CN109970896A - A method of building temperature sensitive type carbon nano tube compound material is modified based on carbon dots - Google Patents
A method of building temperature sensitive type carbon nano tube compound material is modified based on carbon dots Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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Abstract
The present invention relates to a kind of methods for modifying building temperature sensitive type carbon nano tube compound material based on carbon dots.The technical solution adopted is that: using carbon nanotube CNT as substrate, carbon dots CDs is added, through ultrasound, stirs, centrifugation obtains compound CNT-CDs；Regulation system is alkalinity; under nitrogen protection; the NIPAM (n-isopropyl acrylamide) and initiator of purifying are added in CNT-CDs; prior to 35~40 DEG C 2~3h of reaction; then at 80~90 DEG C of 4~6h of reaction; centrifuge washing obtains and modifies building temperature sensitive type carbon nano tube compound material CNT-CDs-PNIPAM based on carbon dots.The temperature sensitive type composite material CNT-CDs-PNIPAM prepared using method of the invention realizes losslessization modification, and obtained temperature sensitive intelligent response material had not only maintained the property and pattern of CNTs, but also had the Thermo-sensitive of PNIPAM concurrently simultaneously.
Description
Technical field
The invention belongs to the field of chemical synthesis, are specifically related to one kind and are assembled based on carbon dots, CNTs and PNIPAM is passed through
Losslessization modification is realized in the connection of CDs, and obtained temperature sensitive intelligent response material had both maintained the property and pattern of CNTs,
Have the Thermo-sensitive of PNIPAM concurrently simultaneously again.
Background technique
Due to the minor change of the external environments such as external temperature, pH value, illumination, zoom, salt, electric field and pressure, intelligence
Significant change can occur for the performance (for example, volume change) of equipment.They are anti-in organizational project, medicine controlled release carrier, regeneration
Fields should be waited to have potential application prospect.The researcher of material science and polymer science pays close attention to always them in decades
Inherent response characteristic.Wherein, temperature sensing material is most study, however, its can not and the combination of inorganic matter to constrain it wide
General application.
Carbon as famous one of inorganic matter, by its it is unique it is one-dimension based on, shown in various researchs huge
Potentiality, have excellent machinery, optics and Electronic Performance and higher chemical stability.These characteristics composite material,
Field emission display, energy storage, sensor, scanning probe, load drug carrier etc. have a wide range of applications.However, to realize
The abundant prospect of its Development of Novel functionality high-quality product in various applications, separation and it is evenly dispersed be basic premise.It is more
Wall carbon is interacted by non-supercritical realize stabilization in an aqueous medium, is had in practical applications to the material potential excellent
Point.
Carbon dots become a kind of emerging carbon materials because of its excellent emission performance, good water-soluble and energy transfer capability
Material.The straightforward procedure synthesized from inexpensive carbon source makes carbon dots be widely used in sensor and imaging along with the reprocessing on surface
Equal fields.It is heteroatomic to adulterate and introduce different surface functionalities using different precursors in the synthesis process and directly adjust
Save physicochemical properties.Equally, carbon dots can interact with hydrophobic material, make the hydrophilic functional on hydrophobic core and carbon dots surface
Group assigns their surfactants such as amphipathic characteristic together.In recent years, carbon dots composite material was developed, and in the devices
It is widely used.In these methods, either chemical method or polymer investment, all be used to be dispersed in water
In, the class surfactant behavior of carbon dots causes carbon dots to form stable carbon dots compound in water.
PNIPAM has the lower critical solution temperature (32 DEG C or so) of completely reversibility in water, because this temperature is between room
Between mild body temperature, so that PNIPAM is very interested in biologic applications.More than critical-temperature, polymer phase and solution point
From, and the polymer lower than critical-temperature is soluble.PNIPAM is a kind of the new of typical lower critical solution temperature (32 DEG C)
Type macromolecule.It by it is easy closely under random neutrality be changed into the closelypacked neutral particle in height.It is this kind of to be quick on the draw
Polymer be explored the application for modified and film.Butt material with high response polymer can be with composite wood
Material/hybrid material combines.By chemistry or atom transfer radical polymerization in situ, carried out with high-performance reactive polymer
Research.In these randomization strategies, since it is easily obtained, height extends, relatively stable, reversible, and carbon network is not influenced
Structural intergrity, therefore have received widespread attention.But at this stage, and the combination of inorganic matter usually will be inorganic to destroy
Object surface is cost, directly in conjunction with inorganic matter or can not modify, destroy its own structure and properties, limit his answer
With so to develop one kind can be by the connection type of itself and the modification of inorganic matter losslessization.
