CN107488135A - Graphene quantum dot is grafted azo derivative composite and preparation method and application - Google Patents
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Abstract
The invention discloses a kind of graphene quantum dot grafting azo derivative composite and preparation method and application.The preparation process of the composite includes：Graphene quantum dot GQDs is scattered in thionyl chloride and N, back flow reaction is carried out in N dimethylformamides (DMF), obtains the graphene quantum dot of chloride（GQDs‑COCl）Material；P-aminobenzene sulfonic acid azophenol (SUL Ph) is reacted with GQDs COCl materials in tetrahydrofuran, graphene quantum dot grafting azo derivative composite is made.Graphene quantum dot produced by the present invention is grafted azo derivative composite, have the advantages that in molecular fluorescence it is strong to the recognition capability of metal ion, selectivity is high, stability is good, be expected to be applied in biological medicine, sensor, optics and electricity device, solar cell, electronic equipment, optics fuel and multiple microparticles system etc..
Description
Technical field
The invention belongs to light, electricity and transductive material technical field, and in particular to a kind of graphene quantum dot grafting azo spreads out
Biocomposite material and preparation method thereof.
Background technology
Azo derivative has unique photic cis-trans isomerism characteristic, is not only widely used in traditional chemical industry, will also
Applied to photochemistry molecular switch, the identification of Subjective and Objective supramolecular chemistry, self assembly liquid crystal material, biomedical imaging and chemistry point
Many emerging scientific domains such as analysis and CD-ROM drive molecular motor.Especially tool challenge is that exploitation has high chemical stability and heat
The azo chromophore that stability easily detects again.The photochromic characteristic of azo derivative is due to that-N=N- the groups of intramolecular exist
Carried out in the presence of light or heat caused by cis- anti-or trans- suitable isomery, in recent years by the highest attention of researchers.
Particle diameter less than 100nm graphene nanometer sheet be referred to as graphene quantum dot (graphenequantumdots,
GQDs), it is a kind of emerging carbon material.Not only the electric conductivity with graphene is good, intensity is big for graphene quantum dot, compares surface
The advantages that accumulating the excellent specific property such as big, and combining the quantum confined effect, small-size effect and edge effect of quantum dot, shows
The characteristics such as good biocompatibility, hypotoxicity, strong water-soluble, high fluorescent stability, make it in biological medicine, sensor, light
Before and electricity device, solar cell, electronic equipment, optics fuel and multiple microparticles system etc. have potential application
Scape.
Therefore, carry out graphene quantum dot grafting azo derivative composite research have it is extremely important value and
Meaning.
The content of the invention
It is an object of the invention to provide a kind of graphene quantum dot grafting azo derivative composite and its preparation side
Method, graphene quantum dot grafting azo derivative composite, has in molecular fluorescence to the recognition capability of metal ion
By force, the advantages that selectivity is high, stability is good, its preparation method are simple, economical.
To reach above-mentioned purpose, the present invention adopts the technical scheme that：
A kind of graphene quantum dot is grafted azo derivative composite, and the material is by p-aminobenzene sulfonic acid azophenol one end
Oh group on phenyl ring and the acid chloride groups on the graphene quantum dot of chloride are formed by connecting.
It is specific as follows present invention also offers the preparation method of graphene quantum dot grafting azo derivative：
1) graphene quantum dot is scattered in the mixed liquor that the chloride with chloride effect forms with organic solvent,
Reacted at 65-75 DEG C 24-36 hours, reaction is evaporated under reduced pressure after stopping and removes chloride, and product is dried in vacuo at 50-70 DEG C
12-24 hours, obtain the graphene quantum dot of chloride；
The chloride with chloride effect is one kind in thionyl chloride, phosphorus trichloride, phosphorus pentachloride or POCl3；
The organic solvent is one kind in anhydrous DMF, tetrahydrofuran, hexamethylene, benzene or toluene；
2) by p-aminobenzene sulfonic acid azophenol, the graphene quantum dot of above-mentioned chloride and tetrahydrofuran in mass ratio 1:
2-3: 200-300 mixing, for ultrasonic disperse uniformly after being reacted at 40-60 DEG C of temperature 48-72 hours, reaction end is cooled to room
Temperature, product is filtered and washed twice with ethanol, collected filter cake and be dried in vacuo 60-72 hours, obtain graphene quantum dot and connect
Branch azo derivative composite.
