CN106243365B - A kind of preparation method and applications of CNFs, CPFD nano hybridization aeroge - Google Patents
A kind of preparation method and applications of CNFs, CPFD nano hybridization aeroge Download PDFInfo
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- CN106243365B CN106243365B CN201610616821.7A CN201610616821A CN106243365B CN 106243365 B CN106243365 B CN 106243365B CN 201610616821 A CN201610616821 A CN 201610616821A CN 106243365 B CN106243365 B CN 106243365B
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Abstract
The invention discloses a kind of preparation methods of CNFs, CPFD nano hybridization aeroge, comprising the following steps: (1) preparation of water-soluble cationic conjugated polymer (CPFD)；(2) preparation of CNFs suspension；(3) preparation of CNFs/CPFD hybrid aerogel；(4) preparation of CNFs/CPFD hybrid aerogel.Application of CNFs, CPFD nano hybridization aeroge in the super sensitivity detection of trace nitro-aromatic explosive vapors.CNFs of the invention can be environmentally friendly effective and steadily disperses CPFD.CNFs/CPFD hybrid aerogel can detecte nitro-aromatic explosive (NACs) steam of ultra trace, the fluorescent quenching of CPFD film of the fluorescent quenching efficiency of CNFs/CPFD hybrid aerogel than using spin coating technique to prepare is 3.6 times high-efficient, and CNFs/CPFD hybrid aerogel, which is used as, has good recycling as fluorescent optical sensor.
Description
Technical field
The present invention relates to the preparation of nano hybridization aeroge and its application field, specifically a kind of CNFs, CPFD nanometer miscellaneous
Change the preparation method and applications of aeroge.
Background technique
In recent years, anti-terrorism, Environmental security control and in terms of, a urgent problem to be solved is pair
Trace explosive steam quickly delicately detect.Most of explosive is the organic compound that nitro replaces.Wherein
Nitro-aromatic explosive (NACs) the most typical, for example, 2,4,6-trinitrotoluene (TNT), 2,4 dinitrotoluene (DNT)s (DNT) and
Picric acid (PA), is important military explosives, at the same be also bury in the world the primary chemical that does not blow up a mine in underground at
Point.Currently, the detection based on trace explosive mainly uses thermal neutron analysis method, gas-chromatography-electronics capture mass spectrum, X-ray
The large scale equipments such as imaging, electrochemistry and ion mobility spectrometry.But these equipment volumes are not huge, portable, expensive, need
The operation of professional is wanted, the on-line quick detection of different location is difficult to realize.On the contrary, glimmering based on conjugated polymer (CP)
Optical sensor has proven to the best candidate material of rapid sensitive detection nitro-aromatic explosive vapors.This is because with
Traditional detection method is compared, CP sensor with higher sensitivity, it is easily operated, cheap, NACs is put with fluorescence
Greatly (super quenching) effect the advantages that.Therefore, detection NACs is usually utilized to using different CP films prepared by spin coating technique to steam
Gas.But since analysis agent steam is spread very slowly in the fine and close CP film in not hole, the thickness of film has seriously affected this
The sensing capabilities of a little fluorescent sensing materials.[14] according to research reports, in order to reach optimal fluorescent quenching efficiency, CP film
Need very thin thickness.But in order to reach measurable fluorescence signal intensity and reduce the interference of photobleaching, CP film needs one
Fixed thickness.Meanwhile in solid film state, the pi-pi accumulation of CP skeleton can generate serious fluorescence intensity self-quenching.Separately
Outside, there is the spin coating CP sensor of different structure, preparation process needs cumbersome chemical modification or polymer backbone/side chain
Functionalization.In order to reduce sensing capabilities to the dependence of film thickness and find simple and effective preparation method, have a large amount of
The hybrid aerogel in hole is a kind of method solved the problems, such as, this is because aeroge has very big specific surface area, it is very high
Porosity is easy to the penetrating of analysis agent as sensing material.
In recent years, Tokyo Univ Japan Akira Isogai seminar is prepared for cellulose Nanowire by catalytic oxidation
It ties up (CNFs).It not only has suitable nanometer geometry (3-4nm wide, micron-size long), but also has good hydrophilic
Property (CNFs under drying regime is very easy to be moistened by electrolyte to rise).Meanwhile CNFs has largely at repetitive unit C-6
Carboxyl, and CNFs suspension is easy to be prepared into the aeroge with height hole.In addition, CNFs is with some other excellent
Performance, such as raw material sources are extensive, good portability, cheap, biocompatibility and environmentally friendly property.Cause
This, compared with nano silica, general fibre element, glass etc., CNFs in conjunction with conjugated polymer, expand containing a large amount of by preparation
Dissipate the fluorescent optical sensor in hole undoubtedly with higher academic and practical significance
Summary of the invention
The purpose of the present invention is to provide a kind of preparation method and applications of CNFs, CPFD nano hybridization aeroge.