Therefore, inventing one can be under the premise of retaining temperature sensitive performance in conjunction with inorganic matter and inorganic matter itself
The technical solution of performance is just particularly important.
Summary of the invention
The object of the present invention is to provide a kind of methods for modifying building temperature sensitive type carbon nano tube compound material based on carbon dots.It adopts
The temperature sensitive type composite material CNT-CDs-PNIPAM prepared with method of the invention realizes losslessization modification, obtained temperature
Quick intelligent response material had not only maintained the property and pattern of CNTs, but also had the Thermo-sensitive of PNIPAM concurrently simultaneously.
The technical solution adopted by the present invention is that: a kind of side for modifying building temperature sensitive type carbon nano tube compound material based on carbon dots
Method includes the following steps:
1) using carbon nanotube CNT as substrate, carbon dots CDs is added, through ultrasound, stirs, centrifugation obtains compound CNT-CDs；
2) regulation system is alkalinity, under nitrogen protection, NIPAM (the N- isopropyl propylene of purifying is added in CNT-CDs
Amide) and initiator, prior to 35~40 DEG C 2~3h of reaction, then at 80~90 DEG C of 4~6h of reaction, centrifuge washing is obtained based on carbon dots
Modification building temperature sensitive type carbon nano tube compound material CNT-CDs-PNIPAM.
Preferably, step 1) specifically: using carbon nanotube CNT as substrate, carbon dots CDs is added, first 3~4h of ultrasound, then
Stir 3~4h, repeat ultrasound and stirring 3~5 times after, mixed liquor is poured into centrifuge tube, in 11000r centrifugation 30min leave from
Black object on heart tube wall is added after deionized water dissolving black object and is centrifuged 30min then at 11000r, black on tube wall by being centrifuged
Color object obtains compound CNT-CDs repeatedly plus after water centrifugation 4~5 times.
Preferably, the preparation method of the carbon dots CDs includes the following steps: to take citric acid and glycine, adds water, ultrasound is extremely
Dissolution is placed in reaction kettle, and 6~7h is reacted at 170~190 DEG C, is stood, cooling, and filtering obtains carbon dots CDs.
It is furthermore preferred that in mass ratio, citric acid: glycine=1:1.
Preferably, step 2), the pH value for adjusting CNT-CDs is 9~10.
Preferably, the NIPAM of the purifying is that NIPAM is successively carried out purification process through acetone and n-hexane.
Preferably, the initiator is azodiisobutyronitrile (AIBA).
Preferably, centrifuge washing described in step 2) is: carrying out centrifuge washing with 60~70 DEG C of distilled water.
The beneficial effects of the present invention are:
1) present invention uses multi-walled carbon nanotube to be prepared for CNT-CDs for carbon source, and CNT is tied by ultrasound, stirring and CDs
It is combined.Due to the hydrophily of carbon dots, CNT-CDs has apparent hydrophily, so that CDs is in CNT surface compared with CNT
Losslessization modification is carried out.Using CNT-CDs as substrate, it is compound that CNT-CDs-PNIPAM is prepared for by functional group reactions
Object forms the intelligent carbon pipe with temperature-sensitive assembled based on carbon dots.CNT after CDs and PNIPAM modification has
Hydrophily, but also with Thermo-sensitive and performance itself that remain CNT.
2) preparation method of this simplicity of one-step method is introduced into the design of CNT-CDs-PNIPAM, in synthesis by the present invention,
It is successfully prepared the intelligent carbon nanotube that novel intelligent material is assembled based on carbon dots, and establishes a kind of losslessization modification CNTs
New method.
3) present invention has investigated the modification of CNT-CDs losslessization, mostly uses sour destruction for the modification of CNTs in the prior art
Its surface is modified, and the present invention is acted on using the π-π of CDs and CNTs, so that hydrophilicity can be presented in the CNTs after modification,
It is able to maintain itself good performance again, so that embodying conventional CNTs modifies the huge advantage that cannot be compared, keeps CNTs true
Subsequent applications are put into its high quality in positive meaning.