Further, the step 1）, graphene quantum dot, the chloride with chloride effect, the dosage of organic solvent
Than for：100mg∶20-25ml∶0.5-1ml.
Further, the step 2）, p-aminobenzene sulfonic acid azophenol, the graphene quantum dot of chloride and tetrahydrochysene furan
The mass ratio muttered is 1: 2: 200.
The step 1）The preparation method of middle graphene quantum dot is as follows：2.5g citric acids are placed in 175 DEG C of oil bath pan
Middle heating 30min, citric acid is taken out and is dissolved in 250 ml 10mg/ml sodium hydroxide solution after reaction, then uses water
It is 0.22um filtering with microporous membrane, until invisible particulate matter, the bag filter for being then 3000Da with molecule interception are saturating
Analysis, a ultra-pure water is changed every 1h, until dialysis system stabilization and outer liquid pH=7 of bag filter, obtain quantum dot solution, centrifuge,
Freeze-drying, obtains solid graphite alkene quantum dot.
The step 2）The Preparation Method of middle p-aminobenzene sulfonic acid azophenol is as follows：0.01mol p-aminobenzene sulfonic acid is molten
Solution obtains the hydrochloric acid solution of p-aminobenzene sulfonic acid in 7.7mL hydrochloric acid；
Under agitation, the sodium nitrite in aqueous solution that solutes content is 0.690g is added to the hydrochloric acid of above-mentioned p-aminobenzene sulfonic acid
In solution, 0.5h is reacted under the conditions of 0-5 DEG C of temperature, generates diazonium salt solution；
Weigh and be dissolved in the phenol of p-aminobenzene sulfonic acid respective amount in deionized water, obtain phenol solution, it is 0-5 to control temperature
DEG C, phenol solution is added in above-mentioned diazonium salt solution under agitation and adjusts pH=4-7, is stood overnight, suction filtration obtains thick
Product, recrystallized and purified with absolute ethyl alcohol again after crude product is washed, obtain p-aminobenzene sulfonic acid azophenol.
Preparation process of the present invention is simple, the graphene quantum dot that is obtained grafting azo derivative composite, in acetone,
There is good dissolubility, on molecular fluorescence, the composite is to metal ion in the organic solvent such as acetonitrile, methanol, ethanol
With higher selectivity, can by the heavy metal ion in luminescent photochemical sensing detection environment, as the tin in contaminant water from
Son, mercury ion etc..The present invention graphene quantum dot grafting azo derivative composite be expected to biological medicine, sensor,
Optics and electricity device, solar cell, electronic equipment, optics fuel and multiple microparticles system etc. are applied.
Brief description of the drawings
Fig. 1 is that the SEM of the graphene quantum dot of embodiment 1 schemes；
Fig. 2 is the SEM figures that the graphene quantum dot of embodiment 3 is grafted p-aminobenzene sulfonic acid azophenol；
Fig. 3 is that the graphene quantum dot of embodiment 7 is grafted dissolubility curve map of the azo derivative composite in different solvents；
Fig. 4 is that the graphene quantum dot of embodiment 8 is grafted recognition performance figure of the azo derivative composite to metal ion.
Embodiment
Below in conjunction with the specific embodiment content that the present invention is furture elucidated, but these embodiments are not intended to limit the present invention
Protection domain.
Embodiment 1：Graphene quantum dot（GQDs）Preparation
Weighing 2.5g citric acids, which are put into 175 DEG C of oil bath pan, in measuring cup heats 30min, is taken out after reaction, and its is abundant
It is dissolved in 250 ml 10mg/ml sodium hydroxide solution, then with water system 0.22um filtering with microporous membrane, is seen up to visually
Lose particulate matter, the bag filter for being 3000Da with molecule interception is dialysed, and a ultra-pure water is changed every 1h, until dialysis system
The outer liquid of stable and bag filter measures pH=7 with pH test paper, and the flaxen quantum dot solution prepared is placed on into low-temperature dark
Place preserves.Take and centrifuged in right amount, be freeze-dried 48h, obtain solid graphite alkene quantum dot.
