CN105968347B - The preparation method of N substitution carboxyls polyaniline/cadmium sulfide quantum dot composite material - Google Patents
The preparation method of N substitution carboxyls polyaniline/cadmium sulfide quantum dot composite material Download PDFInfo
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Abstract
A kind of preparation method of the N substitutions polyaniline grafted cadmium sulfide quantum dot composite material of carboxyl, methods described is using N phenylglycines as monomer, by introducing cadmium source in its in-situ polymerization system, generate presoma containing cadmium, again by introducing sulphur source, using the mechanism of nucleation between cadmium and sulphur, the N for preparing chemical graft substitutes carboxyl polyaniline cadmium sulfide quantum dot composite material.There is very big lifting compared with cadmium sulfide, polyaniline using composite its electron transfer rate prepared by the method for the present invention, improve the anti-light corrosive nature of cadmium sulfide, opto-electronic conversion and photocatalytically degradating organic dye can be carried out under visible light, improve the solubility property and stability of material.The composite of gained can be applied to the fields such as photochemical catalyst, sensor, solar cell.
Description
Technical field
The present invention relates to a kind of preparation method of N- substitution carboxyls polyaniline/cadmium sulfide quantum dot composite material, category are conductive
Technical field of polymer materials.
Background technology
The energy lack and environmental pollution be faced now it is most urgent the problem of, countries in the world all seek one kind can
Successfully manage energy crisis, the new industry alleviating environmental pressure, develop low-carbon economy, realizing sustainable development.And solar energy
Photovoltaic because its cleaning, it is safe and convenient, efficient the features such as, flourished all over the world, and be described as meeting the new energy epoch to arrive
The rising industry come.Meanwhile with the gradual maturation of organic solar batteries and Photocatalyst, it is compound by polymer
Semiconductor-quantum-point is also increasingly favored to prepare light active material by numerous researchers.
Polyaniline is a kind of new efficent electronic and hole transfer, because of its conjunction as a kind of conducting polymer composite
Into many advantages, such as simple, mechanism of doping effect is unique, good conductivity, high specific capacitance electrode material for super capacitor, photochemical catalyst,
There is important researching value in the research of sensor, but the rigid structure of polyaniline causes its dissolving processing characteristics poor,
And under visible light it is difficult to carry out opto-electronic conversion.In addition, cadmium sulfide（CdS）It is a kind of excellent N-type semiconductor material, its forbidden band
Width is 2.42eV, and electron mobility is 2 × 10-2m2.V-1.s-1, there is unique photoelectrochemical behaviour, in solar cell and
Photoelectricity clothing arts have a very tempting application prospect, and the optical property of CdS semiconduct material crystal grain with itself
The size of size is related to morphology, therefore the cadmium sulphide particle for preparing certain particle size turns into and studies its optical property
Basis.However, only drawback is that cadmium sulfide compound nucleartion speed is very fast, easily reunite, and under visible light
Photoetch easily occurs for cadmium sulfide, and these defects bring certain influence to the further application of cadmium sulfide.Therefore, either
All Shortcomings and defect is used alone in photoelectric conversion device in conducting polyaniline material or cadmium sulfide material, in order to abundant
The advantages of using two kinds of materials, its cooperative effect is played, cadmiumsulfide quantum dot is compound a kind of visible to prepare with polyaniline
Opto-electronic conversion can be carried out at high speed under light, polyaniline/cadmiumsulfide quantum dot composite photoelectric material of good cycling stability have it is non-
Often important realistic meaning.
Many trials were done in order to prepare the domestic and international researcher of polyaniline cadmium sulfide quantum dot composite material.Because polyphenyl
Amine sheet, can be with the 3d of cadmium as the big pi-electron structure of conjugation5/2Track occurs π-π and stacked, in addition, negatively charged in polyaniline chain
N and positively charged Cd ions, they can be attached by electrostatic interaction.Acted in numerous research by pi-pi accumulation,
Electrostatic interaction and hydrogen bond action are stacked into being most common preparating mechanism, wherein having：Situ aggregation method, electrochemical polymerization method,
Sol-gal process, self-assembly method.The polyaniline cadmium sulfide composite material prepared with this, there is preferable photoelectricity to imitate under visible light
The pattern of cadmium sulfide and should can be controlled to a certain extent.But composite prepared by these approach, due to different groups
Power effect is weaker between point causes interface distance larger, and electronics and hole separating effect are poor, and the purity of product is not high, anti-light
Corrosivity is poor.In order to promote electronics quickly to be moved in two kinds of storerooms, and improve cadmium sulfide simultaneously and easily send out under visible light
The defects of third contact of a total solar or lunar eclipse corrodes, common ameliorative way is that cadmium sulfide and polyaniline are formed into nucleocapsid structure, by cadmiumsulfide quantum dot bag
It is rolled in organic conductive polyaniline to make protective layer effect, but this method can reduce the light conversion efficiency and stable circulation of cadmium sulfide
Property.