To achieve the above object, the invention provides the following technical scheme:
A kind of preparation method of CNFs, CPFD nano hybridization aeroge, comprising the following steps:
(1) preparation of water-soluble cationic conjugated polymer CPFD
Successively by 15mL THF, 246mg 1,4- to the bromo- 9,9- of benzene hypoboric acid propylene glycol ester 1mmol and 494mg 2,7- bis-
Bis- [3- (dimethylamino) propyl] fluorenes 1mmol are added in there-necked flask, and after electromagnetic agitation to reactant dissolves, 10mL concentration, which is added, is
The K2CO3 aqueous solution of 2mol/L；After logical nitrogen 30min, mixed solution is warming up to 69 DEG C of reflux temperature, under nitrogen protection fastly
24mg Pd (PPh3) 4 catalyst is added in speed；After reaction system reacts 48h at a reflux temperature, reaction solution is cooled to room temperature,
Be subsequently transferred in the beaker for filling 50mL methanol, there is an insoluble matter precipitation, after suction filtration by insoluble matter successively with distilled water, methanol,
The sequence of distilled water is washed five times, respectively to remove the residues such as sylvite and catalyst；Solid after washing is in Soxhlet extraction
Acetone extraction 48h is used in device, with the oligomer in removing system；Product is finally transferred in vacuum drying oven at room temperature to vacuum is done
Dry 48h obtains conjugated polymer solid powder PFD；
100mg PFD is dissolved in the THF/DMSO solvent that 50mL volume ratio is 4:1, is subsequently added into 2g bromoethane；Reaction
, there is insoluble matter precipitation in system magnetic agitation 5 days at 50 DEG C in reaction system, suitable water is added and dissolves insoluble matter；Instead
After answering, THF, water and remaining bromoethane are rotated；Then the DMSO solution containing subject polymer is poured into largely
Ether in, have a Precipitation, acetone washed product repeatedly used after suction filtration；Finally 40 DEG C of vacuum drying in vacuum drying oven
48h obtains the conjugated polymer CPFD of cation；
(2) preparation of CNFs suspension
It weighs 0.033g TEMPO and 0.33g NaBr to be added sequentially in the distilled water of 400mL, magnetic force is utilized at 10 DEG C
Said mixture is sufficiently stirred in blender；After TEMPO, NaBr are completely dissolved, the wet wood pulp cellulose of 10g is added into reaction system
Element；It is vigorously stirred to wood pulp cellulose after being uniformly dispersed, then 150mmol NaClO is added into system, by being constantly added dropwise
0.5mol/L NaOH solution controls the pH of reaction system in 9-10；After reacting 6h, oxycellulose is filtered, is used in combination
Deionized water washs 3~5 times and obtains oxycellulose；Then oxycellulose is configured to the slurry of 2mg/mL using distilled water
Expect, in ice-water bath, it is cellulose nano-fibrous that ultrasound 15min, which removes oxycellulose, under 300W power；Then by fiber
Plain nanofiber suspension is centrifuged 10min at 10000g and removes unstripped oxycellulose；It will finally be prepared
CNFs suspension is placed in 4 DEG C of refrigerators and stores for future use；
(3) preparation of CNFs/CPFD hybrid aerogel
0.25% CNFs suspension is placed in 20mL glass mold, and is exposed to 12h in salt acid vapour, CNFs suspends
Liquid is changed into CNFs hydrogel；CNFs hydrogel is washed repeatedly using a large amount of distilled water, until CNFs hydrogel pH is in neutrality；Make
CNFs hydrogel is pre-processed with liquid nitrogen, CNFs aeroge is then prepared by Freeze Drying Technique；
(4) preparation of CNFs/CPFD hybrid aerogel
It weighs 50mg CPFD and is dissolved into 10mL distilled water, it is 0.25% that 20g mass fraction, which is then added,
CNFs suspension；Under ice bath after ultrasound 300W, 15min, mixed liquor becomes uniform CNFs/CPFD and is total to suspension；By suspension
Be placed in 20mL glass mold, and be exposed to 12h in salt acid vapour, CNFs/CPFD suspension be changed into CNFs/CPFD nanometers it is miscellaneous
Change hydrogel；CNFs/CPFD nano hybridized hydrogel is washed repeatedly using a large amount of distilled water, until CNFs/CPFD nano hybridization
Hydrogel pH is in neutrality；CNFs/CPFD nano hybridized hydrogel is pre-processed using liquid nitrogen, then passes through freeze-drying skill
CNFs/CPFD nano hybridization aeroge is prepared in art.
As a further solution of the present invention: 8mg solid CPFD is dissolved in 20mLTHF solvent to be configured to CPFD molten
Liquid, it is 1200r/min that CPFD solution is then added drop-wise to revolving speed dropwise, and time for adding is 20s on high-speed rotating quartz plate, so
The quartz plate is placed in vacuum drying oven 30 DEG C of vacuum drying for 24 hours afterwards, obtains spin coating CPFD film.
As further scheme of the invention: the size of the quartz plate are as follows: length × wide=24mm × 24mm, thickness=
1mm。
As further scheme of the invention: CNFs, CPFD nano hybridization aeroge is in trace nitro-aromatic
Application in the super sensitivity detection of explosive vapors.
As further scheme of the invention: the CNFs/CPFD hybrid aerogel has as fluorescent optical sensor to be followed
Ring usability.
Compared with prior art, the beneficial effects of the present invention are: CNFs can be environmentally friendly effective and steadily disperses CPFD.