4) present invention is prepared for CNT-CDs nano material, and as the material of CNT-CDs-PNIPAM reaction, not only
It makes simply, low in cost, and yield is high, and obtained CNT-CDs nano material can completely remove unreacted CDs,
Reduce interference of the CDs to reaction.
5) the intelligent carbon nanotube CNT-CDs- that the designed novel intelligent material synthesized of the present invention is assembled based on carbon dots
PNIPAM is acted on by functional group, and CNT-CDs and PNIPAM losslessization is linked together, the intelligent carbon nanometer after making assembling
The intelligent response of the existing Thermo-sensitive material PNIPAM of pipe CNT-CDs-PNIPAM, and the property of CNTs is combined, it is with CDs
Connection is truly realized losslessization modification.
Detailed description of the invention
Fig. 1 is the TEM figure of CDs, CNTs, CNT-CDs, CNT-PNIPAM and CNT-CDs-PNIPAM；
Wherein,
A:CDs (Inset: I is the partial enlarged view of CDs, and II is digital photograph)；
B:CNTs (Inset: I is the partial enlarged view of CNTs, and II is digital photograph)；
C:CNT-CDs (Inset: I is the partial enlarged view of CNT-CDs, and II is digital photograph)；
D:CNT-PNIPAM (Inset: I is the partial enlarged view of CNT-PNIPAM, and II is digital photograph)；
E:CNT-CDs-PNIPAM (Inset: I is the partial enlarged view of CNT-CDs-PNIPAM, and II is digital photograph).
Fig. 2 be CDs (a) and CNT-CDs (b) emission spectrum (Inset: I be CDs, II be CNT-CDs ultraviolet lamp photograph
Digital photograph under penetrating).
Fig. 3 is the UV-Vis of CNT-CDs (a), CNT-CDs-PNIPAM (b) and CDs (c).
Fig. 4 is the infrared figure of CNTs (a), CNT-CDs (b), CNT-CDs-PNIPAM (c), PNIPAM (d) and CDs (e).
Fig. 5 is the TGA curve of CNTs (a), CNT-CDs (b), CDs (c), CNT-CDs-PNIPAM (d) and PNIPAM (e).
Fig. 6 is the Raman figure of CNT-CDs (a), PNIPAM (b), CNT-CDs-PNIPAM (c) and CNTs (d).
Fig. 7 is UV-Vis figure (Inset:CNT-CDs-PNIPAM of the CNT-CDs-PNIPAM at 20 DEG C (a) and 40 DEG C (b)
The relational graph of temperature cycles and UV-V is absorption peak).
Fig. 8 a is CNTs (a), CNT-PNIPAM (b), PNIPAM (c) and CNT-CDs-PNIPAM (d) under 20 DEG C of environment
Digital photograph.
Fig. 8 b is CNTs (a), CNT-PNIPAM (b), PNIPAM (c) and CNT-CDs-PNIPAM (d) under 40 DEG C of environment
Digital photograph.
Fig. 9 a is the Zeta potential figure of CNTs in aqueous solution.
Fig. 9 b is the Zeta potential figure of CNT-CDs in aqueous solution.
Specific embodiment
Technical solution for a better understanding of the present invention, spy are described in further detail with specific embodiment, but side
Case is without being limited thereto.
The method that embodiment 1 modifies building temperature sensitive type carbon nano tube compound material based on carbon dots
(1) preparation method
1, the preparation of CDs
In beaker, 5g citric acid and 5g glycine is added, 20ml water is added, ultrasound is placed in reaction kettle to after dissolving,
6h is reacted at 180 DEG C, is stood, is cooled to room temperature, filters to take filtrate, obtain CDs.
2, the preparation of CNT-CDs
In a round bottom flask, 0.5g carbon nanotube CNTs and 60ml CDs is added, first ultrasound 3h, is stirred for 3h, repeat super
Sound and whipping step 3 times rock round-bottomed flask without obvious black particle until CNT is completely dissolved.Mixed liquor is poured into centrifuge tube
In, it is centrifuged 30min in 11000r, yellow green CDs solution is abandoned and leaves the black object being centrifuged on tube wall, carry out centrifuge washing, that is, add
Enter appropriate amount of deionized water, by black object dissolution after, then at 11000r be centrifuged 30min, abandon yellow green CDs Solutions Solution leave again from
Black object on heart tube wall, repeats plus water is centrifuged 4~5 times to noresidue CDs, and the black object left on centrifugation tube wall is as compound
Object CNT-CDs is diluted to 140mL with deionized water, collects stand-by.Yield 0.5279g after drying.