In summary, the polyaniline cadmium sulfide quantum with high-photoelectric transformation efficiency, anti-light corrosion can be developed
Point composite, and find a kind of economical and effective and be very with the method for preparing such composite of general applicability
Important.
The content of the invention
Prepare that anti-light corrosivity is strong, carboxy-modified polyphenyl of photoelectric conversion superior performance it is an object of the invention to provide a kind of
The preparation method of amine cadmium sulfide quantum dot composite material.
The technical scheme is that：
The present invention uses two-step synthesis method, is carried out first in the solution containing N-phenylglycine and cadmium ion in situ poly-
The N- substitution carboxyl polyaniline presomas of cadmium must be contained by closing；Then by slowly introducing sulphur source, mechanism of nucleation system between sulphur and cadmium is utilized
It is standby cadmiumsulfide quantum dot is grafted on polymer, to form N- substitution carboxyl polyaniline cadmium sulfide quantum dot composite materials.
The N- of the present invention for preparing substitutes the method and step of carboxyl polyaniline cadmium sulfide quantum dot composite material as follows：
Weigh a certain amount of N-phenylglycine to be dissolved in the HCl solution for determining concentration of certain volume with cadmium source, and pass through
Ultrasonic disperse forms homogeneous mixed solution, is designated as solution A；Oxidant ammonium persulfate is dissolved in certain density HCl solution again
It is middle to form homogeneous mixed solution, it is designated as B solution；B solution is slowly dropped into the solution A being positioned in ice-water bath；Reaction is certain
After time, certain time is persistently stirred under normal temperature, product is washed repeatedly with water, ethanol, product is in vacuum drying chamber
Dry, obtain the composite material precursor containing cadmium；Finally by slowly introducing sulphur source, reaction one in the case of ice-water bath no light
Fix time, N- substitution carboxyl polyaniline cadmium sulfide composite materials are prepared using the mechanism of nucleation between sulphur source and cadmium source.
N- substitutions carboxyl polyaniline cadmium sulfide quantum dot composite material name polymerisation formula is as follows：
The composite is rendered as lilac shape in aqueous, with presoma color（It is blackish green）It is different, in advance
Show the generation of polymer.
Successfully confirm that cadmiumsulfide quantum dot is chemically grafted to N- through FTIR, UV-Vis, XRD spectrum and XPS technologies
In the structure for substituting carboxyl polyaniline, the pattern of material is studied through SEM and TEM technologies and found, N- substitution carboxyl polyaniline sulphur
Cadmium composite is the pattern that dots structure is closely attached on fibre structure, and this pattern remains polyaniline and vulcanization
The integrality and regularity of cadmium structure, research show that cadmium sulfide is grafted on N- substitution carboxyl polyaniline polymer chains, formd
Composite with compared with strong interaction.
In the present invention, the presoma containing cadmium is prepared under strong acid environment, hydrochloric environment improves the reactivity of monomer, such as
Fruit will become very slow without the presence polymerisation of acid.In the present invention, it is 0.5 ~ 2 that hydrochloric acid, which should keep its hydrogen ion concentration,
mol/L。
In the present invention, due to using the carboxyl on N-phenylglycine as reactivity point, the formation of the presoma of cadmium and carboxylic
The concentration of base has certain dependence, therefore in the present invention, the optimum molar ratio of N-phenylglycine and cadmium ion is 1:
0.5~1:4。
In the present invention, the concentration of hydrochloric acid is 0 ~ 6mol/L in aqueous hydrochloric acid solution.
In the present invention, presoma containing cadmium has large effect with sulphur source mol ratio for cadmiumsulfide quantum dot generation, most
The content of cadmium sulfide in composite is directly influenced eventually.Therefore, in the present invention, the mol ratio of presoma containing cadmium and sulphur source is
1:0.2~1:5, most preferably 1:0.5~1:3.
Have a considerable influence to nucleation due to belonging to nucleation process, time and temperature between the presoma and sulphur source of cadmium, it is too low or
Too high reaction temperature and time are all unfavorable for reacting, therefore in the present invention, polymeric reaction temperature is preferably 0~10 DEG C, liquid
The phase reaction time is 0.5 ~ 3h.