CNFs/CPFD hybrid aerogel can detecte nitro-aromatic explosive (NACs) steam of ultra trace, the CNFs energy of unidimensional scale
The pi-pi accumulation of conjugated polymer CPFD skeleton is enough effectively inhibited, CNFs/CPFD hybrid aerogel possesses the three-dimensional apertures of High Level
Gauge structure, this can effectively improve the surface area of hybrid material and provides a large amount of hole or channel, be conducive to NACs steam to
Infiltration and diffusion inside CNFs/CPFD hybrid aerogel.Therefore, this novel fluorescence aeroge sensor is to NACs steam
With very high response sensitivity, after being exposed to 2,4- dinitrotoluene (DNT) (DNT) steam 120s, CNFs/CPFD hydridization airsetting
The fluorescent quenching of CPFD film of the fluorescent quenching efficiency of glue than using spin coating technique to prepare is 3.6 times high-efficient, and CNFs/CPFD is miscellaneous
Change aeroge to be used as fluorescent optical sensor with good recycling.
Detailed description of the invention
Fig. 1 is the synthetic route chart of CPFD in the preparation method of CNFs, CPFD nano hybridization aeroge.
Fig. 2 is the GPC spectrogram of CPFD in the preparation method of CNFs, CPFD nano hybridization aeroge.
Fig. 3 is the synthetic route chart of CNFs, CPFD nano hybridization aeroge.
Fig. 4 is CNFs/CPFD hybridized hydrogel and CNFs water-setting in the preparation method of CNFs, CPFD nano hybridization aeroge
Relation curve between glue Dynamic Viscoelastic modulus and rotation angular frequency.
The XPS narrow scan spectrum that Fig. 5 is CNFs aeroge C 1s in the preparation method of CNFs, CPFD nano hybridization aeroge
Figure.
Fig. 6 is the XPS of CNFs/CPFD hybrid aerogel C 1s in the preparation method of CNFs, CPFD nano hybridization aeroge
Narrow scan spectrogram.
Fig. 7 is the SEM figure of CNFs/CPFD hybrid aerogel in the preparation method of CNFs, CPFD nano hybridization aeroge.
Fig. 8 be CNFs, CPFD nano hybridization aeroge application in CPFD respectively the solution in THF and aqueous solvent,
The uv absorption spectra of CNFs/CPFD hybrid aerogel and CPFD film.
Fig. 9 be CNFs, CPFD nano hybridization aeroge application in CPFD respectively the solution in THF and aqueous solvent,
The fluorescence emission spectrogram of compound of CNFs/CPFD hybrid aerogel and CPFD film.
Figure 10 is exposed in DNT steam CNFs/ under different time in for CNFs, CPFD nano hybridization aeroge
The figure of fluorescence intensity changes of CPFD hybrid aerogel.
Figure 11 is exposed in DNT steam CNFs/ under different time in for CNFs, CPFD nano hybridization aeroge
The figure of fluorescence intensity changes of CPFD hybrid aerogel and CPFD film.
Figure 12 is exposed to different time in DNT, TNT and PA steam in for CNFs, CPFD nano hybridization aeroge
The figure of fluorescence intensity changes of lower CNFs/CPFD hybrid aerogel.
Figure 13 is sound of the CNFs/CPFD hybrid aerogel to DNT steam in of CNFs, CPFD nano hybridization aeroge
Answer invertibity.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other
Embodiment shall fall within the protection scope of the present invention.
In the embodiment of the present invention, a kind of preparation method of CNFs, CPFD nano hybridization aeroge, comprising the following steps:
(1) preparation of water-soluble cationic conjugated polymer (CPFD)
Successively by 15mL THF, 246mg 1,4- to benzene hypoboric acid propylene glycol ester (1mmol) and 494mg 2,7- bis- bromo- 9,
Bis- [3- (dimethylamino) propyl] fluorenes (1mmol) of 9- are added in there-necked flask, and after electromagnetic agitation to reactant dissolves, it is dense that 10mL is added
Degree is the K of 2mol/L2CO3Aqueous solution；After logical nitrogen 30min, mixed solution is warming up to 69 DEG C of reflux temperature, in nitrogen protection
Under rapidly join 24mg Pd (PPh3)4Catalyst；After reaction system reacts 48h at a reflux temperature, reaction solution is cooled to room
Temperature is subsequently transferred in the beaker for filling 50mL methanol, there is an insoluble matter precipitation, by insoluble matter successively with distilled water, first after suction filtration
The sequence of alcohol, distilled water is washed five times, respectively to remove the residues such as sylvite and catalyst；Solid after washing is in Soxhlet
Acetone extraction 48h is used in extractor, with the oligomer in removing system；Finally product is transferred in vacuum drying oven true at room temperature
The dry 48h of sky, obtains conjugated polymer solid powder (PFD)；
100mg PFD is dissolved in the THF/DMSO solvent that 50mL volume ratio is 4:1, is subsequently added into 2g bromoethane；Reaction
, there is insoluble matter precipitation in system magnetic agitation 5 days at 50 DEG C in reaction system, suitable water is added and dissolves insoluble matter；Instead
After answering, THF, water and remaining bromoethane are rotated；Then the DMSO solution containing subject polymer is poured into largely
