CN105621407A - Method for synthesizing sulfur-doped graphene quantum dots in one step - Google Patents

Method for synthesizing sulfur-doped graphene quantum dots in one step Download PDF

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Publication number
CN105621407A
CN105621407A CN201610117614.7A CN201610117614A CN105621407A CN 105621407 A CN105621407 A CN 105621407A CN 201610117614 A CN201610117614 A CN 201610117614A CN 105621407 A CN105621407 A CN 105621407A
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graphene quantum
quantum dot
sulfur
quantum dots
gains
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李明
骆毅
文剑锋
李新宇
唐涛
肖剑荣
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Guilin University of Technology
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Guilin University of Technology
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2204/00—Structure or properties of graphene
    • C01B2204/20—Graphene characterized by its properties
    • C01B2204/32—Size or surface area
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer

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Abstract

The invention discloses a method for synthesizing sulfur-doped graphene quantum dots in one step. Pyrene which is low in price and has already been industrially produced serves as a precursor, the surface of pyrene is nitrated at low temperature, the nitro group on the surface of pyrene is removed through a hydrothermal reaction at high temperature and high pressure, the hexagonal annular structure of pyrene is cut, graphene quantum dots which are excellent in water solubility, stable in structure, free of toxin, excellent in optical characteristic and small in size are prepared, the obtained graphene quantum dots are synthesized with sublimed sulfur at a temperature of 150-200 DEG C through a hydrothermal reaction in one step to prepare the sulfur-doped graphene quantum dots with excellent optical performance, and the average granularity of grains is 4-6 nm. The preparation method is simple, raw materials are low in price, the requirement for a device is low, the prepared sulfur-doped graphene quantum dots have excellent light-emitting performance, and a sulfur-doped graphene quantum dot/P25 TiO2 composite prepared after the product is compounded with P25 TiO2 has excellent performance on the aspect of photocatalysis.