The post processing such as separating-purifying is carried out to composite products using known method in the present invention.The processing includes removing
The monomer for not participating in reaction, accessory substance, the oligomer of reaction generation of reaction generation of residual in the reactive mixture, and it is residual
The oxidant stayed.Processing step is：Centrifugation, organic solvent washing, deionized water washing, organic solvent washing, precipitation and drying.
Present invention has the advantages that：N- substitution carboxyl polyaniline sulphur can be made using the chemical oxidative polymerization method of the present invention
Cadmium quantum dot composite material, the inventive method economical and effective, there is general applicability, and the introducing of carboxyl is for quantum dot
Scattered play an important role.Between N- substitution carboxyl polyaniline cadmium sulfide quantum dot composite materials interface obtained by the present invention
Active force is significantly strengthened, and has greatly improved the defects of easy reunion for cadmium sulfide and easily photoetch, and in opto-electronic conversion
During, there is high cyclical stability.
The N- substitution carboxyl polyaniline cadmium sulfide quantum dot composite materials of gained of the invention can be applied to photochemical catalyst, sensing
Make conducting polymer composite in the fields such as device, solar cell.
Brief description of the drawings
Fig. 1 is a kind of chemical oxidation preparation method of N- substitutions carboxyl polyaniline cadmium sulfide quantum dot composite material of the present invention
Flow chart；
Fig. 2 is the N- substitution carboxyl polyaniline cadmium sulfide quantum dot composite materials of chemical graft and mechanical blending（NPANI/
CdS）And the infrared spectrum of homogenous material；
A is pure N- substituted carboxylic acid polyanilines in figure（NPNAI）Infrared ray diffraction spectrogram, b is the poly- of simple and mechanical blending
The infrared ray diffraction spectrogram of aniline cadmium sulfide quantum dot composite material, c are that the infrared of polyaniline cadmium sulfide quantum dot composite material is spread out
Penetrate spectrogram.Represented respectively for pure NPANI each characteristic peak of infrared spectrum：Wavelength is 3447 cm-1With 1665 cm-1Suction
Receive peak and correspond to N-H stretching vibration and carboxyl C=O stretching vibrations in its structure；Wavelength is 1557 cm-1And 1480cm-1Absorption
It is C=C RESONANCE ABSORPTIONs in quinone ring and phenyl ring in structure that peak is corresponding respectively；Wavelength is 801cm-1Absworption peak corresponding to be phenyl ring
Contraposition two substitute structure.NPANI/CdS infrared signature absorption peak and NPANI contrast, found relative to NPANI
The peak of the O-H stretching vibrations of appearance, almost illustrate the H on O-H keys on composite without the appearance at peak on NPANI/CdS
Substituted by other atoms；And 1665 cm on NPANI-1Locate the stretching vibration peak of C=O keys occurred, on the composite
It is red to have been moved to 1684cm-1, illustrate Cd2+Presence destroy phenyl ring, amino, carboxyl formed conjugated system, reduce the system
Electron cloud density so that there is Red Shift Phenomena in these functional groups.By the NPANI/CdS intermingling materials of simple and mechanical blending
On the peak of O-H stretching vibrations and the stretching vibration peak of C=O keys with pure NPANI contrast, find these functional groups
Corresponding peak position fits like a glove, and does not occur shift phenomenon, again illustrates, the CdS grains on NPANI/CdS composites
Son is to be connected in a manner of chemical graft with NPANI.
Fig. 3 is the N- substitution polyaniline cadmium sulfide quantum dot composite materials of chemical graft and the XRD spectra of homogenous material；
A curves are pure NPANI X ray diffracting spectrum in figure, and b curves spread out for the X ray of NPANI/CdS composites
Penetrate collection of illustrative plates.Because NPANI is a kind of polymeric material of non-crystalline, it is more difficult to find out its diffraction from X ray diffracting spectrum
Angle, therefore, scheme in a, only nearby a larger diffraction maximum occur at 21 ° or so.A is schemed to be contrasted with b figures, it is not ugly
Go out that the X ray diffracting spectrum of composite is substantially different with single NPANI materials, and the spectrogram of composite is in NPANI
On the basis of have also appeared the angle of diffraction as 25.6o、42.1o、54.1oThese three diffraction maximums, correspond respectively to CdS and exist（111）,
（220）,（311）Three crystal faces, this demonstrate that CdS materials in composite be present.