Ether in, have a Precipitation, acetone washed product repeatedly used after suction filtration；Finally 40 DEG C of vacuum drying in vacuum drying oven
48h obtains the conjugated polymer CPFD of cation；
(2) preparation of CNFs suspension
It weighs 0.033g TEMPO and 0.33g NaBr to be added sequentially in the distilled water of 400mL, magnetic force is utilized at 10 DEG C
Said mixture is sufficiently stirred in blender；After TEMPO, NaBr are completely dissolved, the wet wood pulp cellulose of 10g is added into reaction system
Element；It is vigorously stirred to wood pulp cellulose after being uniformly dispersed, then 150mmolNaClO is added into system, by being constantly added dropwise
0.5mol/L NaOH solution controls the pH of reaction system in 9-10；After reacting 6h, oxycellulose is filtered, is used in combination
Deionized water washs 3~5 times and obtains oxycellulose；Then oxycellulose is configured to the slurry of 2mg/mL using distilled water
Expect, in ice-water bath, it is cellulose nano-fibrous that ultrasound 15min, which removes oxycellulose, under 300W power；Then by fiber
Plain nanofiber suspension is centrifuged 10min at 10000g and removes unstripped oxycellulose；It will finally be prepared
CNFs suspension is placed in 4 DEG C of refrigerators and stores for future use；
(3) preparation of CNFs/CPFD hybrid aerogel
0.25% CNFs suspension is placed in 20mL glass mold, and is exposed to 12h in salt acid vapour, CNFs suspends
Liquid is changed into CNFs hydrogel；CNFs hydrogel is washed repeatedly using a large amount of distilled water, until CNFs hydrogel pH is in neutrality；Make
CNFs hydrogel is pre-processed with liquid nitrogen, CNFs aeroge is then prepared by Freeze Drying Technique；
(4) preparation of CNFs/CPFD hybrid aerogel
It weighs 50mg CPFD and is dissolved into 10mL distilled water, it is 0.25% that 20g mass fraction, which is then added,
CNFs suspension；Under ice bath after ultrasound (300W) 15min, mixed liquor becomes uniform CNFs/CPFD and is total to suspension；By suspension
Be placed in 20mL glass mold, and be exposed to 12h in salt acid vapour, CNFs/CPFD suspension be changed into CNFs/CPFD nanometers it is miscellaneous
Change hydrogel；CNFs/CPFD nano hybridized hydrogel is washed repeatedly using a large amount of distilled water, until CNFs/CPFD nano hybridization
Hydrogel pH is in neutrality；CNFs/CPFD nano hybridized hydrogel is pre-processed using liquid nitrogen, then passes through freeze-drying skill
CNFs/CPFD nano hybridization aeroge is prepared in art；
(5) preparation of CPFD film
8mg solid CPFD is dissolved in 20mL THF solvent and is configured to CPFD solution, then drips CPFD solution dropwise
Being added to revolving speed is the (size of quartz plate are as follows: length × wide=24mm × 24mm, thickness on the high-speed rotating quartz plate of 1200r/min
=1mm), time for adding 20s；Then the quartz plate is placed in vacuum drying oven 30 DEG C of vacuum drying for 24 hours, obtains spin coating CPFD
Film.
CNFs/CPFD nano hybridization aeroge is for testing NACs steam:
(a) ultraviolet-visible absorption spectroscopy
Ultravioletvisible absorption (UV) spectrum is surveyed using Shimadzu, Japan UV-1700 type ultraviolet specrophotometer
It is fixed, test scope 200-550nm.When the test of solution state UV spectrum, it is 10- that polymer powder, which is configured to concentration,6M number
The THF solution of grade eliminates absorbed by the substrate with THF solvent before testing；In the test of CNFs/CPFD hybrid aerogel UV spectrum, use
CNFs aeroge eliminates absorbed by the substrate, then surveys its UV spectrum.
(b) fluorescence spectrum
Fluorescence spectrum (FL) is measured by the F-4500 type Fluorescence Spectrometer of Japanese Hitachi company, and excitation wavelength is sample
Corresponding wavelength at corresponding UV absorption peak (300~400nm) peak-peak.In solution state test, sample is placed in quartz cuvette
In ware；When solid-state is tested, directly the solid of preparation is placed on the solid support in instrument and is measured.
(c) gel permeation chromatography
The molecular weight of CPFD is measured using Waters, US's GPC 515-2410 type gel permeation chromatograph, with
THF is mobile phase, and flow velocity 1mL/min, test temperature is 40 DEG C, and sample correction is used as standard using polystyrene (PS), is used
Amount is 10mg.
(d) rheological property
Using 301 rheometer of Physica MCR to the rheology of CNFs/CPFD nano hybridization aeroge and CNFs hydrogel
Performance is tested at 25 DEG C.
(e) scanning electron microscope (SEM)
The microscopic appearance of sample is observed using Hitachi S-4800 field emission scanning electron microscope.Acceleration voltage
For 15kV.
(f) photoelectron spectroscopy
X-ray photoelectron spectroscopy (XPS) is carried out in VG Scientific ESCALab220i-XL type photoelectron spectrograph, is swashed
It rises for Al K α X-ray, power about 300W.Base vacuum when analysis is 3 × 10-9mbar.Electron binding energy pollution carbon
The peak C 1s (284.8eV) correction.
