CN104760990A - Hydrothermal method for preparing luminous water-soluble CuS quantum dots in visible region - Google Patents
Hydrothermal method for preparing luminous water-soluble CuS quantum dots in visible region Download PDFInfo
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Abstract
The invention discloses a hydrothermal method for preparing luminous water-soluble CuS quantum dots in a visible region. The hydrothermal method comprises the following steps: dissolving 0.0242-0.0969g of L-cysteine in 90mL of purified water under the protection of nitrogen, adding 1-4mL of CuCl2 solution with concentration of 0.1mol/L, uniformly mixing, then adjusting the pH value of a system to 10-11 by using a NaOH solution with the concentration of 1mol/L, transferring the obtained solution to a stainless steel reaction kettle with a lining prepared from polytetrafluoroethylene and with filling volume of 70-85%, putting into a 60-140 DEG C drying oven, and reacting for 2-12 hours. The luminous water-soluble CuS fluorescent quantum dots in the visible region are high in fluorescence intensity, small in particles and uniform in dispersion. The synthetic method is green, environmentally-friendly, simple in operation process, low in synthetic cost and applicable to the fields of photoelectricity, mecial science and the like.
Description
Technical field
The present invention relates to field of nanometer material technology, be specifically related to a kind ofly to utilize Cys to be modifier and sulphur source, prepare good dispersity under hydrothermal conditions, method at the water-soluble CuS fluorescence quantum of visible region luminescence.
Background technology
Because quantum dot has quantum size effect, surface effects, quantum confined effect and macro quanta tunnel effect, thus show the character of some uniquenesses, such as: there is wide excitation spectrum and narrow emmission spectrum, larger Stokes shift, can change luminous position etc. by the size of quantum point.These character make quantum dot be widely used in the fields such as electron device, solar cell and biology.CuS nanoparticle, as a kind of important transition metal semiconductor material, is with a wide range of applications in the field such as optics, catalysis.The method of current synthesis copper sulfide nano material generally needs organic solvent, the waste liquid that synthesis produces and the easy contaminate environment of preparation process, and agglomeration is the important factor affecting its application simultaneously.Therefore exploring a kind of green synthesis method, to prepare the CuS nano material of polymolecularity and excellent in optical properties most important.
Summary of the invention
The invention provides a kind of method that hydrothermal method is prepared in the water-soluble CuS fluorescence quantum of visible region luminescence.
Concrete steps are:
(1) 0.0242 ~ 0.0969g Cys is dissolved in the purified water of 90ml, adds the CuCl that 1 ~ 4mL concentration is 0.1mol/L
2solution, makes Cys and CuCl
2mol ratio be 4:4 ~ 4:1, after mixing, be NaOH solution regulation system pH value to 10 ~ 11 of 1mol/L by concentration, whole process lasts pass into nitrogen and with stir.
(2) step (1) gained solution being transferred to liner is immediately in the stainless steel cauldron of tetrafluoroethylene, loading level is 70% ~ 85%, be placed in 60 ~ 140 DEG C of baking oven reactions 2 ~ 12 hours, naturally cool to the water-soluble CuS quantum dot colloid that room temperature obtains visible region luminescence.
(3) anhydrous organic solvent adding 30 ~ 60mL in the water-soluble CuS quantum dot colloid of the visible region luminescence prepared in step (2) makes its coagulation, through centrifugal, washing, puts into dry 8 ~ 14 hours of the vacuum drying oven of 40 ~ 60 DEG C, obtains CuS quantum dot powder by gained precipitation.
(4) voltage of 600V is adopted, the fluorescence spectrum exciting slit and transmitting slit to be the water-soluble CuS quantum dot colloid of the visible region luminescence of fluorescence spectrophotometer measurement step (2) gained of 10nm shows, when excitation wavelength is 390 ~ 410nm, emission peak is maximum in the fluorescence intensity at 490 ~ 520nm place; Transmission electron microscope (TEM) is observed and is shown, the CuS particle in the water-soluble CuS quantum dot colloid of visible region luminescence is spherical, and median size is 1.0 ~ 4.0 nm, good dispersity; Adopt X-ray powder diffractometer (XRD) structural characterization to step (3) gained CuS quantum dot powder to show, CuS quantum dot powder is the CuS of hexagonal crystal structures.