Fig. 4 chemical grafts and the N- of mechanical mixture substitution carboxyl polyaniline cadmium sulfide quantum dot composite materials and homogenous material
Fluorescence spectrum；
In the collection of illustrative plates of cadmium sulfide, it is in 480cm-1And 540cm-1There are two wide and strong absworption peaks in left and right, and they divide
The trap emission of the intrinsic exciton emission and cadmium sulfide of cadmium sulfide is not correspond to；And compared to cadmium sulfide, mechanical mixture
NPANI/CdS materials and the NPANI/CdS materials that covalent bond connects are same in 480cm-1And 540cm-1There is characteristic peak in left and right,
But its intensity has larger decrease, this is proved because high-velocity electrons receiving body NPANI presence, cadmium sulfide produce under visible light
Raw electronics is quickly conducted to NPANI, which suppress the quick compound of electronics in cadmium sulfide and hole, and simultaneously because
Photoelectronic transfer is quenched electronics, reduces the trap emission of cadmium sulfide significantly.And the composite wood for passing through chemical graft
Material fluorescence intensity has bigger decrease, and further demonstrating NPANI and cadmium sulfide is linked together by chemical graft effect
And this effect can reduce boundary's distance between the surface, accelerate the separation of photoelectron, hole.
Fig. 5 is the XPS spectrum figure of the N- substitution carboxyl polyaniline cadmium sulfide quantum dot composite materials of chemical graft；
As seen from the figure, two kinds of materials are all containing these three elements of C, N, O, the XPS spectrum figure compared to NPANI, composite
NPANI/CdS can be that 400eV and 160eV or so Cd3d occur respectively in combination5/2And S2pTwo new peaks, this explanation CdS particle
Successfully it is present on NPANI.Further, since C/O ratios are respectively 4.39 Hes in NPANI and NPANI-CdS materials
4.31, two is basically identical, further demonstrates CdS and is mainly reacted with the carboxyl in NPANI, so as to strengthen NPANI
With CdS interface interaction.
Fig. 6 is the N- substitution carboxyl polyaniline cadmium sulfide quantum dot composite materials of chemical graft and NPANI O1sXPS swarmings
Spectrogram；
Fig. 6（a）, Fig. 6（b）It is the O of NPANI and CdS/NPANI composites respectively1sSwarming spectrogram, Fig. 6（c）With Fig. 6
（d）, be respectively Cd and S in composite characteristic absorption peak, further prove wherein have CdS.
Compared to Fig. 6（a）, Fig. 6（b）In the new peak that occurs at 532.30eV be O-Cd structures, Fig. 6 in addition（b）In
O-H structure proportions at 532.19 are compared with Fig. 6（a）There is certain reduction, connect this demonstrate that Cd is successfully formed with NPANI
Branch effect.And because Fig. 5 to observe contains cadmium sulfide in composite, therefore this further demonstrates and answered in CdS/NPANI
In condensation material, CdS and NAPNI is to act on connecting with chemical graft.
Fig. 7 is TEM the and HRTEM spectrograms of the N- substitution carboxyl polyaniline cadmium sulfide quantum dot composite materials of chemical graft；
Fig. 7（a）Scheme for pure NPANI TEM, Fig. 7（b）Scheme for the TEM of NPANI/CdS composites, Fig. 7（c）For more
The TEM figures of NPANI/CdS composites, Fig. 7 under big multiple（d）For CdS particle interplanar distances in the composite under HR-TEM
Figure.As can be observed from Figure, N substitutes carboxyl polyaniline (figure a) to be the uniform fiber up to hundreds of nanometers, a width of 35-55nm
List structure, and the dark colour in figure deepens thickness of sample partially due to NPANI reel chain freely crimps link.Fig. 7
(b) (c) (d) is the TEM figures of the CdS/NPANI under different amplification respectively, can be with visible in detail from Fig. 7 (b) (c)
The different dim spot of a certain amount of depth that is scattered here and there on each NPANI reel chains, correspond to CdS particles, and the particle diameter of the CdS particles
Between 5-30 nanometers, without obvious agglomeration, this is further demonstrated there is CdS particles on NPANI chains, and by
In NPANI presence, CdS reunion is inhibited to a certain extent；Fig. 7（d）For NPANI/CdS high powers transmission electron microscope (HR-TEM)
Photo, it is observed that two Rotating fields that light and shade is different, wherein edge are the NPANI layers of undefined structure, middle dark colour
There is the hexagonal structure that correspond to Nano cadmium sulphide particle that certain rule arranges part, and by calculating its crystalline substance before photocatalysis
Compartment is away from for 0.271nm.