Embodiment 2：The preparation of p-aminobenzene sulfonic acid azophenol
Take 1.732g（0.01mol）P-aminobenzene sulfonic acid makes in 50mL beakers, then toward addition 7.7mL hydrochloric acid, stirring in beaker
P-aminobenzene sulfonic acid dissolves, and obtains in the hydrochloric acid solution of p-aminobenzene sulfonic acid；0.690g nitrous is prepared in another beaker
Acid sodium aqueous solution, pour under agitation in the hydrochloric acid solution of p-aminobenzene sulfonic acid, react 0.5h in the environment of 0-5 DEG C of low temperature,
Generate colourless diazol.
Weigh the phenol with p-aminobenzene sulfonic acid respective amount（About 0.941g）It is dissolved in deionized water, it is 0- to control temperature
5 DEG C, add in above-mentioned diazonium salt solution and adjusted in the range of pH=4-7 under agitation；Reaction 2h increasingly generates yellowish-brown pasty liquid
Body, stand overnight.Pair suction filtration obtains crude product, is recrystallized and purified with absolute ethyl alcohol again after product washing, obtains yellowish-brown product, i.e.,
Aminobenzenesulfonic acid azophenol, labeled as SUL-Ph.
Embodiment 3：Graphene quantum dot is grafted p-aminobenzene sulfonic acid azophenol（GQDs-g-SUL-Ph）Preparation
1) 100mg graphene quantum dot is scattered in 20ml thionyl chloride and 0.5ml anhydrous DMF
In, flowed back 24 hours at 70 DEG C, reaction is evaporated under reduced pressure after stopping and removes thionyl chloride, and it is small that product is dried in vacuo 24 at 60 DEG C
When, obtain the graphene quantum dot of chloride；
2) presses p-aminobenzene sulfonic acid azophenol and the graphene quantum dot of chloride and tetrahydrofuran made from step 1)
Mass ratio 1: 1: 200 mixes, and for ultrasonic disperse uniformly after being reacted 55 hours under temperature 45 C, reaction end is cooled to room temperature, will
Product is filtered and washed twice with ethanol, is collected filter cake and is dried in vacuo 72 hours, is obtained graphene quantum dot grafting azo and is spread out
Biocomposite material.
Embodiment 4：Graphene quantum dot is grafted the preparation of p-aminobenzene sulfonic acid azophenol
1) 100mg graphene quantum dot is scattered in 20ml phosphorus trichloride and 0.5ml tetrahydrofuran, at 65 DEG C
Backflow 36 hours, reaction are evaporated under reduced pressure after stopping and remove phosphorus trichloride, and product is dried in vacuo 24 hours at 50 DEG C, obtains acyl chlorides
The graphene quantum dot of change；
2) presses p-aminobenzene sulfonic acid azophenol and the graphene quantum dot of chloride and tetrahydrofuran made from step 1)
Mass ratio 1: 2: 250 mixes, and ultrasonic disperse uniformly react 72 hours after at 40 DEG C of temperature, and reaction end is cooled to room temperature, general
Product is filtered and washed twice with ethanol, is collected filter cake and is dried in vacuo 72 hours, is obtained graphene quantum dot grafting azo and is spread out
Biocomposite material.
Embodiment 5：Graphene quantum dot is grafted the preparation of p-aminobenzene sulfonic acid azophenol
1) 100mg graphene quantum dot is scattered in 25ml phosphorus pentachloride and 1ml hexamethylene, flowed back at 75 DEG C
24 hours, reaction was evaporated under reduced pressure after stopping and removes phosphorus pentachloride, and product is dried in vacuo 12 hours at 70 DEG C, obtains chloride
Graphene quantum dot；
2) presses p-aminobenzene sulfonic acid azophenol and the graphene quantum dot of chloride and tetrahydrofuran made from step 1)
Mass ratio 1: 3: 300 mixes, and for ultrasonic disperse uniformly after being reacted 48 hours under temperature 60 C, reaction end is cooled to room temperature, will
Product is filtered and washed twice with ethanol, is collected filter cake and is dried in vacuo 60 hours, is obtained graphene quantum dot grafting azo and is spread out
Biocomposite material.