Described organic solvent is the one in methyl alcohol, ethanol, acetone and Virahol.
The present invention adopts hydrothermal method, utilizes Cys for modifier and sulphur source, synthesize polymolecularity, water-soluble CuS fluorescence quantum in visible region luminescence, that prepares is high in the water-soluble CuS fluorescence quantum fluorescence intensity of visible region luminescence, particle is little and be uniformly dispersed, synthetic method environmental protection, operating process is simple, and synthesis cost is low, can be applicable to the field such as photoelectricity and medical science.
Accompanying drawing explanation
Fig. 1 is the fluorescence pattern of CuS quantum dot prepared by the embodiment of the present invention 1.
Wherein: a is excitation spectrum, b is fluorescence emission spectrum.
The TEM collection of illustrative plates of the CuS quantum dot of Fig. 2 prepared by example 1 of the present invention.
Fig. 3 is that the embodiment of the present invention 2 gained CuS quantum dot is at modifier and CuCl
2mol ratio be fluorescent emission collection of illustrative plates under the condition of 4:1,4:2,4:3,4:4.
Fig. 4 is the fluorescent emission collection of illustrative plates of the embodiment of the present invention 3 gained CuS quantum dot under differential responses time conditions.
Fig. 5 is the fluorescence spectrum figure of the embodiment of the present invention 4 gained CuS quantum dot and blank.
Embodiment
embodiment 1:
(1) 0.0485g Cys is dissolved in the purified water of 90mL, adds the CuCl that 2mL concentration is 0.1mol/L
2solution, after mixing, is the NaOH solution regulation system pH value to 10.5 of 1mol/L by concentration, and whole process lasts passes into nitrogen and adjoint stirring.
(2) step (1) gained solution being transferred to liner is immediately in the stainless steel cauldron of tetrafluoroethylene, loading level is 75%, be placed in 100 DEG C of baking oven reactions 6 hours, naturally cool to the water-soluble CuS fluorescence quantum colloid that room temperature obtains visible region luminescence.
(3) voltage of 600V is adopted, the fluorescence spectrum exciting slit and transmitting slit to be the water-soluble CuS quantum dot colloid of the visible region luminescence of fluorescence spectrophotometer measurement step (2) gained of 10nm shows, when excitation wavelength is 410nm, emission peak is in the maximum (see figure 1) of fluorescence intensity at 510nm place, visible region; Adopt tem observation to be spheroidal particle to the pattern of the water-soluble CuS quantum dot of visible region luminescence, median size is that 2.56 ± 0.74nm(is shown in Fig. 2), good dispersity.
(4) the anhydrous methanol solvent adding 40mL in the water-soluble CuS fluorescence quantum colloid of the visible region luminescence prepared in step (2) makes its coagulation, through centrifugal, washing, gained precipitation is put into dry 12 hours of the vacuum drying oven of 60 DEG C, obtain CuS quantum dot powdered sample, the characterization result of XRD shows, powder is the CuS of hexagonal structure.
embodiment 2:
(1) under the protection of nitrogen, fill in the Erlenmeyer flask of 90mL purified water to four, add 0.0485g Cys respectively, after it dissolves, add the CuCl that 1mL, 2mL, 3mL, 4mL concentration is 0.1mol/L respectively
2solution, makes Cys and CuCl in four systems
2mol ratio be respectively 4:1,4:2,4:3 and 4:4, after mixing, regulate the pH value to 10.5 of four systems respectively by the NaOH solution that concentration is 1mol/L, whole process lasts pass into nitrogen and with stir.
(2) step (1) gained solution being transferred to four liners immediately is respectively in the stainless steel cauldron of tetrafluoroethylene, loading level is 75%, be placed in 100 DEG C of baking oven reactions 6 hours, naturally cool to the water-soluble CuS quantum dot colloid that room temperature obtains four groups of visible region luminescences.