Fig. 8 is the TG spectrograms of chemical graft N- substitution carboxyl polyaniline cadmium sulfide quantum dot composite materials and homogenous material
Fig. 8（a）For N-AN monomers 800 DEG C in hot weightless picture, Fig. 8（b）For heat of the pure NPANI in 800 DEG C
Weightlessness figure, Fig. 8（c）For hot weightless picture of the NPANI/CdS composites in 800 DEG C, Fig. 8（d）For the heat of tri- kinds of materials of a, b, c
Weightless stacking chart.From Fig. 8（a）In it can be found that：Monomer N-AN is just decomposed completely before 600 DEG C.Fig. 8 before 300 DEG C
（a）In thermal weight loss linearly downward trend, this is the scission of link temperature of-COOH and-NH2 in monomer, and 400 DEG C or so are then
For the scission of link temperature of phenyl ring-C=C- on monomer.
Comparison diagram 8（a）, Fig. 8（b）Two figures are it was found that warm of the NPANI before temperature is increased to 300 DEG C after polymerization
Weight-loss ratio wants low more compared to the thermal weight loss rate of N-AN monomers.Illustrate that the thermostabilization of the NPANI after polymerization is stronger so that-
The decomposition temperature of COOH and-NH2 functional groups is improved.At the same time, the generation of polymerisation also cause-C on NPANI=
C- scission of link temperature has risen to 497 DEG C from 400 DEG C of monomer, and temperature when whole polymer decomposes completely, due to benzene
The generation of ring conjugated system, 100 DEG C or so are also increased, the temperature that pure NPANI is finally decomposed completely in system also reaches
680℃。
From Fig. 8（b）, Fig. 8（c）We can intuitively see that NPANI reaches 680 DEG C in temperature on the TGA curves of two figures
When just decomposed completely, and the material that composite NPANI/CdS has 22% or so when temperature reaches 800 DEG C is not divided
The reason for solution is complete, and this is due to material this containing cadmium in composite, the decomposition temperature of cadmium is very high, 800 DEG C of temperature
Degree can not decompose it.Before temperature is increased to 300 DEG C, the thermogravimetric curve of NPANI/CdS composites is compared to
Relative smooth for pure NPANI, this is due to that CdS and-COOH on phenyl ring and-NH2 generates interaction on composite
Power so that their stability enhances, therefore is not easy to decompose, this demonstrate that because the presence composite of cadmium sulfide is stable
Property has certain raising.
Fig. 9 is the HRTEM spectrums before and after chemical graft N- substitution carboxyl polyaniline cadmium sulfide quantum dot composite material photocatalysis
Figure；
In figure, Fig. 9（a）For the crystal structure figure of the CdS particles before NPANI/CdS composites photocatalysis under HR-TEM；
Fig. 9（b）For the crystal structure figure of the CdS particles after NPANI/CdS composites photocatalysis under HR-TEM.It can be seen that
The spacing of lattice of NPANI/CdS composites CdS particles before photocatalysis is 0.271nm, between the lattice after one circulation of illumination
Away from for 0.272nm.Before and after illumination, CdS spacing of lattice does not almost change on composite, illustrates there are NPANI protections
The crystal structures of CdS particles do not destroyed after illumination.HR-TEM more intuitively illustrates-COOH pairs on NPANI
CdS particles serve stable and protective effect well, improve the anti-light corrosive nature of cadmium sulfide.
Embodiment
Embodiment 1：
The present embodiment will illustrate the inventive method with the mol ratio 1 of N-phenylglycine and cadmium acetate:2, it is poly- by original position
Symphysis is into presoma containing cadmium, then under ice-water bath, using the presoma of cadmium and nine hydrated sodium sulfide mol ratios as 1:1, the reaction time
For 2h, realized according to the response path of two steps synthesis.
Weigh 0.756gN- phenylglycines and 2.66g cadmium acetates to be dissolved in 40ml concentration be ultrasound in 1M HCl solution
Uniform solution is formed to mixed liquor is scattered in 30min, marked as A；The ammonium persulfate for weighing 1.427g is dissolved in 60ml concentration and is
In 1M HCl solution, ultrasonic 5min forms uniform solution to scattered, marked as B；Under ice-water bath, A liquid is kept persistently to stir,
B liquid is slowly dropped into A liquid, reacted the 6h times, then 18h times at normal temperatures, reaction stands centrifugation after terminating, and with water and nothing
Water-ethanol is washed for several times to be dried except the oligomer and inorganic impurity that are generated in dereaction, then as in baking oven and at 60 DEG C
24h is standby；The precursor samples containing cadmium for weighing the above-mentioned drying of 0.1g again are dissolved in 50ml deionized water, and ultrasonic 30min extremely divides
Dissipate and form uniform solution marked as C, and be kept stirring under ice-water bath no light, then take 2.4g nine hydrated sodium sulfides to be dissolved in
It is fully dispersed marked as D in 50ml deionized waters, D liquid is slowly dropped into C liquid, reacts 2h, stands and centrifuges and be washed with water number
It is secondary with unnecessary inorganic impurity of going out, and dried in baking oven at 60 DEG C.