3, the preparation of CNT-CDs-PNIPAM
The purifying of NIPAM: being added 10g NIPAM monomer in two mouthfuls of round-bottomed flasks, and acetone is added dropwise at 50 DEG C to NIPAM
N-hexane, (V until there is whiteness after n-hexane is added is added dropwise in all dissolutions, cooling for refluxAcetone: VN-hexane=1:6),
Stop heating, is cooled to room temperature, is transferred to 0 DEG C of placement 10h, is transferred to -10 DEG C of placement 20h.It after crystal precipitation, takes out and filters, use
N-hexane washing.Vacuum drying at room temperature.
In a round bottom flask, 10ml CNT-CDs aqueous solution is taken (about containing CNT-CDs 0.03g), ammonium hydroxide to be added and adjusts pH
After value is 9~10, NIPAM the and 0.017g AIBA of 1.000g purifying is added, in N2Under protection, prior to 35 DEG C reaction 2h, then at
80 DEG C of reaction 3h, obtain CNT-CDs-PNIPAM and PNIPAM mixed liquor.Centrifuge washing is into solution without PNIPAM, that is, centrifugation
Washing operation is the deionized water that about 60 DEG C are added in mixed liquor, abandons solution and leaves hydrophobic block, after being cooled to room temperature,
Block becomes hydrophilic loose, and about 60 DEG C of deionized water is added repeatedly, filters, and cooling, 4~5 times, the block finally obtained is i.e.
For CNT-CDs-PNIPAM, it is 0.1257g after yield drying, collects sample.
(2) coherent detection
1, Fig. 1 is CDs (A) (Inset:CDs partial enlarged view I, digital photograph II), (Inset:CNTs is local by CNTs (B)
Enlarged drawing I, digital photograph II), CNT-CDs (C) (Inset:CNT-CDs partial enlarged view I, digital photograph II), CNT-
PNIPAM (D) (Inset:CNT-PNIPAM partial enlarged view I, digital photograph II) and CNT-CDs-PNIPAM (E) (Inset:
CNT-CDs-PNIPAM partial enlarged view I, digital photograph II) TEM figure.
From A- I in Fig. 1, it can be seen that many stains are evenly dispersed in copper mesh, are not assembled significantly, this
Show that prepared CDs is uniform nano spherical particle.A- II is CDs digital photograph under fluorescent light in Fig. 1, can by photo
See that CDs is uniformly distributed in the solution in yellow green.
By B in Fig. 1 as it can be seen that CNTs is rambling on copper mesh arranges and have a large amount of nodes.It can be seen by B- I in Fig. 1
Out, it is hollow state that the surface CNTs is intact and intermediate.B- II is CNTs digital photograph under fluorescent light in Fig. 1, is shone by the number
The visible CNTs of piece is not soluble in water, and hydrophobicity is presented.
By C- I in Fig. 1 as it can be seen that CNT-CDs dispersed preferable and node compared with CNTs is reduced, carbon pipe surface is intact
And intermediate is hollow state, and it is similar to CNTs pattern, show that the structure of carbon pipe is complete and CDs and CNTs success is compound.By
Black is presented as it can be seen that CNT-CDs is evenly dispersed in II CNT-CDs digital photograph of C- in water and under fluorescent light in Fig. 1, also indicates that
CDs and CNTs success is compound.
By D- I in Fig. 1 as it can be seen that PNIPAM is disorderly and unsystematic to be scattered in the surface CNTs, and not it is grown on CNTs.By Fig. 1
For middle D- II as it can be seen that hydrophobicity is presented in CNT-PNIPAM, compound can not directly be formed by also demonstrating CNTs and PNIPAM.
It is shown by E- I in Fig. 1, rambling carbon pipe surface successful growth has gone out the surface of PNIPAM and CNTs not
It is destroyed.Show that the CNTs after the modification of CDs can not only be compound with PNIPAM success, and can retain CNTs's itself
Property.By II CNT-CDs-PNIPAM digital photograph of E- in Fig. 1 as it can be seen that compared with Fig. 1 D- II, Fig. 1 E- II presents uniform black
Color, it was demonstrated that CNT-CDs and PNIPAM success is compound.
