure
Material, and by the control of the concentration of concentrated ammonia liquor between 20~25%, structure will not change.
This illustrates that the dosage of reaction dissolvent, concentration of reaction dissolvent etc. also compare the influence of the structure of silicon nano material of the present invention
It is larger.
Embodiment 5
On the basis of above-described embodiment 2, other reaction conditions are remained unchanged, by chiral small molecule template L-
16Ala11PyPF6 concentration in mixed solution is adjusted to 8mg/mL, has obtained preparing spherical SiO 2 nano material shown in Fig. 8.
On the basis of above-described embodiment 2, other reaction conditions are remained unchanged, by chiral small molecule template L-
16Ala11PyPF6 concentration in mixed solution becomes 6mg/mL, has obtained what spherical shape shown in Fig. 9 was mixed with random structure
Silica nano material.
It is also bigger that this illustrates that the concentration of chiral small molecule template influences the structure of silicon nano material of the present invention.
At the same time, if the silicon source tetraethoxysilane in above-described embodiment 2 is substituted for the bis- (triethoxysilicanes of Isosorbide-5-Nitrae-
Base) any one in benzene, the structure of obtained silicon nano material remains unchanged, this illustrates silicon source to silicon nano material of the present invention
Structure influence it is little.
In addition, if small molecule template L-16Ala11PyPF6 of the invention is substituted for L-16Ala11PyBr, it will not
Obtain the nano-tube material for having structure of the invention.
For tube wall produced by the present invention in the right-handed helix nano-tube material of radiation hole arrangement, Figure 10 shows this hair
The bright pore-size distribution for implementing 2 gained nano-tube materials shows that the curve is that the absorption of typical IV type is bent in 4nm or so, Figure 11
Line shows there is meso-hole structure in sample.
Therefore, the present invention provides one kind using cationic colloidal as template, and tube wall is successfully prepared in the arrangement of radiation hole
Right-handed helix nano-tube material, not only preparation method is simple, and the specific surface area of nano-tube material obtained is preferable, table
The aperture in hole is radiated up to 2~50nm in face, which can be used as the nano-carrier of drug, albumen and gene for controlling in vivo
It treats, meanwhile, the chiral nanotubes for having the structure, which can also be assembled further, the fields such as also can be used for chiral catalysis and splits.
Above embodiments are only best citing, rather than a limitation of the embodiments of the present invention.Except above-described embodiment
Outside, there are also other embodiments by the present invention.All technical solutions formed using equivalent substitution or equivalent transformation, all fall within the present invention
It is required that protection scope.
Claims (10)
1. a kind of tube wall in radiation hole arrangement right-handed helix nano-tube material, it by one or more length be 100nm~
20 μm, nano-tube of the diameter between 3nm~100nm rearrange in space, the every nano-tube is opened for one end
The hollow cavity that mouth, other end closing are arranged, is distributed with more than one duct, each hole on the side wall of hollow cavity
Road is the radial duct from center to fringe radiation, and average pore size is 2nm~50nm.
2. the right-handed helix nano-tube material that tube wall is arranged in radiation hole according to claim 1, it is characterised in that: described
The specific surface area of nano-tube material is 600~1400m2/g。
3. tube wall described in a kind of claim 1 is in the preparation method of the right-handed helix nano-tube material of radiation hole arrangement, it is wrapped
It includes and uses cationic colloidal for template, using esters of silicon acis as silicon source, the chiral silicon that tube wall duct is arranged radially is prepared
Nanotube.
4. preparation method of the tube wall in the right-handed helix nano-tube material of radiation hole arrangement according to claim 3, spy
Sign is: the cationic colloidal includes the compound for having following structural formula:
Wherein, m=2~18, n=2~20；R is CH3, (CH3)2CH-, (CH3)2CH2H- or Ph-CH2-。
5. according to the preparation method for the right-handed helix nano-tube material that the tube wall of claim 3 or 4 is arranged in radiation hole,
Be characterized in that: the preparation method includes following detailed process:
1) cationic colloidal is added in deionized water, preparation obtains cationic aqueous solution；
2) aqueous slkali and alkylol are added into the cationic aqueous solution that step 1) obtains, adjustment solution ph is 7.5~14, is stirred
It mixes to obtain mixed solution；
3) esters of silicon acis is added into mixed solution made from step 2), reaction generates white colloidal, then washed and calcining obtains
The right-handed helix nano-tube material that tube wall is arranged in radiation hole.
6. preparation method of the tube wall in the right-handed helix nano-tube material of radiation hole arrangement according to claim 5, spy
Sign is: the volume ratio of aqueous slkali described in step 2) and alkylol is 9:1~8:2.
7. preparation method of the tube wall in the right-handed helix nano-tube material of radiation hole arrangement according to claim 6, spy
Sign is: aqueous slkali described in step 2) include one of tetramethylammonium hydroxide, ammonium hydroxide, sodium hydroxide or potassium hydroxide with
Upper configuration acquired solution.
8. the preparation method for the right-handed helix nano-tube material that tube wall described according to claim 6 or 7 is arranged in radiation hole,
Be characterized in that: alkylol described in step 2) includes at least one of ethyl alcohol, normal propyl alcohol, isopropanol, n-butanol or isobutanol.
9. preparation method of the tube wall in the right-handed helix nano-tube material of radiation hole arrangement according to claim 5, spy
Sign is: esters of silicon acis described in step 3) includes tetraethyl orthosilicate, positive quanmethyl silicate, bis- (triethoxysilicane) second of 1,2-
At least one of bis- (triethoxysilicane) benzene of alkene, 1,2- or bis- (triethoxy silicon substrate) benzene of 1,4-.
10. preparation method of the tube wall in the right-handed helix nano-tube material of radiation hole arrangement according to claim 5, spy
Sign is: calcination condition described in step 3) is to control 500~600 DEG C of temperature, calcines 4~8h.
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| CN113562737A (en) * | 2021-07-29 | 2021-10-29 | 沈阳药科大学 | Mesoporous silica nanoparticle with adjustable chiral structure and preparation method and application thereof |
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