Can preferably it be disperseed as the N- substitution carboxyl polyaniline cadmium sulfide quantum dot composite materials obtained by the present embodiment
In water, wherein the content of cadmium sulfide is 12.89%, and photocatalytically degradating organic dye rhodamine B can reach 80%, cyclical stability
Height, the anti-light corrosivity of cadmium sulfide are greatly lifted.
Successfully confirm that cadmiumsulfide quantum dot is bonded to polyaniline through FTIR, UV-Vis, XRD spectrum and XPS technologies
Structure on, the Study on surface topography of material is found through SEM and TEM technologies, N- substitution carboxyl polyaniline cadmium sulfide composite woods
Expect the pattern being closely attached to for dots structure on fibre structure, this pattern remains N- substitution carboxyl polyanilines and vulcanization
The integrality and regularity of cadmium structure, by detect prove N- substitute carboxyl polyaniline and cadmium sulfide it is good pass through the company of grafting
Connect, form composite.
Embodiment 2
The present embodiment will illustrate the inventive method using the mol ratio of N-phenylglycine and cadmium acetate as 1:2, pass through original position
Polymerization generation presoma containing cadmium, then under ice-water bath, using the presoma of cadmium and nine hydrated sodium sulfide mol ratios as 1:0.5, reaction
Time is 2h, is realized according to the response path of two steps synthesis.
Weigh 0.756gN- phenylglycines and 2.66g cadmium acetates to be dissolved in 40ml concentration be ultrasound in 1M HCl solution
Uniform solution is formed to mixed liquor is scattered in 30min, marked as A；The ammonium persulfate for weighing 1.427g is dissolved in 60ml concentration and is
In 1M HCl solution, ultrasonic 5min forms uniform solution to scattered, marked as B；Under ice-water bath, A liquid is kept persistently to stir,
B liquid is slowly dropped into A liquid, reacted the 6h times, then 18h times at normal temperatures, reaction stands centrifugation after terminating, and with water and nothing
Water-ethanol is washed for several times to be dried except the oligomer and inorganic impurity that are generated in dereaction, then as in baking oven and at 60 DEG C
24h is standby；The precursor samples containing cadmium for weighing the above-mentioned drying of 0.1g again are dissolved in 50ml deionized water, and ultrasonic 30min extremely divides
Dissipate and form uniform solution marked as C, and be kept stirring under ice-water bath no light, then take 1.2g nine hydrated sodium sulfides to be dissolved in
It is fully dispersed marked as D in 50ml deionized waters, D liquid is slowly dropped into C liquid, reacts 2h, stands and centrifuges and be washed with water number
It is secondary with unnecessary inorganic impurity of going out, and dried in baking oven at 60 DEG C.
Can preferably it be dissolved as the N- substitution carboxyl polyaniline cadmium sulfide quantum dot composite materials obtained by the present embodiment
In water, wherein the content of cadmium sulfide is 5.6%, and photocatalytically degradating organic dye rhodamine B can reach 53%, and cyclical stability
Height, the anti-light corrosivity of cadmium sulfide are greatly lifted.
Embodiment 3
The present embodiment will illustrate the inventive method using the mol ratio of N-phenylglycine and cadmium acetate as 1:2, pass through original position
Polymerization generation presoma containing cadmium, then under ice-water bath, using cadmium acetate and nine hydrated sodium sulfide mol ratios as 1:1, the reaction time is
0.5h, realized according to the response path of two steps synthesis.