2, (Inset:CDs (I), CNT-CDs (II) ultraviolet lamp shine the emission spectrum that Fig. 2 is CDs (a) and CNT-CDs (b)
Digital photograph under penetrating).The interaction between carbon dots and carbon nanotube is had studied with fluorescent spectrometry, Fig. 2 is excitation wavelength
The transmitting spectrogram of the CDs (a) and CNT-CDs (b) of 368nm, launch wavelength 448nm, insertion figure be CDs (I), CNT-CDs (II)
Digital photograph under ultraviolet light irradiation has studied carbon dots and the fluorescence intensity after carbon nanotube interaction, as seen from Figure 2 CNT-
CDs fluorescent quenching, by insertion scheme visible CNT-CDs success it is compound after, CNT-CDs is dispersed in water, and in ultraviolet lamp
No fluorescence under irradiation, it was confirmed that CNT-CDs success is compound.
3, Fig. 3 is the UV-Vis of CNT-CDs (a), CNT-CDs-PNIPAM (b) and CDs (c).As seen from Figure 3: CNT-CD
There is an absorption peak at 260nm；CDs has an absorption peak at 348nm；CNT-CDs-PNIPAM has one at 258nm
Absorption peak, CNT-CDs-PNIPAM absorption peak blue shift, it was demonstrated that CNT-CDs-PNIPAM success is compound.
4, Fig. 4 is the infrared of CNTs (a), CNT-CDs (b), CNT-CDs-PNIPAM (c), PNIPAM (d) and CDs (e)
Figure.By the FT-IR of CNT (a) as it can be seen that in 3427cm-1, 1631cm-1And 1107cm-1Place occurs respectively and O-H, C=O and C-O
The corresponding several peak of functional group, but intensity is very weak.By CNT-CDs (b) as it can be seen that in 3409cm-1, 1634cm-1And 1125cm-1
Place occurs respectively and the corresponding several peak of O-H, C=O and C-O functional group.This may be compound in CNT-CDs due to CDs
There are caused by Oxygenation function, show CDs in the fixation of CNT surface in material.By CNT-CDs-PNIPAM (c) as it can be seen that CNT-
CDs-PNIPAM is in 3435cm-1And 2923cm-1There are multiple vibration peaks at place, belong to the stretching vibration of-OH and C-H.In addition,
1631cm-1Peak value it is related with C=O stretching vibration, and C-O (1033cm-1) vibrated with the stretching vibration of aromatic rings and bone
And other eigen vibrations are related.It can be seen that not only to contain O-H, C=O and C-O corresponding on the surface CNT-CDs-PNIPAM (b)
The characteristic peak of CNTs-CDs, and the characteristic peak containing the corresponding PNIPAM of C-H, therefore provable CNT-CDs and PNIPAM success
It is compound.By PNIPAM (d) as it can be seen that 3434cm-1Peak indicate compound-OH, 2973cm-1Peak corresponding to C-H stretching shake
It is dynamic, in 1037cm-1Place observes a peak, this is because absorption peak is in 1657-1605cm caused by C-O oxygen-containing group-1Range
Inside represent C=O stretching.By the FT-IR of CDs (e) as it can be seen that CDs is in 3413cm-1、2950cm-1And 1386cm-1There are multiple vibrations at place
Dynamic peak, belongs to the stretching vibration of-OH/-NH, C-H and C-NH-C.In addition, in 1606cm-1Peak value have with C=O stretching vibration
It closes, and C-O (1137cm-1) and C-H (759cm-1) with the stretching vibration of aromatic rings and bone vibration and other eigen vibrations
It is related.It can be seen that CDs is made of the aromatic structure that the organic groups such as a large amount of amino and phenolic hydroxyl group are contained on surface.
5, the TGA that Fig. 5 is CNTs (a), CNT-CDs (b), CDs (c), CNT-CDs-PNIPAM (d) and PNIPAM (e) is bent
Line.It can be seen that CNT and CNT-CDs good thermal stability from a and b and CNT-CDs be similar with CNT, show that CNT-CDs weightlessness is
As caused by CNT.After being compounded to form CNT-CDs-PNIPAM with PNIPAM, (d) can be seen that CNT-CDs- from Fig. 5
PNIPAM has 85% weightlessness at 800 DEG C, similar with PNIPAM, shows that the weightlessness of CNT-CDs-PNIPAM is since PNIPAM is caused
's.