In order to prepare CNFs/CPFD hybrid aerogel, the present invention uses water-soluble cationic conjugated polymer CPFD.It is closed
At route as shown in Figure 1: with Pd (PPh3)4For catalyst, using Suzuki coupling reaction, be prepared for can be quaternized conjugation it is poly-
Close object PFD.It is quaternized to PFD progress using bromoethane, obtain CPFD.Prepared CPFD is equal in water, THF, DMF equal solvent
It can dissolve, can satisfy going on smoothly for this experiment.
Fig. 2 shows the GPC curve of CPFD, gel chromatography analysis shows that, the number-average molecular weight (M of CPFDn) and polymer
Molecular weight distribution (PDI) is respectively 6980 and 1.38.
CNFs/CPFD hybrid aerogel synthetic route is shown in Fig. 3.Under the ultrasonication effect of sonicator, CPFD
It can uniformly be distributed in CNFs aqueous solution and form uniform and stable CNFs/CPFD suspension, after its static placement 3 months
There is no any Precipitation.The suspension shows good stability, is hardly influenced by external condition, such as at one
Wider pH range (pH 0.85-13.2).This shows that CNFs is a kind of very efficient, environmentally protective and stable CPFD dispersion
Agent.
CNFs/CPFD nano hybridized hydrogel can be prepared by being acidified CNFs/CPFD suspension by salt acid vapour.CNFs/
The formation of CPFD hydrogel can be indicated with rheological property.Fig. 4 is CNFs/CPFD hybridized hydrogel and CNFs hydrogel dynamic
Relation curve between viscoelastic modulus and rotation angular frequency.It can be seen from the figure that CNFs/CPFD hybridized hydrogel and CNFs
For hydrogel, within the scope of entire angle of rotation frequency test (0.1-100Hz), dynamic storage modulus (G ') is higher by loss modulus
(G ") an order of magnitude, and dynamic storage modulus and loss modulus do not occur apparent substantially with the change of rotation angular frequency
Variation.This illustrates that CNFs/CPFD hybridized hydrogel and CNFs hydrogel all have steadily network structure, and elastic response occupies
Ascendancy (has good mechanical performance).
When rotating angular frequency is 10rad/s, the dynamic storage modulus of CNFs hydrogel is about 390Pa, and CNFs/
The dynamic storage modulus of CPFD hybridized hydrogel is up to 1.03kPa.It is obvious that the dynamic energy storage of CNFs/CPFD hybridized hydrogel
Modulus is much higher than the dynamic storage modulus of CNFs hydrogel.This phenomenon illustrates that CPFD changes cellulose nanometer significantly
The network structure of fiber.On the other hand, CNFs hydrogel is prepared by hydrogen bond action, and CNFs/CPFD hybridized hydrogel
Mechanical performance ratio CNFs hydrogel it is stronger.This phenomenon shows CNFs/CPFD hybridized hydrogel in addition to hydrogen bond action
Outside, also there is stronger crosslinked action.Since CNFs has a large amount of C-6 carboxyl, CPFD has the quaternary ammonium salt of cation, therefore can
Strong electrostatic interaction is formd to say for certain, between CNFs and CPFD.
By hypothermic lyophilization technology, CNFs/CPFD hybridized hydrogel is changed into CNFs/CPFD hybrid aerogel.With
XPS is made that characterization to the chemical environment of carbon on CNFs/CPFD hybrid aerogel surface.CNFs/CPFD hybrid aerogel
And the XPS narrow scan spectrogram of CNFs aeroge C 1s is shown in Fig. 5 and Fig. 6 respectively.The C 1s narrow scan peak of CNFs aeroge can be seen
It is the peak C-C/C=C (the non-oxide carbon sp by 284.8eV2Hydridization), the peak C-O at 286.6eV, the peak C=O at 288.4eV
And the peak the O-C=O composition at 289.8eV.For CNFs/CPFD hybrid aerogel, C 1s narrow scan peak can regard as by
The peak C-C/C=C (non-oxide carbon sp at 284.8eV2Hydridization), the peak C-O at 286.6eV, the peak C=O at 288.4eV,
The peak C-N at 286.0eV and the peak the O-C=O composition at 289.8eV.Compared with the C 1s narrow scan peak of CNFs aeroge,
CNFs/CPFD hybrid aerogel intensity at the peak C-C/C=C at 284.8eV increases, and CNFs/CPFD hybrid aerogel
There is the new peak C-N.This illustrates that CPFD has been distributed among in CNFs/CPFD hybrid aerogel.
It is characterized using microscopic appearance and nano-level structure of the SEM to CNFs/CPFD hybrid aerogel, sees Fig. 7.
CNFs/CPFD hybrid aerogel has shown equally distributed hole network structure, this shows that CNFs can be used as CNFs/CPFD
The producer of the multi-level nanostructure of hybrid aerogel.In addition, CNFs/CPFD hybrid aerogel has the three-dimensional aperture of High Level
Structure, this can effectively improve the surface area of hybrid material and provides a large amount of hole or channel.Therefore, the present invention can choose
Chemical sensor of the CNFs/CPFD hybrid aerogel as detection nitro-aromatic explosive vapors.