Weigh 0.756gN- phenylglycines and 2.66g cadmium acetates to be dissolved in 40ml concentration be ultrasound in 1M HCl solution
Uniform solution is formed to mixed liquor is scattered in 30min, marked as A；The ammonium persulfate for weighing 1.427g is dissolved in 60ml concentration and is
In 1M HCl solution, ultrasonic 5min forms uniform solution to scattered, marked as B；Under ice-water bath, A liquid is kept persistently to stir,
B liquid is slowly dropped into A liquid, reacted the 6h times, then 18h times at normal temperatures, reaction stands centrifugation after terminating, and with water and nothing
Water-ethanol is washed for several times to be dried except the oligomer and inorganic impurity that are generated in dereaction, then as in baking oven and at 60 DEG C
24h is standby；The precursor samples containing cadmium for weighing the above-mentioned drying of 0.1g again are dissolved in 50ml deionized water, and ultrasonic 30min extremely divides
Dissipate and form uniform solution marked as C, and be kept stirring under ice-water bath no light, then take 2.4g nine hydrated sodium sulfides to be dissolved in
It is fully dispersed marked as D in 50ml deionized waters, D liquid is slowly dropped into C liquid, reacts 0.5h, is stood and is centrifuged and be washed with water
For several times with unnecessary inorganic impurity of going out, and dried in baking oven at 60 DEG C.
Can preferably be dissolved as the N- substitution carboxyl polyaniline cadmium sulfide quantum dot composite materials obtained by the present embodiment
In water, wherein the content of cadmium sulfide is 6.71%, and photocatalytically degradating organic dye rhodamine B can reach 62%, cyclical stability
Height, the anti-light corrosivity of cadmium sulfide are greatly lifted.
4~embodiment of embodiment 8 will illustrate to change in the present invention mol ratio of N-phenylglycine and cadmium acetate to compound
Vulcanize the influence of cadmium content and photocatalytic degradation efficiency in material.
Embodiment 4：
Embodiment 1 is repeated, but the mol ratio of N-phenylglycine and cadmium acetate is 1：0.5, obtain vulcanizing in composite
The content of cadmium is 5.91%, and photocatalytically degradating organic dye rhodamine B can reach 57%.
Embodiment 5：
Embodiment 1 is repeated, but the mol ratio of N-phenylglycine and cadmium acetate is 1:1.5, obtain composite wherein sulphur
The content of cadmium is 9.87%, and photocatalytically degradating organic dye rhodamine B can reach 71%.
Embodiment 6：
Embodiment 1 is repeated, but the mol ratio of N-phenylglycine and cadmium acetate is 1:2.5, obtain composite wherein sulphur
The content of cadmium is 12.90%, and photocatalytically degradating organic dye rhodamine B can reach 80%.
Embodiment 7：
Embodiment 1 is repeated, but the mol ratio of N-phenylglycine and cadmium acetate is 1:3.5, obtain composite wherein sulphur
The content of cadmium is 12.91%, and photocatalytically degradating organic dye rhodamine B can reach 80%.
Embodiment 8：
Embodiment 1 is repeated, but the mol ratio of N-phenylglycine and cadmium acetate is 1:4, obtain composite and wherein vulcanize
The content of cadmium is 12.92%, and photocatalytically degradating organic dye rhodamine B can reach 80%
Embodiment 9~10:
Embodiment 7- embodiments 9 will illustrate that different cadmium acetates and nine hydrated sodium sulfide mol ratios are to composite in the present invention
The influence of middle vulcanization cadmium content and photocatalytic degradation efficiency.
Embodiment 9:
Embodiment 2 is repeated, but makes the presoma of cadmium and nine hydrated sodium sulfide mol ratios be 1:1.5, obtained composite
The content of middle cadmium sulfide is 12.90%, and photocatalytically degradating organic dye rhodamine B can reach 80%.
Embodiment 10：
Embodiment 2 is repeated, but the presoma of cadmium and nine hydrated sodium sulfide mol ratios are 1:2.5, in obtained composite
The content of cadmium sulfide is 12.81%, and photocatalytically degradating organic dye rhodamine B can reach 79.5%.
Embodiment 11~14：
Embodiment 11- embodiments 14 will illustrate that the different vulcanization reaction times in composite to vulcanizing cadmium content in the present invention
And the influence of photocatalytic degradation efficiency.
Embodiment 11：
Embodiment 3 is repeated, but makes the vulcanization reaction time be 1h, the content of cadmium sulfide is 8.91% in obtained composite,
Photocatalytically degradating organic dye rhodamine B can reach 69%.
Embodiment 12：
Embodiment 3 is repeated, but makes the vulcanization reaction time be 1.5h, the content of cadmium sulfide is in obtained composite
10.35%, photocatalytically degradating organic dye rhodamine B can reach 73%.
Embodiment 13：
Embodiment 3 is repeated, but makes the vulcanization reaction time be 2.5h, the content of cadmium sulfide is in obtained composite
11.51%, photocatalytically degradating organic dye rhodamine B can reach 78%.