(3) voltage of 600V is adopted, the fluorescence spectrum exciting slit and transmitting slit to be the water-soluble CuS quantum dot colloid of four groups of visible region luminescences of fluorescence spectrophotometer measurement step (2) gained of 10nm shows, when excitation wavelength is 410nm, Cys and CuCl
2mol ratio be the fluorescence intensity the strongest (see figure 3) of system at 510nm place, visible region of 4:2; Cys and CuCl
2mol ratio be that the system of 4:4 has precipitation to produce, and have multiple emission peak.In tem observation to four systems, CuS quantum dot is spheroidal particle, wherein Cys and CuCl
2mol ratio when being respectively 4:1,4:2 and 4:3, the median size of CuS quantum dot is respectively 2.96 ± 0.84nm, 2.56 ± 0.74nm and 1.25 ± 0.39nm, and the even particle size distribution of CuS quantum dot.
embodiment 3:
(1) fill in the Erlenmeyer flask of 90mL purified water at five, add 0.0485g Cys respectively, after it dissolves, add the CuCl that 2mL concentration is 0.1mol/L respectively
2solution, after mixing, regulates pH value respectively to 10.5 of five individual system by the NaOH solution that concentration is 1mol/L, whole process lasts passes into nitrogen and adjoint stirring.
(2) step (1) gained solution being transferred to five liners immediately is respectively in the stainless steel cauldron of tetrafluoroethylene, loading level is 75%, be placed in 100 DEG C of baking ovens and react 2 hours, 4 hours, 6 hours, 8 hours and 10 hours respectively, naturally cool to the water-soluble CuS quantum dot colloid that room temperature obtains visible region luminescence.
(3) voltage of 600V is adopted, the fluorescence spectrum exciting slit and transmitting slit to be the water-soluble CuS quantum dot colloid of the visible region luminescence of fluorescence spectrophotometer measurement step (2) gained of 10nm shows, when excitation wavelength is 410nm, emission peak is positioned at 500 ~ 520nm place, visible region, wherein when reacted between be 6 hours, fluorescence intensity is the strongest.Tem observation is the water-soluble CuS quantum dot of the visible region luminescence obtained for 6 hours to the reaction times is spheroidal particle, and median size is 2.56 ± 0.74 nm, good dispersity.
(4) the anhydrous methanol solvent adding 40mL in the water-soluble CuS quantum dot colloidal dispersion of five groups of visible region luminescences step (2) prepared respectively makes its coagulation, through centrifugal, washing, puts into dry 12 hours of the vacuum drying oven of 60 DEG C, obtains powdered sample by gained precipitation.The result of XRD shows, powder is the CuS of hexagonal structure.
embodiment 4:
(1) under the protection of nitrogen, add the purified water of 90mL respectively in three Erlenmeyer flasks after, in first Erlenmeyer flask, add 0.0485g Cys, after it dissolves, add the CuCl that 2mL concentration is 0.1mol/L
2solution, regulates the pH value to 10.5 of this system by the NaOH solution that concentration is 1mol/L; To in second Erlenmeyer flask, add 0.0485g Cys, after it dissolves, regulate the pH value to 10.5 of this system by the NaOH solution that concentration is 1mol/L; The CuCl that 2mL concentration is 0.1mol/L is added in the 3rd Erlenmeyer flask
2solution, regulates the pH value to 10.5 of this system by the NaOH solution that concentration is 1mol/L; Whole process lasts passes into nitrogen and adjoint stirring.
(2) step (1) gained solution being transferred to three liners immediately is respectively in the stainless steel cauldron of tetrafluoroethylene, loading level is 75%, be placed in 100 DEG C of baking ovens reaction 6 hours, naturally cool to room temperature and obtain the water-soluble CuS quantum dot colloid (quantum dot system) of one group of visible region luminescence and two blank samples (are respectively Cys system and CuCl
2system).
(3) voltage of 600V is adopted, the fluorescence spectrum exciting slit and transmitting slit to be fluorescence spectrophotometer measurement step (2) gained three individual system of 10nm shows, CuS fluorescence quantum system is only had to have fluorescence emission peak at 510nm place, visible region, and Cys and CuCl
2system does not all have obvious emission peak.Explanation only has CuS fluorescence quantum luminous in visible region.