The ultraviolet suction of the CPFD solution in THF and aqueous solvent, CNFs/CPFD hybrid aerogel and CPFD film respectively
It receives spectrum and fluorescence emission spectrum is shown in Fig. 8 and Fig. 9 respectively.CPFD is respectively in THF and the ultraviolet maximum absorption band wavelength in water
369nm and 382nm.Corresponding fluorescence maximum emission peak wavelength is respectively 398nm and 414nm.It is obvious that polyelectrolyte CPFD
Electronics peak is determined by solvent: with the increase of solvent polarity, red shift is had occurred in electronics peak.It is molten in polarity that this is primarily due to CPFD
Chain aggregation phenomenon in agent becomes apparent from.
In addition, the maximum absorption band wavelength and maximum emission peak wavelength of CPFD film are distinguished compared with CPFD is in THF solution
The red shift (i.e. 348nm) of 21nm and 26nm has occurred.And CNFs/CPFD hybrid aerogel with respect to CPFD THF solution maximum
The red shift of 17nm and 21nm only has occurred in absorption peak wavelength and maximum emission peak wavelength respectively.
Since polymer almost isolates dispersion in a solvent with molecular state in THF weak solution state, can be considered as to each other
Without chain aggregation phenomenon, the wavelength of maximum absorption band or maximum emission peak is minimum at this time.CPFD film uses common straight chain
Type CPFD has serious chain aggregation phenomenon by the film that spin coating technique is prepared into, so that serious π-π chain accumulation is generated,
Compared with the CPFD of solution state, the wavelength of maximum absorption band or maximum emission peak shows clearly Red Shift Phenomena.And
The red shift that CNFs/CPFD hybrid aerogel ratio CPFD film occurs is small, and reason may be between CNFs and CPFD there is electrostatic to make
With enabling CNFs effectively to prevent the pi-pi accumulation of conjugated polymer skeleton.
The present invention does CNFs/CPFD hybrid aerogel detection nitro-aromatic explosive (by taking DNT, TNT, PA as an example) steam
The research of sensing capabilities.Concrete operations are as follows: a little nitro-aromatic explosive powder is put in the bottle of sealing (25mL).
In order to maintain the saturated vapour pressure that nitro-aromatic explosive is constant in bottle, and avoid CNFs/CPFD hybrid aerogel directly with
A certain amount of absorbent cotton is placed above in powder in nitro-aromatic powder contact.Before detection, by a series of bottle of sealings in room temperature
Lower placement for 24 hours, reaches saturated vapour pressure with the nitro-aromatic explosive guaranteed in bottle.When detection, by CNFs/CPFD hydridization airsetting
In glue quick insertion sealed vials, be exposed to nitro-aromatic steam after a certain period of time to fluorescence sense aeroge, immediate record its
Fluorescence emission spectrum under 386nm excitation.Fluorescent quenching efficiency is usually indicated with the percentage that fluorescence intensity reduces, is calculated
Equation is as follows:
η=(I0-I)/I0(1)
In formula, η is fluorescent quenching efficiency, I0The fluorescence intensity of conjugated polymer when for no quencher, I are the presence of quenching
The fluorescence intensity of conjugated polymer after agent.
Figure 10 gives the fluorescence intensity change for being exposed to CNFs/CPFD hybrid aerogel under different time in DNT steam.
As can be seen that significant ground fluorescent quenching has occurred in CNFs/CPFD hybrid aerogel in DNT steam: being such as exposed in DNT steam
After 60s, the fluorescence intensity of CNFs/CPFD hybrid aerogel has dropped 75.57%.
In order to further study CNFs/CPFD hybrid aerogel to the response sensitivity of nitro-aromatic explosive, pass through rotation
The CPFD film of painting technology preparation is also used for detection DNT steam as a comparison.DNT steam to CNFs/CPFD hybrid aerogel with
The fluorescent quenching efficiency of CPFD film is shown in Figure 11.As shown, being exposed in DNT steam after 120s, the fluorescence of CPFD film is sudden
Efficiency of going out is only 24.1%.And the fluorescent quenching efficiency of CNFs/CPFD hybrid aerogel is 3.6 times of CPFD film, up to
85.9%.It is obvious that CNFs/CPFD hybrid aerogel shows higher response sensitivity to DNT steam.
Diffusion rate of the nitro-aromatic molecule in fluorescent optical sensor is to influence the principal element of sensor response sensitivity.
Obviously, the fluorescence signal for guaranteeing measurement has enough thickness, while CPFD itself by CPFD film prepared by spin coating technique
It is straight chain polymer.These factors result in the compact texture of CPFD film, this can very big ground resistance delayed DNT steam into film
The infiltration and diffusion in portion, cause the fluorescence of conjugated polymer internal layer not to be quenched and substantially reduce the quenching efficiency of film.On the contrary
Ground, CNFs/CPFD hybrid aerogel intrinsic high surface area and a large amount of hole or channel, is conducive to DNT molecule to hydridization gas
Diffusion and infiltration, make the fluorescent quenching efficiency of CNFs/CPFD hybrid aerogel much higher than CPFD film inside gel.
The thickness of CPFD film is only 10.2nm, and CNFs/CPFD hybrid aerogel with a thickness of 30 μm, this shows
The fluorescence sense performance of CNFs/CPFD hybrid aerogel is independent of thickness.