6, Fig. 6 is the Raman figure of CNT-CDs (a), PNIPAM (b), CNT-CDs-PNIPAM (c) and CNTs (d).By Fig. 6
As it can be seen that CNT-CDs (a) is in 1309cm-1And 1568cm-1There are two characteristic peaks in place, can belong to the D of CNT-CDs (a) respectively
Band and G band.In compound CNT-CDs (a), the intensity ratio of D and G band is 1.13, in compound CNT-CDs-PNIPAM (c)
In, in 1395cm-1And 1558cm-1There are two characteristic peaks, the D band and G band of CNT-CDs-PNIPAM (c) can be respectively belonging to.
The intensity ratio of D and G band is 1.35, and ratio becomes larger, and defect increases.
7, Fig. 7 is UV-Vis figure (Inset:CNT-CDs- of the CNT-CDs-PNIPAM at 20 DEG C (a) and 40 DEG C (b)
The relational graph of PNIPAM temperature cycles and UV-Vis absorption peak).Temperature has been investigated to CNT- using uv-visible absorption spectra
The influence of CDs-PNIPAM.As seen from Figure 7, at 20 DEG C, CNT-CDs-PNIPAM has absorption peak at 258nm, is heated to 40
DEG C do not have obvious absorption peaks, thus can illustrate CNT-CDs-PNIPAM 40 DEG C from solution be precipitated be sunken to sample bottom of pond portion, because
This can't detect absorption peak, heat again, be restored to original state again, in cycles, show the transformation of hydrophilic-hydrophobic.
8, Fig. 8 a is CNTs (a), CNT-PNIPAM (b), PNIPAM (c) and CNT-CDs-PNIPAM (d) in 20 DEG C of environment
Under digital photograph.By (a) in Fig. 8 a as it can be seen that CNTs in water can not be evenly dispersed, hydrophobicity is presented.By in Fig. 8 a
(b) as it can be seen that hydrophobicity is presented in PNIPAM solution by CNTs and CNTs and PNIPAM is clearly separated, there is no form with PNIPAM
Compound.It is transparent by (c) in Fig. 8 a as it can be seen that PNIPAM in aqueous solution can be evenly dispersed.It can by (d) in Fig. 8 a
See, CNT-CDs-PNIPAM can be very good to be dispersed in water, and show hydrophily, and carbon nanotube is effectively gone after showing modification
Agglomeration, solution are in black.
Fig. 8 b is CNTs (a), CNT-PNIPAM (b), PNIPAM (c) and CNT-CDs-PNIPAM (d) under 40 DEG C of environment
Digital photograph.By (a) in Fig. 8 b as it can be seen that CNTs in water can not be evenly dispersed, hydrophobicity is presented.By (b) in Fig. 8 b
It can be seen that, it can be seen that CNTs can not disperse well in PNIPAM solution, and the CNTs of black swim in it is transparent
In PNIPAM solution.By (c) in Fig. 8 b as it can be seen that PNIPAM in aqueous solution can be evenly dispersed, it is creamy white at 40 DEG C.
Shape is rolled up as it can be seen that CNT-CDs-PNIPAM assembles at high temperature by (d) in Fig. 8 b, this is because compound is with PNIPAM's
Black is presented in Thermo-sensitive.
9, Fig. 9 a is the Zeta potential figure of CNTs in aqueous solution.Fig. 9 b is the Zeta potential of CNT-CDs in aqueous solution
Figure.Test result, Fig. 9 a show, CNTs shows stronger electronegativity in aqueous solution, Zate potential value about-
12.9mV, Fig. 9 b shows, CNT-CDs also shows stronger electronegativity in aqueous solution, Zeta potential value about-
23.7mV.Its absolute value becomes ± 29.5mV from ± 26.35mV, before absolute value becomes larger, therefore CNT-CDs stability becomes larger and is compound
Its current potential is negative value afterwards, illustrates that the electronics electronegativity on the compound rear surface CNT-CDs is constant.