Description

The method of one-step synthesis sulfur doping graphene quantum dot
Technical field
The present invention relates to one and have excellent water-soluble structure, stability, the preparation method of nontoxic graphene quantum dot, the basic previous step synthesis at this kind of graphene quantum dot has excellent optical property sulfur doping graphene quantum dot.
Background technology
Owing to having special optical property, characteristic electron, chemical stability and spin character etc., graphene quantum dot (GQDs) has become a great focus in the numerous research field of material at present. The method of the preparation method of graphene quantum dot is of all kinds, mainly contains High Temperature High Pressure hydro-thermal method, chemical vapour deposition, electrochemical process, polynuclear aromatics pyrolysis method etc.
GQDs not only shows to the same excellent properties of Graphene, also has good bio-compatibility, hypotoxicity simultaneously, the low property buried in oblivion, the excellent properties such as stable chemical property so that it is at photoelectric device, sensor, there is good application prospect the aspects such as bio-imaging.
Although GQDs has so many advantage, but not yet obtain at optoelectronic areas at present and apply widely, trace it to its cause, mainly because still lacking one at present graphene quantum dot to be carried out effective level structure, the effective technique means of optical property modulation.
Applying bottleneck at present to change graphene quantum dot, open the band gap of Graphene, one of them is feasible and can change material level structure, optical property, and the effective means-doping of electrical properties is shown great attention to. Because nitrogen-atoms has five valence electrons, and carbon atom has suitable atomic size size to be widely used in the chemical doping of carbon material, and such as nitrogen-doped carbon nanometer pipe (N-CNT) etc., but sulfur doping carbon material aspect but rarely has people to pay close attention to.
Prepare sulfur doping graphene quantum dot main method at present and have polynuclear aromatics hydrolysis method, the methods such as organic chemical synthesis method and electrochemistry, but many methods all cannot avoid raw material to obtain difficulty, apparatus expensive, operation trouble is consuming time, and technique is loaded down with trivial details, and yield rate is low, the factors such as impurity is more affect, thus limit the extensive preparations and applicatio of sulfur doping graphene quantum dot. Therefore, research and development preparation method simple, sulfur doping graphene quantum dot efficiently has important practical significance.
Summary of the invention
It is an object of the invention to the shortcoming existed to overcome above-mentioned prior art, it is provided that the preparation method of a kind of sulfur doping graphene quantum dot with excellent optical property. Particularly being stressed that, building-up process step of the present invention is simple, product rate height, and after reaction, yield rate height, impurity is few, and raw material obtains simple simultaneously.
Concrete steps are:
(1) 1g pyrene and 80-100mL nitrosonitric acid being stirred after evenly, return stirring 12 hours at 80-100 DEG C, carry out nitro functionalization, naturally cooling by pyrene crystal grain surface.
(2) reactant step (1) prepared takes out, and adopts 0.22 ��m of micro-pore-film filtration removing waste liquid, and with deionized water cleaning and filtering thing 3-5 time.
(3) step (2) gains are added 0.2-0.6gNaOH, it is placed in 300W ultrasonic disperse 1 hour, then put into pyroreaction still immediately, 180-200 DEG C of incubation water heating reaction 10-12 hour, naturally cooling.
(4) dialyse with 3500Da dialysis tubing after step (3) gains being removed solid impurity with 0.22 ��m of microporous membrane and remove ion unnecessary in reactant in 48 hours; At 70 DEG C, evaporation is dried, and obtains graphene quantum dot.
(5) by 0.1g step (4) gained graphene quantum dot, add 180-220mL deionized water, degrade 10 minutes with ultrasonic wave 300W, after making graphene quantum dot fully be dissolved in deionized water, under magneton agitation condition, slowly add 0.25g sublimed sulphur, stir and within 30 minutes, make sublimed sulphur be well dispersed in graphene quantum dot solution.
(6) being transferred in polytetrafluoroethyltank tank by step (5) gains, in pyroreaction still, 150-200 DEG C of incubation water heating reacts 24 hours, naturally cooling.
(7) dialyse with 3500Da dialysis tubing after step (6) gains being removed solid impurity with 0.22 ��m of microporous membrane and remove ion unnecessary in reactant in 48 hours; At 70 DEG C, evaporation is dried, and obtains sulfur doping graphene quantum dot, and crystal grain median size is 4-6nm.
The present invention has relatively compared following advantage in prior art:
(1) to obtain sulfur doping graphene quantum dot comparatively simply controlled in production technique in the present invention, yield rate height, and in preparation process, avoid and introduce other foreign ion, reaction product purity height, and raw material obtains simple simultaneously.
(2) the sulfur doping graphene quantum dot that prepared by the present invention, can stable dispersion in water, Stability Analysis of Structures, excellent in optical properties, simultaneously in photochemical catalysis, sulfur doping graphene quantum dot/P25TiO2Matrix material has outstanding representation, and crystal grain median size is 4-6nm, and rich surface is containing group.
Accompanying drawing explanation
Fig. 1 is transmission electron microscope (TEM) photo of graphene quantum dot prepared by the embodiment of the present invention.
Fig. 2 is high power transmission electron microscope (HRTEM) photo of graphene quantum dot prepared by the embodiment of the present invention.
The X-ray photoelectron spectroscopic analysis (XPS) that Fig. 3 is sulfur doping graphene quantum dot prepared by the embodiment of the present invention can spectrogram.
Fig. 4 is that sulfur doping graphene quantum dot prepared by the embodiment of the present invention compares figure with graphene quantum dot fluorescence spectrum.
Sulfur doping graphene quantum dot absorption spectrum prepared by Fig. 5 embodiment.
Fig. 6 is sulfur doping graphene quantum dot/P25TiO prepared by the embodiment of the present invention2Matrix material is photochemical catalysis methyl orange solution photocatalysis efficiency figure under mercury lamp.
Embodiment
Below in conjunction with embodiments of the invention and accompanying drawing, the invention will be further elaborated.
Embodiment:
(1) 1g pyrene and 80mL nitrosonitric acid being stirred after evenly, return stirring 12 hours at 80 DEG C, carry out nitro functionalization, naturally cooling by pyrene crystal grain surface.
(2) reactant step (1) prepared takes out, and adopts 0.22 ��m of micro-pore-film filtration removing waste liquid, and with deionized water cleaning and filtering thing 3 times.
(3) step (2) gains are added 0.4gNaOH, it is placed in 300W ultrasonic disperse 1 hour, then put into pyroreaction still immediately, react 12 hours, naturally cooling at 180 DEG C of incubation water heatings.
(4) dialyse with 3500Da dialysis tubing after step (3) gains being removed solid impurity with 0.22 ��m of microporous membrane and remove ion unnecessary in reactant in 48 hours; At 70 DEG C, evaporation is dried, and obtains graphene quantum dot.
(5) by 0.1g step (4) gained graphene quantum dot, add 200mL deionized water, degrade 10 minutes with ultrasonic wave 300W, after making graphene quantum dot fully be dissolved in deionized water, under magneton agitation condition, slowly add 0.25g sublimed sulphur, stir and within 30 minutes, make sublimed sulphur be well dispersed in graphene quantum dot solution.
(6) being transferred in polytetrafluoroethyltank tank by step (5) gains, in pyroreaction still, 180 DEG C of incubation water heatings react 24 hours, naturally cooling.
(7) dialyse with 3500Da dialysis tubing after step (6) gains being removed solid impurity with 0.22 ��m of microporous membrane and remove ion unnecessary in reactant in 48 hours; At 70 DEG C, evaporation is dried, and obtains sulfur doping graphene quantum dot, and crystal grain median size is 4-6nm, and rich surface is containing group.
Table 1 is prepared sulfur doping graphene quantum dot constituent content cartogram.
Table 1: sulfur doping graphene quantum dot constituent content
Obtained sulfur doping graphene quantum dot/P25TiO2The application of matrix material in photochemical catalysis:
(1) by 0.1g sulfur doping graphene quantum dot, 1gP25TiO2With the mixing of 200mL deionized water, magneton stirs 30 minutes, fully mixes.
(2) step (1) gains are transferred in polytetrafluoroethyltank tank, pyroreaction still maintain 180 DEG C of incubation water heatings and reacts 24 hours, after naturally cooling.
(3) by, after centrifugal for step (2) gains washing 3 times, at 70 DEG C, drying obtains sulfur doping graphene quantum dot/P25TiO2Matrix material.
(4) by the sulfur doping graphene quantum dot/P25TiO prepared by 20mg step (3)2Matrix material is added in the methyl orange solution of the 20ppm that 40mL prepares, ultrasonic degradation 30 minutes, it is positioned in photochemical reaction instrument after making it be well-dispersed in methyl orange solution, under 300W mercury lamp illumination, sampling in every 1 minute once, observes sulfur doping graphene quantum dot/P25TiO by ultraviolet spectrophotometer2Matrix material photocatalysis efficiency. Simultaneously respectively by the P25TiO of 20mg2, graphene quantum dot/P25TiO2Matrix material and sulfur doping graphene quantum dot add in 40mL methyl orange solution and compare sample as ginseng.
Sulfur doping graphene quantum dot/P25TiO2Matrix material photochemical catalysis methyl orange solution photocatalysis efficiency figure under mercury lamp is shown in Fig. 6.