CNFs/CPFD hybrid aerogel not only realizes sensitive response to DNT steam, also the same to TNT and PA steam
With response sensitivity, as shown in figure 12.For example, exposure 120s, CNFs/CPFD hydridization airsetting in TNT and PA steam respectively
The fluorescence intensity of glue has dropped 78.9% and 59.3% respectively, and the fluorescence intensity of CNFs/CPFD hybrid aerogel has dropped
85.9%.It is obvious that opposite TNT and PA steam, CNFs/CPFD hybrid aerogel film shows DNT steam sensitiveer
Responsiveness, being primarily due to DNT ratio TNT and PA has higher vapour pressure.At 25 DEG C, the saturated vapour pressure point of DNT, TNT, PA
It Wei 1.74 × 10-4,8.02×10-6With 5.80 × 10-9mmHg.For ordinary circumstance, in nitro-aromatic explosive vapors to glimmering
In the quenching behavior of light conjugated polymer, the vapour pressure of nitro-aromatic is higher, in the part on CNFs/CPFD hybrid aerogel surface
Concentration is higher, will generate higher fluorescent quenching.
It is found by the studies above, CNFs/CPFD nano hybridization aeroge shows the steam of nitro-aromatic explosive
Sensitive responsiveness.Whether there is good recycling also to have important Practical significance to fluorescent sensing material.Cause
This, the present invention has carried out CNFs/CPFD hybrid aerogel the reversible experiment in DNT steam.CNFs/CPFD is first measured at room temperature
The fluorescence emission spectrum of hybrid aerogel, then the hybrid aerogel is exposed to 60s in saturation DNT steam, survey its fluorescent emission
Spectrum.Then CNFs/CPFD hybrid aerogel is impregnated for several times in methanol solvate, after being dried, measures the CNFs/ again
CPFD hybrid aerogel fluorescence emission spectrum.It repeats the above process several times, CNFs/CPFD hybrid aerogel is to DNT steam
Response invertibity is shown in Figure 13.CNFs/CPFD hybrid aerogel be can be seen that after fluorescent quenching occurs, it can fast quick-recovery
Its fluorescence intensity still shows higher fluorescent quenching efficiency after being exposed to DNT saturated vapor again.In addition, will
CNFs/CPFD hybrid aerogel by five times quenching and recovery process after, quench efficiency and it is restorative still preferably, this shows
CNFs/CPFD hybrid aerogel sensor has good recycling.
In the present invention, under the ultrasonication effect of sonicator, by electrostatic interaction, stable homogeneous has been prepared
CNFs/CPFD water slurry be changed into CNFs/CPFD nano hybridized hydrogel under the acidification of salt acid vapour.Pass through low temperature
Freeze Drying Technique is prepared for a kind of novel C NFs/CPFD nano hybridization aeroge, and the hybrid aerogel is used for trace nitre
In the super sensitivity detection of base aromatic hydrocarbons explosive vapors.Cellulose nano-fibrous can stablize effectively disperses CPFD, and inhibits
The pi-pi accumulation of conjugated polymer CPFD skeleton.In addition, CNFs/CPFD hybrid aerogel possesses the three-dimensional aperture structure of High Level,
This can effectively improve the surface area of hybrid material and provides a large amount of hole or channel, so be conducive to NACs steam to
Infiltration and diffusion inside CNFs/CPFD hybrid aerogel.Therefore, this novel CNFs/CPFD aeroge sensor is to nitre
Base aromatic hydrocarbons steam shows sensitive response: in DNT steam after exposure 120s, the fluorescence of CNFs/CPFD hybrid aerogel
The fluorescent quenching efficiency of quenching efficiency ratio CPFD film is up to 3.6 times.In addition, CNFs/CPFD hybrid aerogel is passed as fluorescence
Sensor has good recycling.
It is obvious to a person skilled in the art that invention is not limited to the details of the above exemplary embodiments, Er Qie
In the case where without departing substantially from spirit or essential attributes of the invention, the present invention can be realized in other specific forms.Therefore, no matter
From the point of view of which point, the present embodiments are to be considered as illustrative and not restrictive, and the scope of the present invention is by appended power
Benefit requires rather than above description limits, it is intended that all by what is fallen within the meaning and scope of the equivalent elements of the claims
Variation is included within the present invention.Any reference signs in the claims should not be construed as limiting the involved claims.
In addition, it should be understood that although this specification is described in terms of embodiments, but not each embodiment is only wrapped
Containing an independent technical solution, this description of the specification is merely for the sake of clarity, and those skilled in the art should
It considers the specification as a whole, the technical solutions in the various embodiments may also be suitably combined, forms those skilled in the art
The other embodiments being understood that.