Claims (1)
1. hydrothermal method prepares a method for the water-soluble CuS quantum dot of visible region luminescence, it is characterized in that concrete steps are:
(1) 0.0242 ~ 0.0969g Cys is dissolved in the purified water of 90ml, adds the CuCl that 1 ~ 4mL concentration is 0.1mol/L
2solution, makes Cys and CuCl
2mol ratio be 4:4 ~ 4:1, after mixing, be NaOH solution regulation system pH value to 10 ~ 11 of 1mol/L by concentration, whole process lasts pass into nitrogen and with stir;
(2) step (1) gained solution being transferred to liner is immediately in the stainless steel cauldron of tetrafluoroethylene, loading level is 70% ~ 85%, be placed in 60 ~ 140 DEG C of baking oven reactions 2 ~ 12 hours, naturally cool to the water-soluble CuS quantum dot colloid that room temperature obtains visible region luminescence;
(3) anhydrous organic solvent adding 30 ~ 60mL in the water-soluble CuS quantum dot colloid of the visible region luminescence prepared in step (2) makes its coagulation, through centrifugal, washing, puts into dry 8 ~ 14 hours of the vacuum drying oven of 40 ~ 60 DEG C, obtains CuS quantum dot powder by gained precipitation;
(4) voltage of 600V is adopted, the fluorescence spectrum exciting slit and transmitting slit to be the water-soluble CuS quantum dot colloid of the visible region luminescence of fluorescence spectrophotometer measurement step (2) gained of 10nm shows, when excitation wavelength is 390 ~ 410nm, emission peak is maximum in the fluorescence intensity at 490 ~ 520nm place; Transmission electron microscope and tem observation show, the CuS particle in the water-soluble CuS quantum dot colloid of visible region luminescence is spherical, and median size is 1.0 ~ 4.0 nm, good dispersity; Adopt X-ray powder diffractometer and the structural characterization of XRD to step (3) gained CuS quantum dot powder to show, CuS quantum dot powder is the CuS of hexagonal crystal structures;
Described organic solvent is the one in methyl alcohol, ethanol, acetone and Virahol.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105016374A (en) * | 2015-08-14 | 2015-11-04 | 天津城建大学 | Method for preparing CuS micro-spheres of hierarchic structures |
| CN108584916A (en) * | 2018-06-05 | 2018-09-28 | 桂林理工大学 | The method for preparing the luminous water-solubility fluorescent carbon quantum dot of visible region with sisal fiber |
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| US7507599B1 (en) * | 2003-12-11 | 2009-03-24 | Industrial Technology Research Institute | ZnX (X=S, Se, Te) quantum dot preparation method |
| CN103937492A (en) * | 2014-04-22 | 2014-07-23 | 桂林理工大学 | Method for preparing near infrared emission CuxS fluorescent quantum dots |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7507599B1 (en) * | 2003-12-11 | 2009-03-24 | Industrial Technology Research Institute | ZnX (X=S, Se, Te) quantum dot preparation method |
| CN103937492A (en) * | 2014-04-22 | 2014-07-23 | 桂林理工大学 | Method for preparing near infrared emission CuxS fluorescent quantum dots |
Non-Patent Citations (1)
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| 王鲁宁,赖广辉,覃爱苗: "无机功能材料硫化铜纳米粉体的溶剂热合成研究", 《化工技术与开发》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105016374A (en) * | 2015-08-14 | 2015-11-04 | 天津城建大学 | Method for preparing CuS micro-spheres of hierarchic structures |
| CN108584916A (en) * | 2018-06-05 | 2018-09-28 | 桂林理工大学 | The method for preparing the luminous water-solubility fluorescent carbon quantum dot of visible region with sisal fiber |
| CN108584916B (en) * | 2018-06-05 | 2022-02-11 | 桂林理工大学 | Method for preparing luminous water-soluble fluorescent carbon quantum dots in visible light region by using sisal fibers |
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Application publication date: 20150708 Assignee: Guangxi shimaoda Technology Co.,Ltd. Assignor: GUILIN University OF TECHNOLOGY Contract record no.: X2022450000494 Denomination of invention: A hydrothermal method for preparing water-soluble CuS quantum dots emitting light in the visible light region Granted publication date: 20160302 License type: Common License Record date: 20221229 |