Embodiment 6：Graphene quantum dot is grafted the preparation of p-aminobenzene sulfonic acid azophenol
1) 100mg graphene quantum dot is scattered in 25ml POCl3 and 1ml toluene, flows back 30 at 70 DEG C
Hour, reaction is evaporated under reduced pressure after stopping and removes POCl3, and product is dried in vacuo 18 hours at 60 DEG C, obtains the stone of chloride
Black alkene quantum dot；
2) presses p-aminobenzene sulfonic acid azophenol and the graphene quantum dot of chloride and tetrahydrofuran made from step 1)
Mass ratio 1: 2: 200 mixes, and for ultrasonic disperse uniformly after being reacted 60 hours under temperature 50 C, reaction end is cooled to room temperature, will
Product is filtered and washed twice with ethanol, is collected filter cake and is dried in vacuo 72 hours, is obtained graphene quantum dot grafting azo and is spread out
Biocomposite material.
Embodiment 7：Fluorescence identifying researchs of the GQDs-g-SUL-Ph in different solvents
Take 1mL GQDs-g-SUL-Ph solution to add 3 mL ultra-pure water wiring solution-formings, be in excitation wavelength 370nm, slit width
Under 5nm, S is usedXZ-4-10 U.S. Varian sepectrophotofluorometer is detected.GQDs-g-SUL-Ph in other solvents
Fluoroscopic examination operation is same as above.Final result is as shown in figure 3, graphene quantum dot grafting azo of the invention spreads out as shown in Figure 3
Biocomposite material, there is good dissolubility, and GQDs-g- in the organic solvents such as acetone, acetonitrile, methanol, ethanol
Fluorescence intensity change rules of the SUL-Ph in different solvents be：Original solution>Acetone>Acetonitrile>Ethanol>Methanol>Water.
Embodiment 8：Study of recognition of the GQDs-g-SUL-Ph aqueous solution to cation
Prepare 1 × 10-4 mol·L-1The GQDs-g-SUL-Ph aqueous solution and 1 × 10-3MolL-1 cationic solution, takes 2
ML GQDs-g-SUL-Ph solution simultaneously adds 2 mL cationic solutions in quartz colorimetric utensil, in 380 nm excitation wavelengths, 10 nm
Its fluorescent absorption light collection of illustrative plates is determined under slit width, as shown in Figure 4, GQDs is grafted on SUL-Ph testing result as shown in Figure 4
When, the fluorescence intensity of GQDs-g-SUL-Ph products is almost quenched completely, and makes GQDs-g-SUL- after adding metal ion solution
Ph fluorescence property is strengthened, wherein Sn2+The Fluorescence Increasing of ion pair product it is more apparent, add 13 times or so.Transmitting
The position at peak is also offset, it was demonstrated that GQDs-g-SUL-Ph can pass through the heavy metal in luminescent photochemical sensing detection environment
Ion.
Claims (7)
1. graphene quantum dot is grafted azo derivative composite, it is characterised in that：The composite is by p-aminophenyl
Oh group on the phenyl ring of sulfonic acid azophenol one end and the acid chloride groups on the graphene quantum dot of chloride are formed by connecting.