Claims (1)

1. one kind is synthesized the method for sulfur doping graphene quantum dot, it is characterised in that concrete steps are:
(1) 1g pyrene and 80-100mL nitrosonitric acid are stirred after evenly, return stirring 12 hours at 80-100 DEG C, naturally cooling;
(2) reactant step (1) prepared takes out, and adopts 0.22 ��m of micro-pore-film filtration removing waste liquid, and with deionized water cleaning and filtering thing 3-5 time;
(3) step (2) gains are added 0.2-0.6gNaOH, it is placed in 300W ultrasonic disperse 1 hour, then put into pyroreaction still immediately, 180-200 DEG C of incubation water heating reaction 10-12 hour, naturally cooling;
(4) dialyse with 3500Da dialysis tubing after step (3) gains being removed solid impurity with 0.22 ��m of microporous membrane and remove ion unnecessary in reactant in 48 hours; At 70 DEG C, evaporation is dried, and obtains graphene quantum dot;
(5) by 0.1g step (4) gained graphene quantum dot, add 180-220mL deionized water, degrade 10 minutes with ultrasonic wave 300W, after making graphene quantum dot fully be dissolved in deionized water, under magneton agitation condition, slowly add 0.25g sublimed sulphur, stir and within 30 minutes, make sublimed sulphur be well dispersed in graphene quantum dot solution;
(6) being transferred in polytetrafluoroethyltank tank by step (5) gains, in pyroreaction still, 150-200 DEG C of incubation water heating reacts 24 hours, naturally cooling;
(7) dialyse with 3500Da dialysis tubing after step (6) gains being removed solid impurity with 0.22 ��m of microporous membrane and remove ion unnecessary in reactant in 48 hours; At 70 DEG C, evaporation is dried, and obtains sulfur doping graphene quantum dot, and crystal grain median size is 4-6nm.
CN201610117614.7A 2016-03-02 2016-03-02 Method for synthesizing sulfur-doped graphene quantum dots in one step Pending CN105621407A (en)

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Cited By (5)

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CN107043104A (en) * 2017-05-11 2017-08-15 桂林理工大学 A kind of graphene quantum dot induces high nitrogen doped photo-reduction graphene oxide preparation method
CN107121454A (en) * 2017-04-17 2017-09-01 云南大学 A kind of different element doping graphene quantum dots are respectively with molecular engram compound gas sensitive and preparation method and application
CN107954414A (en) * 2016-10-14 2018-04-24 云南师范大学 A kind of method that sulfur doping graphene quantum dot is prepared using reflux technique
CN108998014A (en) * 2018-08-21 2018-12-14 温州医科大学 A kind of preparation method and application of the tumour catalytic nanometer reactor based on graphene quantum dot
CN109091666A (en) * 2018-08-21 2018-12-28 温州医科大学 A kind of preparation method and application of the tumour catalytic nanometer reaction system with target tumor function

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CN105044071A (en) * 2015-08-18 2015-11-11 太原理工大学 Method for detecting Hg<2+> of clean water by using nitrogen-doped carbon dots

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CN105044071A (en) * 2015-08-18 2015-11-11 太原理工大学 Method for detecting Hg<2+> of clean water by using nitrogen-doped carbon dots

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107954414A (en) * 2016-10-14 2018-04-24 云南师范大学 A kind of method that sulfur doping graphene quantum dot is prepared using reflux technique
CN107954414B (en) * 2016-10-14 2020-08-04 云南师范大学 Method for preparing sulfur-doped graphene quantum dots by using reflux process
CN107121454A (en) * 2017-04-17 2017-09-01 云南大学 A kind of different element doping graphene quantum dots are respectively with molecular engram compound gas sensitive and preparation method and application
CN107121454B (en) * 2017-04-17 2019-08-30 云南大学 A kind of difference element doping graphene quantum dot is respectively with molecular engram compound gas sensitive and the preparation method and application thereof
CN107043104A (en) * 2017-05-11 2017-08-15 桂林理工大学 A kind of graphene quantum dot induces high nitrogen doped photo-reduction graphene oxide preparation method
CN108998014A (en) * 2018-08-21 2018-12-14 温州医科大学 A kind of preparation method and application of the tumour catalytic nanometer reactor based on graphene quantum dot
CN109091666A (en) * 2018-08-21 2018-12-28 温州医科大学 A kind of preparation method and application of the tumour catalytic nanometer reaction system with target tumor function
CN109091666B (en) * 2018-08-21 2022-08-05 温州医科大学 Preparation method and application of tumor catalysis nano reaction system with tumor targeting function

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Application publication date: 20160601