Embodiment 14：
Embodiment 3 is repeated, but makes the vulcanization reaction time be 3h, the content of cadmium sulfide is in obtained composite
11.33%, photocatalytically degradating organic dye rhodamine B can reach 77.6%.
Claims (6)
- A kind of 1. preparation method of N- substitutions carboxyl polyaniline cadmium sulfide quantum dot composite material, it is characterised in that methods described Cadmium source is introduced in N- substitutes carboxyl polyaniline and obtains presoma containing cadmium, then the polyaniline sulphur of chemical graft is prepared with sulphur source reaction Cadmium quantum dot composite material；Comprise the following steps that：(1) a certain amount of N-phenylglycine and cadmium acetate is taken to be dissolved in HCl solution, and ultrasonic disperse forms uniform solution, mark Number it is A；(2) a certain amount of ammonium persulfate is taken to be dissolved in HCl solution, and ultrasonic disperse forms uniform solution, marked as B；(3) under the conditions of ice-water bath, keep A liquid persistently to stir, B liquid is slowly dropped into A liquid, react certain time, then normal Temperature lower reaction certain time, stand to centrifuge and simultaneously washed for several times with water and absolute ethyl alcohol, be placed in baking oven under certain temperature dry it is standby With；(4) it is presoma containing cadmium to take in a certain amount of (3) that product is dissolved in ultrasonic disperse in certain volume deionized water, marked as C, and It is kept stirring under ice-water bath no light, then takes a certain amount of sulphur source soluble in water fully dispersed, marked as D, D liquid is slowly dripped Enter in C liquid, react certain time, stand and filter and be washed with water for several times, and dried in baking oven.
- 2. N- substitutes the preparation method of carboxyl polyaniline cadmium sulfide quantum dot composite material, its feature according to claim 1 It is, the optimum molar ratio of described N-phenylglycine and cadmium ion is 1:0.5~1:4.
- 3. N- substitutes the preparation method of carboxyl polyaniline cadmium sulfide quantum dot composite material, its feature according to claim 1 It is, hydrogen ion concentration is 0.5~2mol/L in the HCl solution.
- 4. N- substitutes the preparation method of carboxyl polyaniline cadmium sulfide quantum dot composite material, its feature according to claim 1 It is, the optimum molar ratio of the presoma containing cadmium and sulphur source is 1:0.5~1:3.
- 5. N- substitutes the preparation method of carboxyl polyaniline cadmium sulfide quantum dot composite material, its feature according to claim 1 It is, the liquid phase reactor time of the presoma containing cadmium and sulphur source is 0.5~3h.
- 6. N- substitutes the preparation method of carboxyl polyaniline cadmium sulfide quantum dot composite material, its feature according to claim 1 It is, the sulphur source is nine hydrated sodium sulfides；The cadmium source is cadmium acetate.
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| CN106750278A (en) * | 2016-12-07 | 2017-05-31 | 华东交通大学 | The preparation method of the graft-functionalized Graphene composite sulfur cadmium quantum dot of modified polyaniline |
| CN108795408A (en) * | 2017-04-26 | 2018-11-13 | Tcl集团股份有限公司 | A kind of quantum dot containing conducting polymer and preparation method and QLED devices |
| CN108671963B (en) * | 2018-03-16 | 2021-10-22 | 浙江大学宁波理工学院 | Preparation method of micro/nano structured cadmium sulfide/aniline oligomer composite material |
| CN108435260A (en) * | 2018-03-26 | 2018-08-24 | 江苏奥净嘉环保科技有限公司 | A kind of preparation method of nano-titanium dioxide cadmium sulfide composite photo-catalyst |
| CN111349236A (en) * | 2018-12-24 | 2020-06-30 | 上海萃励电子科技有限公司 | Synthetic method of ZnTe supported poly (m-phenylenediamine) |
| CN111346674A (en) * | 2018-12-24 | 2020-06-30 | 上海萃励电子科技有限公司 | Synthesis method of CdSe-loaded poly-1, 4-naphthalene diamine |
| CN110227557B (en) * | 2019-05-20 | 2021-04-20 | 湖南大学 | Silver phosphate and polyaniline synergistically modified bismuth vanadate ternary composite photocatalyst and preparation method and application thereof |
| CN113398996A (en) * | 2021-06-21 | 2021-09-17 | 华东交通大学 | CdS @ UIO-66-NH2Preparation method of core-shell composite material |
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