2. a kind of preparation method of graphene quantum dot grafting azo derivative composite as claimed in claim 1, it is special
Sign is：It comprises the following steps：
1) graphene quantum dot is scattered in the mixed liquor that the chloride with chloride effect forms with organic solvent,
Reacted at 65-75 DEG C 24-36 hours, reaction is evaporated under reduced pressure after stopping and removes chloride, and product is dried in vacuo at 50-70 DEG C
12-24 hours, obtain the graphene quantum dot of chloride；
The chloride with chloride effect is one kind in thionyl chloride, phosphorus trichloride, phosphorus pentachloride or POCl3；
The organic solvent is one kind in anhydrous DMF, tetrahydrofuran, hexamethylene, benzene or toluene；
2) by p-aminobenzene sulfonic acid azophenol, the graphene quantum dot of above-mentioned chloride and tetrahydrofuran in mass ratio 1:
1-3: 200-300 mixing, for ultrasonic disperse uniformly after being reacted at 40-60 DEG C of temperature 48-72 hours, reaction end is cooled to room
Temperature, product is filtered and washed with ethanol, collected filter cake and be dried in vacuo 60-72 hours, it is even to obtain graphene quantum dot grafting
Azepine derivatives composite.
3. the preparation method of graphene quantum dot grafting azo derivative composite according to claim 2, its feature
It is：The step 1）, graphene quantum dot, the chloride with chloride effect, the amount ratio of organic solvent is：100mg∶
20-25ml∶0.5-1ml。
4. the preparation method of graphene quantum dot grafting azo derivative composite according to claim 2, its feature
It is：The step 2）, the mass ratio of p-aminobenzene sulfonic acid azophenol, the graphene quantum dot of chloride and tetrahydrofuran
For 1: 1: 200.
5. the preparation method of graphene quantum dot grafting azo derivative composite according to claim 2, its feature
It is：The step 1）The preparation method of middle graphene quantum dot is as follows：2.5g citric acids are placed in 175 DEG C of oil bath and heated
30min, citric acid is taken out and is dissolved in 250 ml 10mg/ml sodium hydroxide solution after reaction, then uses water system
0.22um filtering with microporous membrane, until invisible particulate matter, is then dialysed with the bag filter that molecule interception is 3000Da,
A ultra-pure water is changed every 1h, until dialysis system stabilization and outer liquid pH=7 of bag filter, obtain quantum dot solution, centrifuge,
Freeze-drying, obtains solid graphite alkene quantum dot.
6. the preparation method of graphene quantum dot grafting azo derivative composite according to claim 2, its feature
It is：The step 2）The Preparation Method of middle p-aminobenzene sulfonic acid azophenol is as follows：
P-aminobenzene sulfonic acid is dissolved in hydrochloric acid, obtains the hydrochloric acid solution of p-aminobenzene sulfonic acid；
Under agitation, sodium nitrite in aqueous solution is added in the hydrochloric acid solution of above-mentioned p-aminobenzene sulfonic acid, in 0-5 DEG C of temperature
Under the conditions of react 0.5h, generate diazonium salt solution；
Phenol solution is added in above-mentioned diazonium salt solution at 0-5 DEG C of temperature, stirring condition and adjusts pH=4-7, was stood
Night, suction filtration obtain crude product, are recrystallized and purified with absolute ethyl alcohol again after crude product is washed, obtain p-aminobenzene sulfonic acid azobenzene
Phenol.
7. the graphene quantum dot grafting azo derivative composite as described in one of claim 2-6 is examined in heavy metal ion
Application in survey.
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| CN109813690A (en) * | 2018-12-20 | 2019-05-28 | 广东省微生物研究所（广东省微生物分析检测中心） | A kind of graphene quantum dot fluorescence probe and its synthetic method and application |
| CN109813690B (en) * | 2018-12-20 | 2021-03-26 | 广东省微生物研究所（广东省微生物分析检测中心） | Graphene quantum dot fluorescent probe and synthetic method and application thereof |
| US20220010188A1 (en) * | 2020-07-07 | 2022-01-13 | Tianjin University | Azobenzene-graphene metal coordination solar photothermal energy storage material and preparation thereof |
| US11898083B2 (en) * | 2020-07-07 | 2024-02-13 | Tianjin University | Azobenzene-graphene metal coordination solar photothermal energy storage material and preparation thereof |
| CN117482034A (en) * | 2023-12-29 | 2024-02-02 | 西部医美生物科技成都有限公司双流医疗分公司 | Human adipose-derived stem cell preparation agent and application thereof |
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