Claims (4)
1. a kind of preparation method of CNFs, CPFD nano hybridization aeroge, which comprises the following steps:
(1) preparation of water-soluble cationic conjugated polymer CPFD
Successively by 15 mL THF, 246 mg 1,4- to the bromo- 9,9- of benzene hypoboric acid propylene glycol ester 1 mmol and 494 mg 2,7- bis-
Bis- 1 mmol of [3- (dimethylamino) propyl] fluorenes are added in there-necked flask, and after electromagnetic agitation to reactant dissolves, it is dense that 10 mL are added
Degree is the K of 2 mol/L2CO3Aqueous solution；After logical 30 min of nitrogen, mixed solution is warming up to 69 oC of reflux temperature, is protected in nitrogen
24 mg Pd (PPh are rapidly joined under shield3)4Catalyst；It is after reaction system reacts 48 h at a reflux temperature, reaction solution is cooling
It to room temperature, is subsequently transferred in the beaker for filling 50 mL methanol, there is an insoluble matter precipitation, by insoluble matter successively with distillation after suction filtration
The sequence of water, methanol, distilled water is washed five times, respectively to remove sylvite and catalyst residue；Solid after washing is in rope
48 h of acetone extraction is used in family name's extractor, with the oligomer in removing system；Product is finally transferred to room temperature in vacuum drying oven
48 h of lower vacuum drying, obtain conjugated polymer solid powder PFD；
100 mg PFD are dissolved in the THF/DMSO solvent that 50 mL volume ratios are 4:1, are subsequently added into 2 g bromoethanes；Reactant
Magnetic agitation 5 days under 50oC are tied up to, there is insoluble matter precipitation in reaction system, suitable water is added and dissolves insoluble matter；Reaction
After, THF, water and remaining bromoethane are rotated；Then the DMSO solution containing subject polymer is poured into largely
In ether, there is Precipitation, acetone washed product repeatedly is used after suction filtration；The finally 40 oC vacuum drying 48 in vacuum drying oven
H obtains the conjugated polymer CPFD of cation；
(2) preparation of CNFs suspension
It weighs 0.033 g TEMPO and 0.33 g NaBr is added sequentially in the distilled water of 400 mL, magnetic force is utilized under 10 oC
Said mixture is sufficiently stirred in blender；After TEMPO, NaBr are completely dissolved, it is fine that the wet wood pulp of 10 g is added into reaction system
Dimension element；It is vigorously stirred to wood pulp cellulose after being uniformly dispersed, then 150 mmol NaClO is added into system, by being constantly added dropwise
0.5 mol/L NaOH solution controls the pH of reaction system in 9-10；After reacting 6 h, oxycellulose is filtered, and
It is washed with deionized 3 ~ 5 times and obtains oxycellulose；Then oxycellulose is configured to the slurry of 2 mg/mL using distilled water
Expect, in ice-water bath, it is cellulose nano-fibrous that 15 min of ultrasound, which remove oxycellulose, under 300 W power；It then will be fine
The plain nanofiber suspension of dimension is centrifuged 10 min at 10000 g and removes unstripped oxycellulose；It will finally be prepared
CNFs suspension be placed in 4 oC refrigerators and store for future use；
(3) preparation of CNFs/CPFD hybrid aerogel
0.25% CNFs suspension is placed in 20 mL glass molds, and is exposed to 12 h in salt acid vapour, CNFs suspension
It is changed into CNFs hydrogel；CNFs hydrogel is washed repeatedly using a large amount of distilled water, until CNFs hydrogel pH is in neutrality；It uses
Liquid nitrogen pre-processes CNFs hydrogel, and CNFs aeroge then is prepared by Freeze Drying Technique；
(4) preparation of CNFs/CPFD hybrid aerogel
It weighs 50 mg CPFD and is dissolved into 10mL distilled water, the CNFs that 20 g mass fractions are 0.25% is then added
Suspension；Under ice bath after ultrasound 300 W, 15 min, mixed liquor becomes uniform CNFs/CPFD and is total to suspension；Suspension is set
In 20 mL glass molds, and be exposed to 12 h in salt acid vapour, CNFs/CPFD suspension be changed into CNFs/CPFD nanometers it is miscellaneous
Change hydrogel；CNFs/CPFD nano hybridized hydrogel is washed repeatedly using a large amount of distilled water, until CNFs/CPFD nano hybridization
Hydrogel pH is in neutrality；CNFs/CPFD nano hybridized hydrogel is pre-processed using liquid nitrogen, then passes through freeze-drying skill
CNFs/CPFD nano hybridization aeroge is prepared in art.
2. a kind of CNFs that the preparation method of CNFs, CPFD nano hybridization aeroge as described in claim 1 is prepared,
Application of the CPFD nano hybridization aeroge in the super sensitivity detection of trace nitro-aromatic explosive vapors.
3. the application of CNFs, CPFD nano hybridization aeroge according to claim 2, which is characterized in that the CNFs/
CPFD hybrid aerogel has recycling as fluorescent optical sensor.
4. the application of CNFs, CPFD nano hybridization aeroge according to claim 2, which is characterized in that CNFs/CPFD is miscellaneous
Change the fluorescent quenching efficiency of the fluorescent quenching efficiency ratio CPFD film of aeroge up to 3.6 times.
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| CN103018223A (en) * | 2012-12-13 | 2013-04-03 | 京东方科技集团股份有限公司 | Fluorescent chemical sensor as well as preparation method and application thereof |
| CN104745192A (en) * | 2014-07-02 | 2015-07-01 | 济南大学 | Magnetic fluorescent double-function nanoion probe and preparation method thereof |
| CN105017555A (en) * | 2014-04-29 | 2015-11-04 | 中国科学院化学研究所 | Cellulose aerogel and preparation method for hybrid aerogel thereof |
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| CN103018223A (en) * | 2012-12-13 | 2013-04-03 | 京东方科技集团股份有限公司 | Fluorescent chemical sensor as well as preparation method and application thereof |
| CN105017555A (en) * | 2014-04-29 | 2015-11-04 | 中国科学院化学研究所 | Cellulose aerogel and preparation method for hybrid aerogel thereof |
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