Claims (9)
1. a kind of method for modifying building temperature sensitive type carbon nano tube compound material based on carbon dots, which is characterized in that including walking as follows
It is rapid: 1) that using carbon nanotube CNT as substrate, carbon dots CDs is added, through ultrasound, stirs, centrifugation obtains compound CNT-CDs；2) it adjusts
Section system is alkalinity, under nitrogen protection, the NIPAM and initiator of purifying is added in CNT-CDs, is reacted prior to 35~40 DEG C
2~3h, then at 80~90 DEG C of 4~6h of reaction, centrifuge washing obtains and modifies building temperature sensitive type carbon nano tube compound material based on carbon dots
CNT-CDs-PNIPAM。
2. the method according to claim 1, wherein step 1) specifically: using carbon nanotube CNT as substrate,
Carbon dots CDs is added, first 3~4h of ultrasound, is stirred for 3~4h, after repeating ultrasound and stirring 3~5 times, mixed liquor is poured into centrifuge tube
In, the black object on centrifugation tube wall is left in 11000r centrifugation 30min, is added after deionized water dissolving black object then at 11000r
It is centrifuged 30min, the black object on tube wall will be centrifuged, repeatedly plus after water centrifugation 4~5 times, obtains compound CNT-CDs.
3. the method according to claim 1, wherein the preparation method of the carbon dots CDs includes the following steps: to take
Citric acid and glycine add water, and ultrasound is placed in reaction kettle to dissolving, and 6~7h is reacted at 170~190 DEG C, is stood, cold
But, it filters, obtains carbon dots CDs.
4. according to the method described in claim 3, it is characterized in that, in mass ratio, citric acid: glycine=1:1.
5. the method according to claim 1, wherein step 2), regulation system is that alkalinity to pH value is 9~10.
6. the method according to claim 1, wherein the NIPAM of the purifying is, by NIPAM successively through acetone
Purification process is carried out with n-hexane.
7. the method according to claim 1, wherein the initiator is azodiisobutyronitrile.
8. the method according to claim 1, wherein centrifuge washing described in step 2) is: with 60~70 DEG C
Deionized water carries out centrifuge washing.
9. the carbon nano tube compound material CNT-CDs-PNIPAM of method preparation according to any one of claims 1 to 8 makees
For the application of Thermo-sensitive material.
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| CN110812341A (en) * | 2019-11-14 | 2020-02-21 | 辽宁大学 | Preparation method of mesoporous silicon composite nanoparticles based on temperature-sensitive polymer/carbon dots |
| CN113198050A (en) * | 2021-04-07 | 2021-08-03 | 西安理工大学 | Preparation method of pH-temperature cooperative response drug release bone cement |
| CN114410372A (en) * | 2022-02-08 | 2022-04-29 | 中国科学院兰州化学物理研究所 | Preparation method of temperature-sensitive composite microgel water-based lubricant |
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| CN108841346A (en) * | 2018-07-13 | 2018-11-20 | 吉林大学 | A kind of high bonding strength environmental protection supermolecule physical gel binder and preparation method thereof |
| WO2019060456A1 (en) * | 2017-09-20 | 2019-03-28 | The Regents Of The University Of Colorado, A Body Corporate | Carbon nanotube-functionalized reverse thermal gel and methods of forming and using same |
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| WO2019060456A1 (en) * | 2017-09-20 | 2019-03-28 | The Regents Of The University Of Colorado, A Body Corporate | Carbon nanotube-functionalized reverse thermal gel and methods of forming and using same |
| CN108841346A (en) * | 2018-07-13 | 2018-11-20 | 吉林大学 | A kind of high bonding strength environmental protection supermolecule physical gel binder and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110812341A (en) * | 2019-11-14 | 2020-02-21 | 辽宁大学 | Preparation method of mesoporous silicon composite nanoparticles based on temperature-sensitive polymer/carbon dots |
| CN113198050A (en) * | 2021-04-07 | 2021-08-03 | 西安理工大学 | Preparation method of pH-temperature cooperative response drug release bone cement |
| CN114410372A (en) * | 2022-02-08 | 2022-04-29 | 中国科学院兰州化学物理研究所 | Preparation method of temperature-sensitive composite microgel water-based lubricant |
| CN114410372B (en) * | 2022-02-08 | 2022-10-25 | 中国科学院兰州化学物理研究所 | Preparation method of temperature-sensitive composite microgel water-based lubricant |
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